Abstracts S S P - SSPC-15 - California Institute of Technology

S S P C 15
The 15 th International Conference on
Solid State Protonic Conductors
Abstracts
August 15 - 19, 2010
Santa Barbara, USA

The 15 th International Conference on
Solid State Protonic Conductors
August 15, 2010 – August 19, 2010
Conference Chairs
Sossina M. Haile, Chair
California Institute of Technology
Sangtae Kim, Co-Chair
University of California, Davis
Stephen J. Paddison, Co-Chair
University of Tennessee
Lutgarde De Jonghe, Co-Chair
University of California, Berkeley
Lawrence Berkeley National Labs
International Advisory Committee and SSPC Board
John T.S. Irvine, St. Andrews University
Sossina M. Haile, California Institute of Technology
M. Saiful Islam, University of Bath
Deborah Jones, University of Montpellier
Junichi Kawamura, Tohoku University
Klaus-Dieter Kreuer, Max Planck Institute for Solid State Research
Truls Norby, University of Oslo
Stephen J. Paddison, University of Tennessee
Eivind M. Skou, University of Southern Denmark
Robert C.T. Slade, University of Surrey
Josh O. Thomas, University of Upsala
Shu Yamaguchi, University of Tokyo

Local Organizing Committee
Sossina M. Haile
Áron Varga (co-chair)
Yoshihiro Yamazaki (co-chair)
Ayako Ikeda
Mary W. Louie
Chatr Panithipongwut
California Institute of Technology

Financial Support:
Acknowledgements
The US National Science Foundation, Division of Materials Research
US Army Research Office, Chemical Sciences
The US Department of Energy, Office of Basic Energy Sciences
Dokiya Symposium Fund, The Electrochemical Society (ECS)
The Electrochemical Society, High Temperature Material Division
Supporting Organizations:
The Electrochemical Society
The Materials Research Society

General Information
Conference Location
Loma Pelona Center
The University of California, Santa Barbara, CA 93106, USA
Tel: +1 (805)893-6161
Alternate: +1 (805)698-2992
E-mail: sspc@caltech.edu
Meeting Rooms
Oral Presentations: Room 1108
Poster Presentations: Room 1100A (continuous access 8/15 – 8/17)
Conference Registration-Desk Hours
8/15 (Sun) 15:00-20:00
8/16 (Mon) 7:30-16:00
8/17 (Tue) 7:30-10:00
Welcome Reception
16:00-18:00 Sunday, 15 August
Loma Pelona Center 1108 Patio
Meals
Breakfast: 07:15-08:15
Lunch: 12:30-13:45 (except Wednesday: 11:30-13:00)
Dinner 18:00-19:15 (except Wednesday banquet)
Carillo Dining Commons
Excursion
13:00-18:00 Wednesday, 18 August
Santa Ynez valley wine tour
*pickup/drop-off (1:15/5:45pm) Manzanita Village bus loop
Banquet
18:30-21:00 Wednesday, 18 August
Las Encinas Quad, Manzanita Village

Loma Pelona

The 15 th International Conference on
Solid State Protonic Conductors
Program
Sunday, August 15
Registration 15:00-20:00
Outside Loma Pelona Center, University of California, Santa Barbara
Welcome Reception 16:00-18:00
Loma
Pelona Center 1108 Patio
Opening Remarks 8:45-8:55 Sossina Haile
Plenary Lecture
Monday, August 16
8:55-9:55 …………………………………………………………………………………………………….. 1
Oxide protonics: Electronic structure and acid base reactions in bulk and surface
Shu Yamaguchi
(Coffee Break)
Oral Session (1) Chairperson: Steve Paddison
O 01(K) 10:15-11:00 ………………………………………………………………………………………... 2
Ab initio molecular dynamics studies of proton structure and transport in solid acids and acid hydrate
crystals
Mark Tuckerman
O 02 (I) 11:00-11:35 ……………………………………………………………………………………….. 3
Polyelectrolyte multilayers for electrochemical energy applications
Avni A. Argun and P. T. Hammond
O 03 11:35-11:55 …………………………………………………………………………………………… 4
About the evolution of the microstructures of ionomers and polyelectrolytes for PEM fuel cell
applications
Klaus-Dieter Kreuer, C. C. de Araujo, G. Portale, U. Klock and J. Maier
O 04 11:55-12:15 …………………………………………………………………………………………… 5
Coherent proton transport in nafion
George Reiter
(Group Photo)
(Lunch Break)
‐ i ‐
Page

Oral Session (2) Chairperson: Tetsuya Uda
O 05 (K) 14:00-14:45 ……………………………………………………………………………………….. 6
NMR studies of local structure, cation ordering and protonic conduction in perovskites
L. Buannic, F. Blanc, D. Middlemiss, and Clare P. Grey
O 06 (I) 14:45-15:20 ……………………………………………………………………………………….. 7
Recent developments in solid acid fuel cells
Calum R.I. Chisholm
O 07 15:20-15:40 ……………………………………………………………………………………………. 8
Local structure and hydride-ion transport in MgY2H8
Hitoshi Takamura, K. Kurosu, A. Hatakeyama and H. Maekawa
(Coffee Break)
O 08 (K) 16:00-16:45 ………………………………………………………………………………………… 9
Improving the proton conductivity of yttrium-doped barium zirconate electrolytes towards the
development of intermediate temperature solid oxide fuel cells
Enrico Traversa
O 09 16:45-17:05 ……………………………………………………………………………………………. 10
Existence of equilibrium mixture between hydrated and unhydrated proton conducting perovskites and
possible implications
John T.S. Irvine, M. C. Verbraeken, H. Viana, A. K. Azad, I. Ahmed and S. Eriksson
O 10 17:05-17:25 …………………………………………………………………………………………….. 11
Local structure and proton dynamics in In-doped BaZrO3
Maths Karlsson, A. Matic, I. Ahmed, C. S. Knee and S. Eriksson
O 11 17:25-17:45 ……………………………………………………………………………………………. 12
Grain boundary conduction in polycrystalline Y-doped BaZrO3: Space charge analysis
Sangtae Kim, C. Chen and C. Danel
Poster Session 20:00-22:30
Loma Pelona Center 1100A
‐ ii ‐

Oral Session (3) Chairperson: John Irvine
Tuesday, August 17
O 12 (K) 8:30-9:15 ………………………………………………………………………………………….. 13
Atomic-scale insights into proton-conducting oxides: Defects, dopants and transport
M. Saiful Islam
O 13 9:15-9:35 ………………………………………………………………………………………………. 14
DFT-MD study of local structures and proton transport in disordered brownmillerite-based compounds
Karsten Rasim, F. Boucher, O. Joubert, P. Baranek and M. Marrony
O 14 9:35-9:55 ……………………………………………………………………………………………. 15
Ab initio studies of the effect of hydrophobic environment on proton transfer in model perfluorsulfonic
acid systems
Bradley F. Habenicht and S. J. Paddison
(Coffee Break)
O 15 (K) 10:15-11:00 ……………………………………………………………………………………… 16
Analysis of transport through mixed proton, oxygen ion, and electron (hole) conductors: Fuel cell and
electrolyzer modes
Anil Virkar
O 16 (I) 11:00-11:35 ………………………………………………………………………………………… 17
Hydrogen in nominally anhydrous minerals: analysis and implications
George R. Rossman
O 17 (K) 11:35-12:20 ……………………………………………………………………………………… 18
The dynamical behaviour of water and protons in perfluorinated membranes and surfactants
Sandrine Lyonnard, C. Cailleteau, H. Mendil-Jakani, S. Mossa, G. Gebel, A. Guillermo, B. Frick and J. Ollivier
(Lunch Break)
Oral Session (4) Chairperson: Klaus-Dieter Kreuer
O 18 (K) 14:00-14:45 ……………………………………………………………………………………… 19
Tailored tungsten oxide nanoparticles produced with hot wire chemical vapor deposition for protonic
electrochromic and fuel cell applications
Anne C. Dillon, S. Lee, R. Deshpande, K. E. Hurst, S. Kocha, V. R. Anderson and S. M. George
O 19 (I) 14:45-15:20 ………………………………………………………………………………………… 20
Uphill gas permeation due to coupled transport in a mixed proton, oxygen vacancy and hole
conducting perovskite membrane
M. Sanders, J. Tong, H. Zhu, R. Kee and Ryan O’Hayre
O 20 15:20-15:40 ……………………………………………………………………………………….….... 21
Proton migration at Σ5 (310)/[001] tilt grain boundary in Y-doped BaZrO3
Cheonan Kim
(Coffee Break)
‐ iii ‐

O 21 (K) 16:00-16:45 ………………………………………………………………………………………. 22
On the path dependence of the open-cell voltage of a galvanic cell involving a ternary or higher
compound with multiple mobile ionic species under multiple chemical potential gradients
Han-Ill Yoo and M. Martin
O 22 16:45-17:05 ……………………………………………………………………………………………. 23
Development of proton conducting SOFCs based on LaNbO4 electrolytes – Status in Norway
Anna. Magrasó, M. L. Fontaine, G. E. Syvertsen, Y. Larring, H. L. Lein, T. Grande, Reidar Haugsrud and T. Norby
O 23 17:05-17:25 ……………………………………………………………………………………………. 24
Charge transfer protonation of a manganese-doped strontium zirconate
Hiroshige Matsumoto, T. Sakai, Y. Kawasaki, Y. Sato and T. Ishihara
O 24 17:25-17:45 ……………………………………………………………………………………………. 25
Electronic conduction of Sr-doped Ce-La monazite ceramics
Hannah L. Ray and L. C. De Jonghe
Poster Session 20:00-22:30
Loma Pelona Center 1100A
‐ iv ‐

Oral Session (5) Chairperson: Noriko Sata
Wednesday, August 18
O 25 (K) 8:30-9:15 ………………………………………………………………………………………….. 26
Interfacial proton dynamics in PEM: Theory and molecular modeling
A. Roudgar, S. Vartak and Michael Eikerling
O 26 9:15-9:35 ………………………………………………………………………………………………. 27
Proton transport mechanism and pathways in solid acids from experiment and theory
Boris Merinov
O 27 9:35-9:55 ………………………………………………………………………………………………. 28
Adsorption processes related to the surface properties of LaNbO4
Kianoosh Hadidi, O.M. Løvvik and T. Norby
(Coffee Break)
O 28 (K) 10:15-11:00 ……………………………………………………………………………………… 29
High temperature protonic conduction in rare earth phosphates and borates
Koji Amezawa, H. Takahashi, A. Unemoto, H. Kuwabara, N. Kitamura and T. Kawada
O 29 11:00-11:20 ……………………………………………………………………………………………. 30
Thermodynamics and proton conductivity trends in fluorite-pyrochlore structures: A study on
lanthanum cerate
Vasileios Besikiotis, T. S. Bjørheim, S. Ricote, C. Kjølseth, R. Haugsrud and T. Norby
O 30 11:20-11:40 ……………………………………………………………………………………………. 31
Synthesis of highly Sr-doped lanthanum orthophosphate and polyphosphate in phosphoric acid
solutions
Naoyuki Hatada, A. Kuramitsu, Y. Nose and T. Uda
(Lunch Break)
Excursion 13:00-18:00
Santa Ynez valley wine tour
*pickup/drop-off (1:15/5:45pm) Manzanita Village bus loop
Banquet 18:30-21:00
Las Encinas Quad, Manzanita Village
‐ v ‐

Oral Session (6) Chairperson: Ryan O’Hayre
Thursday, August 19
O 31 (K) 8:30-9:15 …………………………………...……………………………………………………… 32
Characterization of structural change in PLD-fabricated SrZrO3 thin films
Noriko Sata, S. Tamura, Y. Nagao, H. Kageyama, K. Handa, K. Nomura, F. Iguchi and H. Yugami
O 32 9:15-9:35 ………………………………………………………………………………………………. 33
Water uptake and conduction property of nano-grained yttria-doped zirconia
Y. Akao, Shogo Miyoshi, N. Kuwata, J. Kawamura, Y. Oyama and Shu Yamaguchi
O 33 9:35-9:55 ………………………………………………………………………………………………. 34
Proton conductivity in acceptor doped LaVO4
Morten Huse, T. S. Bjørheim and R. Haugsrud
(Coffee Break)
O 34 (I) 10:15-10:50 ………………………………………………………………………………………… 35
Quasielastic neutron scattering (QENS) applied to proton dynamics in bulk and confinement – the
case of phosphoric acid
Bernhard Frick, A. Thomas, S. Lyonnard, L.Vilciauskas and K.D. Kreuer
O 35 (I) 10:50-11:25 ………………………………………………………………………………………… 36
Ambient and high-pressure synchrotron x-ray diffraction studies of heating-induced structural
modifications in phosphate-based solid acids
Cristian E. Botez
O 36 (I) 11:25-12:00 ………………………………………………………………………………………… 37
Proton dynamics of CsH2PO4 and related salts containing organic ions
Hideki Maekawa, A. Ishikawa and A. Kudo
O 37 12:00-12:20 ……………………………………………………………………………………………. 38
Oxygen reduction kinetics at Pt | CsHSO4 by conducting atomic force microscopy
Mary W. Louie, A. Hightower, and S. M. Haile
(Lunch Break)
Oral Session (7) Chairperson: Sangtae Kim
O 38 14:00-14:20 ……………………………………………………………………………………………. 39
Impact of cation nonstoichiometry on phase behavior, mictrostructure, water incorporation and proton
conductivities in yttrium-doped BaZrO3
Yoshihiro Yamazaki, C. K. Yang, R. Hernandez-Sanchez and S. M. Haile
O 39 14:20-14:40 ……………………………………………………………………………………………. 40
Cost-effective solid-state reactive sintering method for proton-conducting ceramics
Jianhua Tong, D. Clark and R. O’Hayre
O 40 14:40-15:00 ……………………………………………………………………………………………. 41
Solid state NMR studies of doped BaSnO3 and BaZrO3 protonic conductors: Defect trapping and ionic
mobility
Lucienne Buannic, F. Blanc and C. P. Grey
O 41 15:00-15:20 ……………………………………………………………………………………………. 42
The thermodynamics and kinetics of the dehydration of CsH2PO4 studied in the presence of SiO2
Ayako Ikeda and S. M. Haile
Closing Remarks 15:20 Sossina Haile
‐ vi ‐

Poster session (Monday-Tuesday 20:00-22:30)
P 01 ...........................................................................................................................................................................................43
Enhancement of proton conductivity in highly oriented poly(aspartic acid) thin film
Yuki Nagao, J. Matsui, T. Abe, H. Yamamoto, T. Miyashita, N. Sata and H.Yugami
P 02 ...........................................................................................................................................................................................44
Crystallinity and morphology of PVDF-HFP-based proton-exchange membranes embedding
polytyrenesulfonic acid-grafted silica particles
M. Maréchal, F. Niepceron, J. Bigarré, H. Mendil-Jakani and G. Gebel
P 03 ...........................................................................................................................................................................................45
Proton mobility in tetragonal and monoclinic LaNbO4 through a second-order phase transition
Kazuaki Toyoura, H. Fjeld, R. Haugsrud and T. Norby
P 04 ...........................................................................................................................................................................................46
NMR measurements on proton mobility in nano-crystalline YSZ
Judith Hinterberg, A. Adams, B. Blümich , M. Wilkening, P. Heitjans, S. Kim, Z. A. Munir, R. A. De Souza and M. Martin
P 05 ...........................................................................................................................................................................................47
Determination of the amount of proton in proton conducting alumina by DC polarization method
Yuji Okuyama, N. Kurita, D. Sato, H. Douhara and N. Fukatsu
P 06 ...........................................................................................................................................................................................48
Dynamic absorption behavior of hydrogen within perfluorosulfonic acid polymer electrolyte
membranes during exposure to water vapor
Bun Tsuchiya, S. Nagata, K. Saito, T. Shikama
P 07 ...........................................................................................................................................................................................49
Preparation of multilayered thin film fuel cell using titanium oxide as anodic catalyst via layer-by-layer
assembly
Hisatoshi Sakamoto, Y. Daiko, H. Muto, M. Sakai and A. Matsuda
P 08 ...........................................................................................................................................................................................50
Hydration kinetics of proton-conducting zirconates upon a change of temperature in wet atmosphere
Jung In Yeon and H. Yoo
P 09 ...........................................................................................................................................................................................51
“In-situ” high temperature neutron diffraction study of lanthanum tungstate: a proton conductor with a
fluorite-type structure
Anna Magrasó, I. Ahmed, R. Haugsrud
P 10 ...........................................................................................................................................................................................52
Periodic long range proton conduction pathways in pseudo-cubic and orthorhombic perovskites
M. A. Gomez, D. Shepardson, L. T. Nguyen and T. Kehinde
P 11 ...........................................................................................................................................................................................53
Proton conductivity and stability of Ba2In2O5 in hydrogen containing atmospheres
Jasna Jankovic, D. P. Wilkinson, R. S. Hui
P 12 ...........................................................................................................................................................................................54
Proton solvation and transport in hydrated nafion
Shulu Feng and G. A. Voth
P 13 ...........................................................................................................................................................................................55
Conductivity study of dense BaZr0.9Y0.1O3-δ obtained by spark plasma sintering
Sandrine Ricote , N. Bonanos , H.Wang and B. A. Boukamp
vii

P 14 ...........................................................................................................................................................................................56
Conductivity study of A- and B-site (co-)doped LaNbO4
M. Ivanova, Sandrine Ricote, W. A. Meulenberg, R. Haugsrud, T. Norby
P 15 ...........................................................................................................................................................................................57
Preparation of Nafion 117�-SnO2 composite membranes using an ion-exchange method
C. F. Nørgaard, U. G. Nielsen and E. M. Skou
P 16 ...........................................................................................................................................................................................58
A study of Pt electrodes on proton conducting Ca-doped LaNbO4
Ragnar Strandbakke, T. Norby and R. Haugsrud
P 17 ...........................................................................................................................................................................................59
Proton conductivity in BCY20-Pd ionic hybrid material
Archana Subramaniyan, J. Tong, R. O’Hayre and N. Sammes
P 18 ...........................................................................................................................................................................................60
Defect chemistry and transport properties of oxide protonic perovskite materials with transition metals
on B-site: BaZr1-xPrxO3-δ
K. E. J. Eurenius, T. Kikuchi, M. Tamaru, S. Miyoshi and S. Yamaguchi
P 19 ...........................................................................................................................................................................................61
Microstructural analysis of Y doped BaZrO3
Yukiko Oyama, T. Tsurui, M. Shogo and S. Yamaguchi
P 20 ...........................................................................................................................................................................................62
Site selectivity of Dopants in BaZr1-yMyO3-δ (M = Dy, Eu, Sm) and measurement of their water contents
and conductivities
Donglin Han, Y. Nose, K. Shinoda and T. Uda
P 21 ...........................................................................................................................................................................................63
Proton conductors based on the double perovskite Ba2YNbO6
Xiaoxiang Xu, E. Konysheva, S. Tao and J. T.S. Irvine
P 22 ...........................................................................................................................................................................................64
Atmosphere dependent temperature evolution phase transition of BaCe0.9Y0.1O2.95 - A neutron powder
diffraction study
Abul K. Azad, A. Kruth and J. T.S. Irvine
P 23 ...........................................................................................................................................................................................65
The effect of cation non-stoichiometry of proton conducting LaNbO4
Guttorm E. Syvertsen, A. Magrasó, M. Einarsrud and T. Grande
P 24 ...........................................................................................................................................................................................66
Solid state NMR studies of CsH2PO4, a protonic conductor for intermediate-temperature solid oxide
fuel cells (IT-SOFCs)
Gunwoo Kim, F. Blanc and C. P. Grey
P 25 ...........................................................................................................................................................................................67
First-principles studies of proton - Ba 2+ interactions in LaPO4
Nicole Adelstein, J. Feng, J. A. Reimer, J. B. Neaton and L. C. De Jonghe
P 26 ...........................................................................................................................................................................................68
High temperature protonic conduction properties of (La,Sr)MO3 – SrZrO3 (M = Cr, Mn and Fe) solid
solutions
Atsushi Unemoto, K. Amezawa and T. Kawada
viii

P 27 ...........................................................................................................................................................................................69
Electrical conductivity and defect structure of Sr-Doped Nd3PO7
Atsushi Unemoto, K. Amezawa and T. Kawada
P 28 ...........................................................................................................................................................................................70
Mechanochemical synthesis of proton conductive CsHSO4-azole composites for medium temperature
dry fuel cells
Song-yul Oh, T. Yoshida, G. Kawamura, H. Muto and A. Matsuda
P 29 ...........................................................................................................................................................................................71
Micro solid oxide fuel cells with perovskite type proton conductive thin electrolytes
Fumitada Iguchi, K. Kubota, S. Tanaka, N. Sata, M. Esashi and H. Yugami
P 30 ...........................................................................................................................................................................................72
Room-temperature protonic conduction in nanocrystalline films of yttria-stabilized zirconia
Sangtae Kim, H. J. Avila-Paredes and Z. A. Munir
P 31 ...........................................................................................................................................................................................73
Fabrication of BaCe0.9Y0.1O3-� thin film on Pd substrate by UV-MOD
Koichi Asano, Y. Kozawa, Y. Mugikura and T. Watanabe
P 32 ...........................................................................................................................................................................................74
First principles calculations of defect equilibria in BaZrO3
Akihide Kuwabara, C. A. J. Fisher, H. Moriwake, F. Oba, K. Matsunaga and I. Tanaka
P 33 ...........................................................................................................................................................................................75
On the symmetry of defects in perovskite-type protonic conductors: A Sc-45 NMR study
Itaru Oikawa, M. Ando, H. Kiyono, M. Tansho, T. Shimizu and H. Maekawa
P 34 ...........................................................................................................................................................................................76
Performances of reversible SOFCs with BaZr0.6Co0.4O3-δ as air electrode
F. He, Ranran Peng and C. Xia
P 35 ...........................................................................................................................................................................................77
Space charge effect and dopant segregation in acceptor-doped BaZrO3 proton conductors
Mona Shirpour, B. Rahmati, W. Sigle, P. A. van Aken, R. Merkle and J. Maier
P 36 ...........................................................................................................................................................................................78
Synthesis and characterization of BaCe0.7Zr0.1Y0.1Yb0.1O3-δ proton conducting ceramic
Siwei Wang, F. Zhao, L. Zhang and F. Chen
P 37 ...........................................................................................................................................................................................79
High flux ND-study of the structural phase transition in LaNbO4
C. S. Knee, Morten Huse, T. Norby, S. G. Eriksson, R. Haugsrud
P 38 ...........................................................................................................................................................................................80
Performance of SOFC with proton-conductor BaCe0.7In0.2Yb0.1O3-δ electrolyte
Fei Zhao, L. Dixon and F. Chen
P 39 ...........................................................................................................................................................................................81
Ionic conduction in Mg–Al and Zn-Al layered double hydroxide intercalated with inorganic anions
Kiyoharu Tadanaga, Y. Furukawa, A. Hayashi and M. Tatsumisago
P 40 ...........................................................................................................................................................................................82
Determination of the enthalpy of hydration of oxygen vacancies by TG-DSC
Christian Kjølseth, A. Løken, L.Wang, R. Haugsrud and T. Norby
ix

P 41 ...........................................................................................................................................................................................83
Proton transfer and hydration in 3M ionomers with different protogenic groups
Jeffrey K. Clark and S. J. Paddison
P 42 ...........................................................................................................................................................................................84
Electrical conductivity and defect structure of Y-doped BaZrO3
Ho-Il Ji, J. Lee, H. Kim, J. Son, H. Lee and B. Kim
P 43 ...........................................................................................................................................................................................85
Enhanced sinterability of Y-doped BaZrO3 powder synthesized with CuO, ZnO addition as a sintering
aid
Jong-Ho Lee, S. Hong, H. Ji, J. Park, H. Kim, J. Son, H. Lee and Byung-Kook Kim
P 44 ...........................................................................................................................................................................................86
Intermediate temperature solid oxide fuel cells based on a thin BaZr1-xYxO3-δ proton conductor
electrolyte
Daniele Pergolesi, E. Fabbri and E. Traversa
P 45 ...........................................................................................................................................................................................87
Does the increase in Y-dopant concentration improve the proton conductivity of BaZr1-xYxO3-δ fuel cell
electrolytes?
Fabbri Emiliana, D. Pergolesi, S. Licoccia and E. Traversa
P 46 ...........................................................................................................................................................................................88
Computational modeling of transport phenomena in polymer electrolyte membranes, nafion and
hydrocarbon membrane
Yoong-Kee Choe
P 47 ...........................................................................................................................................................................................89
Study of proton transport using reactive molecular dynamics
Myvizhi Esai Selvan, D. J. Keffer, S. Cui and S. J. Paddison
P 48 ...........................................................................................................................................................................................90
Hydrogen transport in LaNbO4-LaNb3O9 composites
W. Xing, G. E. Syvertsen, and Reidar Haugsrud
P 49 ...........................................................................................................................................................................................91
Poly(p-phenylene sulfone)s with high ion exchange capacity: Ionomers with unique microstructural and
transport features
C. C. de Araujo, K. D. Kreuer, M. Schuster, G. Portale and J. Maier
P 50 ...........................................................................................................................................................................................92
Rule of superprotonic phase transition in CsxRb1-xH2PO4
Yasumitsu Matsuo, J. Hatori, Y. Yoshida and S. Ikehata
P 51 ...........................................................................................................................................................................................93
Hydration and protonic conductivity in LaAsO4 based ceramics
Tor S. Bjørheim, T. Norby and R. Haugsrud
P 52 ...........................................................................................................................................................................................94
Investigation of hydrogen permeation in mixed conductor LaWOX (La/W = 5.6)
Skjalg Erdal and R. Haugsrud
P 53 ...........................................................................................................................................................................................95
Fabrication of Ca-doped lanthanum niobate electrolyte film by electrophoretic deposition for PCFC
applications
Francesco Bozza and N. Bonanos
x

P 54 ...........................................................................................................................................................................................96
Ab initio molecular dynamics study of proton dynamics and mobility in phosphoric acid
Linas Vilciauskas, G. Bester, K. D. Kreuer, M. E. Tuckerman and S. J. Paddison
P 55 ...........................................................................................................................................................................................97
CsH2PO4 nanoparticle synthesis via electrohydrodynamic atomization – aerosol size measurements
Áron Varga, A. J. Downard, H. Wan Do, R. C. Flagan and S. M. Haile
P 56 ...........................................................................................................................................................................................98
Cobalt and yttrium doped barium zirconates as mixed conducting cathodes for SOFC
Björn Björnsson, Juan C. Lucio-Vega, Y. Yamazaki and S. M. Haile
P 57 ...........................................................................................................................................................................................99
High-temperature phase behavior in the Rb3H(SO4)2-RbHSO4 pseudo-binary system
Chatr Panithipongwut and S. M. Haile
P 58 .........................................................................................................................................................................................100
The phase transition and hysteresis behavior of Cs1-xKxH2PO4
Daniil Kitchaev, A. Ikeda and S. M. Haile
xi

Oxide Protonics: Electronic Structure and Acid Base Reactions in
Bulk and Surface
Shu Yamaguchi
Plenary
Department of Materials Engineering, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyoku,
Tokyo, 113-8656, Japan
The discovery of the high temperature oxide protonics materials, defined as oxides in which
proton has a certain transference number, by Professor Iwahara opened a novel frontier in late 70’s.
The quest for the proton conducting electrolytes was the hottest topics of that period of time in solid
state ionics society and many different approaches were carried out for the breakthrough. The oxide
protonics materials with perovskite structure, which is classified generally as a solid base, has a
unique feature other than simple acid or basic characteristics, since the water incorporation reaction
can be expressed by a combination of following partial acid/base reactions,
H + �- �
(g) � OO� OHO
OH - �� - �
(g) � VO � OHO
in which H + and OH - gas were supplied from
water by H2O(g) � H . Therefore,
the presence of both acid and basic site are
+ (g) � OH - (g)
necessary for the water incorporation.
The electronic band structer in Fermi
energy region of the oxide protonics materials is
characterized by a typical wide band gap
semiconductors doped with acceptor dopants as
shown in Figs. 1-(a) through (d), in which O1s
soft X-ray Absorption Spectra (XAS) are shown.
Within the band gap region, there exist deffectinduced
level (DIL) mainly composed of d- or forbital
of B-site cation and the acceptor level
mainly composed of O2p orbital, present with
large unoccupied level in oxydizing stmosphere is
reduced and split into two levels by proton
incorporation. Also it is eviden that holes are created at the top of valence band by a thermcal
activation. The H1s orbital cannot be observed by XAS and contributes indirectly to the band gap
region.
Fig. 1 O1s XAS spectra under dry and humidified
conditions for (a) Sc-doped SrTiO3, (b) Y-doped
SrZrO3, (c) Y-doped BaCeO3, (d) In-doped
CaZrO3[1]
In contrast to the fact that well-grown micrograins have a stable surface, nano-sized grains
have unstable surface with dangling bonds or, in other words, strong basic site, which is stabilized
by the formation of -OH - group at the surface by the hydration, serving as a strong attracter for water
molecule by the hydrogen bond (H-B) formation. Such surface acid/base reaction site serves as a
platform of the surface protonics in addition to the solid acid modified by conjugate ligands such as
sulphates and phosphates. Further discussion on the basic properties of surface -OH - , its thermal
stability, and proton conductivity will be presented.
REREFENCES
[1] T. Higuchi et al.: Materials Integration [in Japanese], 18(2005), No. 7, p. 28.
- 1 -

O 01 (K)
Ab initio molecular dynamics studies of proton structure and transport in
solid acids and acid hydrate crystals
Mark Tuckerman
Department of Chemistry and Courant Institute of Mathematical Sciences, New York University
We present ab initio molecular dynamics studies of two types of systems: The superprotonic phase
of the solid acid cesium dihydrogen phosphate (CDP), and a series of hydrates of
trifluoromethanesulfonic (triflic) acid, specifically, the mono-, di-, tetra-, and penta-hydrates. The
simulation results for CDP suggest that the cubic, superprotonic phase of the system is dynamically
disordered, and two primary mechanisms of proton transport are obtained. The first involves
rotation of the PO4 groups while the second is a Grotthuss type relay mechanism that can occur
without such PO4 rotational motion. The latter is roughly an order of magnitude faster than the
former. Specific time scales associated with these mechanisms are extracted using a new kinetic
framework introduced by us for analyzing the dynamics of structural defects in hydrogen-bonded
systems. Studies of the hydrates of triflic acid suggest preferred locations and structural
characteristics of Eigen and Zundel type cations in these systems as a function of hydration level.
Because strong nuclear quantum effects are expected in these systems, we have performed ab initio
path integral calculations as well as classical ab initio molecular dynamics calculations, and we will
compare these in order to assess the importance of nuclear quantum effects.
- 2 -

Polyelectrolyte multilayers for electrochemical energy applications
Avni A. Argun and Paula T. Hammond
O 02 (I)
Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, USA
The increasing global focus on alternative energy sources has
led to a renewed interest in electrochemical energy systems
such as fuel cells, batteries, and photoelectrochemical cells.
At the core of these devices is an electrolyte which enables
charge transport between electrodes. Polymeric solid state
electrolytes offer high mechanical strength and great
fabrication flexibility, as well as better physical separation of
electrodes. Desired properties of electrolytes would depend
on the application, but it is essential to utilize approaches that
provide fast proton transport and environmentally friendly
processing. The alternating adsorption of oppositely charged
molecular species, known as the electrostatic layer-by-layer
technique, is a simple and elegant method to construct highly
tailored nanocomposites. This approach presents strong
advantages allowing the incorporation of many different
functional materials within a single film with exceptional
homogeneity. The process is also flexible; by altering
assembly conditions such as deposition pH, additives (salts or
surfactants), and co-solvent choice, it is possible to greatly
affect the final thin film composition and properties. We have
Fig. 1 A picture of a free-standing PEM
(~10 μm) assembled using spray-LbL
method.
utilized this method to engineer a number of systems, including the formation of proton exchange
membranes in fuel cells, solid-state electrolytes for batteries, and mixed proton/electron conduction
for photoelectrolytic water-splitting. In one example, we have developed a membrane with proton
conductivity value of 70.0 mS/cm, the highest conductivity ever obtained from a multilayer
assembled film. These multilayer films also exhibit very low liquid methanol permeability to
improve the power output of a direct methanol fuel cell by over 50%. Finally, we have shown the
rapid preparation of large area films using an automated spray apparatus, which reduces the
processing
time by over 40 times (Figure 1). Combined with the use of inexpensive water-soluble
materials,
this has proven to be a viable alternative to incumbent solution processing technologies.
- 3 -

About the evolution of the microstructures of ionomers and
polyelectrolytes for PEM fuel cell applications
K. D. Kreuer 1 , C. C. de Araujo 1 , G. Portale 2 , U. Klock 1 , and J. Maier 1
1. Max-Planck-Institut für Festkörperforschung, Heisenbergstraβe 1, D-70590 Stuttgart, Germany
2.DUBBLE, BM26 at ESRF, 6 rue Jules Horowitz, BP220, F- 38043 Grenoble, Cedex, France
kreuer@fkf.mpg.de
O 03
The strong relations between the microstructures of polymer electrolyte membranes and their
transport properties (proton conductivity and water transport) are well known for a long time 1-6 , but
the relations to other membrane properties are not investigated yet. Also, knowledge of the
interactions driving the microstructural evolution on the relevant scales are still very scarce.
We have therefore investigated the microstructure of divers PFSA and poly –(phenylene-sulfone)
membranes as a function of RH and T by means of Small Angle X-Ray Scattering (SAXS), and the
results have been related to the ones from Dynamical Mechanical (DMA) and Thermo Gravimetric
Analysis (TGA) recorded under the same conditions.
While the structures on the nano-meter scale are found be controlled by electrostatic interactions
(IEC and degree of dissociation 7 ), the long range structures seems to be the consequence of (e.g.
hydrophobic) backbone / backbone interactions. The first is found to be relevant for the relation
between proton and hydrodynamic water transport (electroosmotic drag and water permeation) and
the second for the viscoelastic properties of the membrane. Also long term structural changes are
explained by the interplay of these two type of driving forces and relaxations.
Finally, the relation between the microstructure of diverse poly-(phenylene-sulfone) based
membranes (PBI-blends, block-copolymeres, branched architectures) and their proton conductivity
under minimum hydration conditions is discussed.
1. K. D. Kreuer, Th. Dippel, and J. Maier: Membrane Materials for PEM-Fuel-Cells, A Microstructural Approach; In
Proton Conducting Membrane Fuel Cells I, Sh. Gottesfeld et al., ed., Vol. PV 95-23, The Electrochemical Society,
Pennington, NJ, 1995, pages 241–246.
2. K. D. Kreuer, M. Ise, A. Fuchs, and J. Maier: Proton and Water Transport in Nano-separated Polymer Membranes; J.
Physique IV 10, Pr7–279–Pr7–281 (2000).
3. K. D. Kreuer: On the Development of Proton Conducting Polymer Membranes for Hydrogen and Methanol Fuel
Cells; J. Membrane Science 185 (1), 29–39 (2001).
4. K. D. Kreuer, M. Schuster, B. Obliers, O. Diat, U. Traub, A. Fuchs, U. Klock, S. J. Paddison, and J. Maier:
5. Short-side-chain proton conducting perfluorosulfonic acid ionomers: Why they perform better in PEM fuel cells; J.
Power Sources 178(2), 499–509 (2008).
6. C. C. de Araujo, K. D. Kreuer, M. Schuster, G. Portale, H. Mendil-Jakani, G. Gebel, and J. Maier:
Poly(p-phenylene sulfone)s with high ion exchange capacity: ionomers with unique microstructural and transport
features; Phys. Chem. Chem. Phys. 11(17), 3305–3312 (2009).
7. A. Telfah, G. Majer, K. D. Kreuer, M. Schuster, and J. Maier: Formation and mobility of protonic charge carriers in
methyl sulfonic acid-water mixtures: A model for sulfonic acid based ionomers at low degree of hydration; Solid State
Ionics 181(11-12), 461–465 (2010).
- 4 -

Coherent Proton Transport in Nafion
George Reiter
Physics Department, University of Houston
O 04
Measurements of the momentum distribution of the protons in Nafion and Dow 858 short side chain
polymer show that, at any instant most of the protons are coherently delocalized in a double well
potential. The potential differs for the two materials, for the same value of lambda(~14), in the
separation of the wells and the fraction of delocalized protons. The transport in these materials
must differ significantly from that for a localized proton that can be approximated as a classical
particle.
- 5 -

O 05 (K)
NMR studies of local structure, cation ordering and protonic conduction in
perovskites
Lucienne Buannic 1 , Frederic Blanc 1 , Derek Middlemiss, and Clare P. Grey 1,2
1 Department of Chemistry, Stony Brook University, Stony Brook, NY 11794-3400 USA
2 Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, UK CB2 1EW
This talk will illustrate the use of high field, multinuclear NMR spectroscopy to investigate the
nature of the defects in materials for solid-state electrolytes. In particular, we focus on electrolytes
that operate via protonic conduction in solid oxide fuel cells. For example, BaZrO3 or BaSnO3 can
be doped with Y 3+ or Sc 3+ to create oxygen vacancies. These vacancies can be filled with H2O, the
water molecules dissociating to form mobile ions that contribute to the long-range ionic transport in
these systems. NMR experiments are used to examine the local structure, the locations of the
vacancies and how this affects protonic/oxygen ion motion in these systems. NMR studies of the
host B cations (Zr, Sn) can be used to quantify (particularly in the case of Sn) the ratio of 5:6 fold
cations, and thus indirectly, the location of the vacancy. NMR studies of the dopants (Sc, Y) can be
used to investigate vacancy trapping. The location of the dopant ion is often ambiguous, and we
show that 89 Y can be used to investigate cation doping on the A vs. B site of the perovskite, the
former reducing the number of oxygen vacancies and thus the number of protons, following
hydration. Finally, 17 O NMR experiments are shown to be extremely sensitive to the nature of the
B cation directly bound to the oxygen site, different resonances being observed for the B-O-B’ sites
on cation doping. Chemical shift calculations, performed by using the CASTEP code, reveal that
oxygen ions in axial and equatorial positions relative to a vacancy (i.e., in a OaxialB(Oeq)-vac local
environment, where vac = oxygen vacancy) can be distinguished. The implications of these
results for protonic conduction will be discussed.
- 6 -

Recent Developments in Solid Acid Fuel Cells
Calum R.I. Chisholm
SAFCell, Inc. 36 South Chester Avenue, Pasadena CA 91106, USA
O 06 (I)
Solid acids are compounds whose chemistry and properties are intermediate between those of a
normal acid, such as H2SO4 or H3PO4, and a normal salt, such as Cs2SO4. The anhydrous, solidstate
proton conductivity of these materials can reach values higher than 10 -2 Ω -1 cm -1 when heated
to moderately elevated temperatures (150-250°C)[1], making solid acids excellent candidates for
fuel cell electrolytes. In particular, fuel cells using cesium dihydrogen phosphate (CsH2PO4), with a
conductivity of 2.5 x10 -2 Ω -1 cm -1 at 250 °C, have been demonstrated with thin (10-25 μm) gas tight
electrolyte layers. [2-5]
Recent developments at the cell and stack level show solid acid fuel cells (SAFCs) using
CsH2PO4 to have sufficiently high enough performance/durability and low enough cost for
commercialization in initial markets such as portable and premium power.[6] To date, SAFCs have
measured peak power densities over 0.5 W/cm 2
on hydrogen/air and lifetimes surpassing a
thousand hours. SAFC stacks have also been
fabricated using both 15 and 110 cm 2 active area
cells with demonstrated power outputs over 250
W. Very importantly, SAFCs have also operated
on fuel streams with high levels of impurities such
as CO, H2S and NH3, making them a fuel flexible
technology capable of running on “dirty”
reformates of commercially available fuels such
as methane, propane, methanol, diesel and
kerosene (JP8).[7, 8]
Talk will highlight the recent promising
developments and remaining challenges for
SAFCs to become a broadly accepted commercial
technology.
- 7 -
IR Corrected
Cell Voltage [mV]
1000
900
800
700
600
250 O C
Stoich 1.2/2 H 2 /O 2
pH 2 O = 0.3 bar
Cell Active Area
1.5 cm 2
15 cm 2
110 cm 2
500
0 100 200 300 400 500 600 700 800
Current Density [mA/cm2]
Fig. 1 Scaling of SAFC membrane electrode
assemblies: area normalized performance is
nearly identical over two orders of
magnitude.
1. A.I. Baranov, L.A. Shuvalov and N.M. Shchagina, JETP
Lett. 36 (1982) (11), p. 459.
2. S.M. Haile, D.A. Boysen, C.R.I. Chisholm and R.B. Merle, Nature 410 (2001), p. 910.
3. D.A. Boysen, T. Uda, C.R.I. Chisholm and S.M. Haile, Science 303 (2004), p. 68.
4. T. Uda and S.M. Haile, Electrochemical and solid-state letters 8 (2005) (5), p. A245.
5. S.M. Haile, R.I.C. Chisholm, K. Sasaki, D.A. Boysen and T. Uda, Faraday Discussions 134 (2007), p. 17.
6. C.R.I. Chisholm, D.A. Boysen, A.B. Papandrew, S. Zecevic, S. Cha, K. Sasaki, A. Varga, K.P. Giapis and S.M.
Haile, Interface Fall (2009), p. 7.
7. T. Uda, D.A. Boysen, C.R.I. Chisholm and S.M. Haile, Electrochemical and solid-state letters 9 (2006) (6), p.
A261.
8. H.H. Duong, Solid Acid Fuel Cell Stack for APU Applications, In: DOE, Editor, DOE Hydrogen Program (2009),
pp. 1177-1182.

Local Structure and Hydride-Ion Transport in MgY2H8
Hitoshi Takamura, Keita Kurosu, Akira Hatakeyama, and Hideki Maekawa
Department of Materials Science, Graudate School of Engineering, Tohoku University,
6-6-11-301-2 Aramaki Aoba, Sendai 980-8579, Japan
As well as metal oxides, metal hydrides comprising of
alkaline- and rare-earth elements such as CaH2 and YH3
exhibit ionic-bonding nature. Depending on crystal structure
and defect concentration, hydrogen can migrate as a form of
hydride ion (H - ) in such metal hydrides[1]. In this study, local
structure and transport property of MgY2H8 having a
defective BiF3-type structure are investigated. MgY2H8 is
prepared by using a cubic-anvil-type apparatus at 800 °C
under 5 GPa [2]. To modify hydrogen content in the hydride,
a hydrogen source comprising of NaBH4 and Ca(OH)2 is
used. Raman spectra of MgY2H8 at room temperature show a
band at around 920 cm -1 corresponding to an F2g mode of Tsite
hydrogen, which corresponds to oxide-ion sites in a
stabilized zirconia, and a broad band at around 500 - 1200
cm -1 presumably suggesting the presence of O-site hydrogen.
The detailed local structure of MgY2H8 will be discussed
based on these spectroscopic analyses. Electrical properties
including hydride-ion transport of MgY2H8 are evaluated by
using AC impedance and NMR spectroscopic techniques.
Figure 1 shows Arrhenius plots of the total electrical
conductivity of MgY2H8 prepared with or without the
O 07
Fig. 1 Arrhenius plots of MgY2H8
prepared with or without a hydrogen
source. Atmosphere is either under
evacuation or H2 flow.
hydrogen source. Even though all the sample show electronic conduction as a major carrier, the
conductivity strongly depends on preparation and measurement atmospheres. This implies that
hydrogen content affects the concentration of electronic carriers. The conductivity of hydride ion in
MgY2H8 is estimated from T1 analysis of 1 H NMR, and also plotted in Fig. 1. The hydride-ion
conductivity is found to be smaller than the electronic conductivity by 2 to 3 orders of magnitude.
The
transport properties of MgY2H8 will be discussed in the context of its local and electronic
structures.
1. S. J. van der Molen, M. S. Welling, and R. Griessen, Phys. Rev. Lett. 85 (2000), 3882.
2. H. Takamura, Y. Goto, A. Kamegawa and M. Okada, Mater. Trans. 44 (2003), 583.
- 8 -

O 08 (K)
Improving the proton conductivity of yttrium-doped barium zirconate
electrolytes towards the development of intermediate temperature solid
oxide fuel cells
Enrico Traversa
International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS),
1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
For the widespread deployment of solid oxide fuel cells (SOFCs), the high cost is an obstacle,
together with the long-term stability due to the high working temperatures. Reducing the SOFC
operating temperature in the 400-700°C range can reduce fabrication costs and overall improve
performance. This aim can be obtained using high temperature proton conductor (HTPC) oxides as
electrolytes, due to by their lower activation energy for proton conduction (0.3-0.6 eV), with respect
to oxygen-ion conductor electrolytes. Moreover, proton conductor electrolytes offer the advantage
of generating water at the cathode, and thus the fuel does not become diluted during cell operation
[1].
Among polycrystalline HTPCs, doped BaCeO3 shows the largest proton conductivity, but it is not
suitable for fuel cell applications since it easily reacts with acidic gases, e.g. CO2, and water vapor.
Doped BaZrO3 offers instead excellent chemical stability against reaction with CO2 and H2O, but
low conductivity values for sintered pellets. The low electrical conductivity is the consequence of
poor conductive grain boundary regions coupled with the material sintering difficulties.
This work reports the various strategies recently followed in our lab to improve the conductivity of
Y-doped barium zirconate [2,3], towards the limitation of grain boundary surface, the use of co-
doping
for improving the sinterability, and the fabrication of films by pulsed laser deposition (PLD)
[ 4,5].
1. E. Fabbri, D. Pergolesi and E. Traversa, Chemical Society Reviews, in press.
2. A. D'Epifanio, E. Fabbri, E. Di Bartolomeo, S. Licoccia and E. Traversa, Fuel Cells 8 (2008), 69.
3. E. Fabbri, A. D'Epifanio, E. Di Bartolomeo, S. Licoccia and E. Traversa, Solid State Ionics 179 (2008), 558.
4. E. Fabbri, A. D’Epifanio, S. Sanna, E. Di Bartolomeo, G. Balestrino, S. Licoccia and E. Traversa, Energy &
Environmental Science 3 (2010), 618.
5.
D. Pergolesi, E. Fabbri and E. Traversa, Electrochemistry Communications 12 (2010), 977.
- 9 -

Existence of equilibrium mixture between Hydrated and Unhydrated
Proton conducting Perovskites and possible implications
John T.S. Irvine 1 , Maarten C. Verbraeken 1 , Hemangildo Viana 1 , Azul K. Azad 1 , Istaq Ahmed 2 , and
Sten Eriksson 2
1. School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UK
2. Department of Chemical and Biological Engineering, Chalmers University of Technology, Sweden
O 09
Neutron powder diffraction offers an excellent technique for the location of protons (or deuterons)
in hydrated perovskite proton conductors. It would be expected that the concentration of these
protons would increase as temperature is decreased or the humidity of equilibrating atmosphere is
increased; however, in recent studies of several systems we have observed some quite dissimilar
behaviour. These systems include members of the BCN family such as Ba3Ca1.18Ta1.82O8.73 and
Indium doped barium zirconates such as Ba0.5In0.5ZrO3-y. Results will be presented from X-ray and
neutron powder diffraction that demonstrate 2 phases with similar structure are present in
equilibrium, with one being essentially hydrated and one essentially unhydrated. In such a system,
as temperature is decreased or humidity increased, then the dominant change will be an increase in
the hydrated phase proportion. This behavior can be simply interpreted in terms of phase equilibria
diagrams and the implications of this deviation from assumed solid solution of water into a single
phase will be discussed.
- 10 -

Local structure and proton dynamics in In-doped BaZrO3
Maths Karlsson 1 , Aleksandar Matic 2 , Istaq Ahmed 3 , Christopher S. Knee 4 , Sten Eriksson 3
O 10
1 European Spallation Source AB, 221 00 Lund, Sweden, 2 Dept. of Applied Physics, Chalmers University of Technology,
412 96 Göteborg, Sweden, 3 Dept. of Chemical and Biological Engineering, Chalmers University of Technology, 412
96 Göteborg, Sweden, 4 Dept. of Chemistry, University of Gothenburg, 412 96 Göteborg, Sweden
Hydrated acceptor-doped perovskite-type
oxides, such as In-doped BaZrO3, have been
widely studied in recent years because of their
high proton conductivities at elevated
temperatures and concomitant promise for use
as electrolytic membrane in future fuel cells
[1]. The acceptor-doping creates an oxygen
deficient structure, which in protons can be
introduced by exposure to a humid
atmosphere [1]. The protons are generally
believed to migrate into the structure through
jumps between oxygens. From this it is easy
to understand that the local structure plays a
key role for the local proton dynamics, as well
as for the long-range diffusion. In this
context, we have during the last years been
investigating the relationship between local
structure and proton dynamics in protonconducting
perovskites, using neutron
diffraction [2], inelastic [3] and quasielastic
[4] neutron scattering, and optical vibrational
spectroscopy [5-7]. The goal with these
studies has been to increase the understanding
of the proton conduction process so that one
can ‘realize’ new compounds with higher
conductivities, which is a critical factor for
practical applications.
As one example of our results, neutron spinecho
data of BaInxZr1-xO3-x/2Hx (x = 0.10 and
0.50) shows that the diffusional proton selfdynamics
are strongly dependent on the In
concentration and the short-range structure of
the material [4], see Figure 1. For the highly
doped material (x = 0.50), we observe a
distribution of translational diffusional rates
of the protons in the structure on the time
scale of nanoseconds and with an effective
activation energy of about 0.75 eV [4]. The
wide range of diffusional rates is found to be
related to dopant-induced short-range
- 11 -
distortions of the average cubic structure,
yielding many structurally different local
configurations of the protons in the structure,
each configuration with its own energy
barriers for proton migration [4,5]. For
comparison, the data of the weakly doped
compound (x = 0.10) reveal dynamics on a
more well defined time scale, ~60 ps at 500
K, as a result of a more ordered local structure
[4,5]. In this presentation, I will describe our
results in more detail.
Figure 1. Intermediate scattering function of In-doped
BaZrO3 obtained from neutron spin-echo at T = 500 K
and Q = 1.05 Å -1 (Q: momentum transfer during the
neutron-proton scattering process).
1. K. D. Kreuer, Annu. Rev. Mater. R. 33 (2003) 333.
2. I. Ahmed, J. Alloys and Compds 450 (2008) 103.
3. M. Karlsson, Phys. Rev. B 77 (2008) 104302.
4. M. Karlsson, J. Phys. Chem. C 114 (2010) 3292.
5. M. Karlsson, Chem. Mater. 20 (2008) 3480.
6. M. Karlsson, Solid State Ionics 181 (2010) 126.
7. M. Karlsson, J. Phys. Chem. C 114 (2010) 6177.

Grain Boundary Conduction in polycrystalline Y-doped BaZrO3: Space
Charge Analysis
Sangtae Kim, Chien-Ting Chen, Christina Danel
Department of Chemical Engineering and Materials Science, University of California, Davis, CA 95616, USA
O 11
Y-doped BaZrO3 (BZY) is one of the most intensively studied high-temperature proton conductors.
The bulk conductivity of this chemically stable solid electrolyte (SE) is reported to be higher than
that of conventional oxygen-ion conducting solid electrolytes such as doped zirconia and ceria in
the so-called intermediate temperature range (ca 400 – 600 C). On the other hand, the grain
boundaries in the polycrystalline ceramic of this material is known to be highly resistive to proton
transport across them, leading to the total conductivity of the polycrystalline BZY being
substantially lower than its bulk conductivity. It has been speculated that such high proton
resistance at the grain boundaries
may be due to proton depletion at
the grain boundaries (namely space
charge effects). In fact, some
researchers have recently applied
the space charge model to explain
the conduction behavior at the
grain boundaries in BZY. In this
contribution, we demonstrate the
results of our investigation on the
potential space charge effects on
the grain boundary conduction in
BZY. We have applied the space
charge model to the bulk and the
grain boundary conductivity
measured from not only our own
samples but also BZY with
log c H+
4 3 2 1 0 0
x / nm
1 2 3 4
different Y-concentration previous reported. The grain boundary activation energies and widths
measured from BZY will be quantitatively discussed based on the space charge model.
H + H + H +
H + H + H +
Fig. 1. Proton concentration profiles in a space charge zone in BZY at
different core charges estimated at 400�C. The dopant concentration is
1�10 20 cm -3 .
- 12 -
0.1V
0.2V
0.3V
0.4V
0.5V

Atomic-Scale Insights into Proton-Conducting Oxides:
Defects, Dopants and Transport
M. Saiful Islam
Department of Chemistry, University of Bath, UK
m.s.islam@bath.ac.uk
O 12 (K)
Ion-conducting oxide materials have been attracting considerable attention owing to their potential
applications in solid oxide fuel cells (SOFCs) and other electrochemical technologies. It is clear that
fundamental materials research is a crucial component in the discovery and characterisation of
materials for such applications. In this context, advanced computational techniques are now
powerful tools for probing the properties of energy materials on the atomic- and nano-scale. This
presentation will highlight recent studies on solid-state proton conductors focusing on perovskitetype
materials (such as doped BaZrO3) and novel oxide structures containing tetrahedral units (such
as LaBaGaO4, doped LaNbO4, and Ge-based apatites). Key solid-state properties investigated
include local protonic sites, defect-dopant association and ion conduction mechanisms. In every
case, our results are closely correlated with the available structural and transport studies (e.g.
diffraction, conductivity, NMR).
1. Kendrick E, Kendrick J, Knight KS, Islam MS and Slater PR, Nature Materials, 6, 871 (2007).
2. Islam MS, Slater PR, MRS Bulletin 34, 935 (2009).
3. Panchmatia PM, Orera A, Kendrick E, Smith ME, Slater PR, Islam MS, J. Mater. Chem. 20, 2766 (2010).
- 13 -

DFT-MD study of local structures and proton transport in disordered
Brownmillerite-based compounds
Karsten Rasim 1,2 , Florent Boucher 1 , Olivier Joubert 1 , Philippe Baranek 2 , Mathieu Marrony 3
1 Institut des Matériaux Jean Rouxel, 2 rue de la Houssinière, BP32229, 44322 Nantes cedex, France
2 EDF R&D, Dep. MMC, Avenue des Renardières, 77818 Moret sur Loing Cedex, France
3 EIFER, Emmy-Noether-Strasse 11, 76131 Karlsruhe, Germany
O 13
A detailed study of heavily cation-substituted, disordered Brownmillerite based compounds is
presented. The focus is on their proton conduction behaviour as well as their structural properties in
the dry state. The study is conducted by DFT calculations (both static and Born-Oppenheimer
molecular dynamics [1]) combined with experimental approaches: XANES and IR-spectra
measurements. Amongst others, by means of these techniques, the coordination preference of
different substituents, the protonic mobility and vibrational spectra can be obtained and compared
to experimental evidence. The focus lies on the Ba2In2(1-x)Ti2xO5+x (BITx)[2] family, proven to be a
well suited electrolyte material for PCFC. Moreover, neighbouring compounds, such as Sr2In2(1x)Ti2xO5+x
(SITx), Ba2In2(1-x)Zr2xO5+x (BIZx) and Ba2In2(1-x)Y2xO5 (BIYx), are being considered as
they prove useful to systematically clarify the influence of different chemical environments on
proton diffusivity (e.g. different "proton affinities" of the Ti, Zr or Y- substituents, more or less
pronounced hydrogen bonding, distinction between extra- and intra-octahedrally bonded protons,).
All those aspects are obtained in
the molecular dynamics
framework, therefore including
temperature or entropic effects,
both vibrational and
configurational in nature.
A key aspect in this study of proton
transport is the detailed analysis of
each of the six unique elementary
displacement steps (shown in
figure 1) that were identified
during the MD-simulations. Each
of them can be characterized by an
effective free-energy barrier at a
given temperature and by combining runs at different
temperatures, activation energies and -entropies can be
extracted. It turns out, that the protonic mobility in this class
of materials is heavily influenced by the existence of the two
distinct proton sites, intra- and extra-octahedral. This is to be
seen in contrast to the case of the well studied perovskite-
related compounds that do usually only enable intra-octahedral proton sites.[4]
[1] G. Kresse, J. Hafner, Phys.Rev.B. 49, 20 (1994) 14251.
[2] Jayaraman et al, Solid State Ionics 170 (2004) 17-24.
[3] E. Quarez et al. Journal of Power Sources, 195 (15), (2010) 4923-4927
[4] K-D. Kreuer, Annu. Rev. Mater. Res. 33, 333-359 (2003)
- 14 -
Fig. 1 The six unique proton
displacement modes in the
Brownmillerite related compounds
studied.

O 14
Ab Initio Studies of the Effect of Hydrophobic
Environment on Proton Transfer in Model Perfluorsulfonic Acid Systems
Bradley F. Habenicht and Stephen J. Paddison
Department of Chemical and Biomolecular Engineering, University of Tennessee Knoxville,1512 Middle Drive,
Knoxville, TN 37996, USA
Single walled carbon nanotubes (CNT) were functionalized
with perfluorosulfonic acid (-CF2SO3H) groups and hydrated
with water molecules (1 and 3 H2O/SO3H) to investigate
proton dissociation and transport in simplified proton
exchange membranes under conditions of minimal hydration
[1]. The systems were studied using ab initio molecular
dynamics (AIMD), which does not require a priori
assumptions about proton dissociation and hydration. The
influence of the hydrophobic environment was studied by
comparing proton mobilities with and without fluorine atoms
attached to the CNT walls (Figure 1). The AIMD trajectories
showed that dissociation of the acidic proton was increased
as sulfonic acid density increased, however, greater densities
also increased trapping of the dissociated proton [2]. The
fluorine atoms accepted hydrogen bonds from the water
molecules, stabilized hydrogen bonding, and enhanced
proton dissociation. The CNT systems with bare walls
exhibited a propensity for Zundel cation (H5O2 + ) formation,
hile the fluorinated systems favoured the hydronium cation
H3O + w
( ) [3].
Fig. 1 Schematic of functionalized CNTs
used
in this study. Atoms have been
removed
from CNT walls for clarity.
1. K.D. Kreuer, S.J. Paddison, E. Spohr and M. Schuster, Chem. Rev. 104 (2004), p. 4637.
2. B.F. Habenicht, S.J. Paddison and M.E. Tuckerman, J. Mater. Chem. In press (2010).
3.
B.F. Habenict, S.J. Paddison and M.E. Tuckerman, Phys. Chem. Chem. Phys. In press (2010).
- 15 -

- 16 -
O 15(K)
Analysis of Transport through Mixed Proton, Oxygen Ion, and Electron
(Hole) Conductors: Fuel Cell and Electrolyzer Modes
Anil Virkar
Utah University
This talk is on the analysis of transport through mixed proton, oxygen ion and electron (hole)
conducting membranes. The predominant transport is by protons and oxygen ions with electronic
conductivity being small. The only permeation of H2, O2, and H2O is assumed to occur via a
coupled transport of H + , O 2- , and e (and/or h). Transport is analyzed for three cases: (1) Fuel cell
under normal operating conditions, (2) A driven fuel cell, and (3) Electrolyzer. Transport equations
are presented in the Onsager format. All coefficients are given in terms of cell parameters and the
operating conditions. Spatial variations of chemical potentials of all neutral species through the
membrane are determined as a function of operating conditions. Implications of the analysis
performed and the results obtained will be discussed. A possible experimental procedure for the
measurement of transport coefficients in the various modes of operation will be described.

O 16 (I)
Hydrogen in nominally anhydrous minerals: analysis and implications
George R. Rossman
Geological and Planetary Sciences, California Inst. Technology, 1200 E California Blvd., Pasadena, CA 91125, USA
Many naturally occuring minerals and their synthetic
counterparts contain minor amounts of hydrous
components, usually as the OH - ion and as the H2O
molecule [1]. These hydrous components can influence
the physical properties of the host phase, in some cases
producing 5- or 6-orders of magnitude change in
properties when incorporated in concentrations at the level
of a few-hundred ppm. For decades, the detection of the
hydrous components has been easily accomplished
through the use of infrared spectroscopy. The
determination of their quantitative concentration has
proven more difficult, especially when their
concentrations is low. Nevertheless, it has been shown
that these components are particularly important in
minerals that come from the earth’s mantle and constitute
a major resevoir of “water” within planet earth. Much
effort has been developed towards determining the
analytical concentrations of hydrous components using
methods such as quantitative infrared spectroscopy,
nucular magnetic resonance (NMR) spectroscopy, thermal
analysis, nuclear profile analysis (NPA), and, more
recently, secondary ion mass spectrometry (SIMS).
Several of these analytical methods reveal a high
concentration of hydrogen on the surface of crystals
compared to the interior (Figure 1).
Fig. 1 The hydrogen content,
expressed as H2O, of a nominally
anhydrous crystal of olivine,
(Mg,Fe)2SiO4 determined by nuclear
profile analysis [1].
1. Rossman GR, Reviews in Mineralogy and Geochemistry 62 (2006), 1.
2. D.R. Bell, G.R. Rossman, J. Maldener, D. Endisch, F. Rauch, Journal of Geochemical Research, 108(B2), 2105,
doi:10.1029/2001JB000679, 2003
- 17 -

The dynamical behaviour of water and protons in perfluorinated
membranes and surfactants.
S. Lyonnard 1 , C. Cailleteau 1 , H. Mendil-Jakani 1 , S. Mossa 1 , Gerard Gebel 1
Armel Guillermo 1 , B. Frick 2 and J. Ollivier 2
1 Structures et Propriétés d’Architectures Moléculaires, UMR 5819 (CEA-CNRS-UJF)
Laboratoire des Polymères Conducteurs Ioniques. INAC/SPrAM – CEA-Grenoble
38054 Grenoble Cedex 9, France
2
Institut Laue Langevin
BP156, 6 rue Jules Horowit z,
38042 Grenoble, France.
- 18 -
O 17 (K)
Perfluorinated ionomers, the reference membranes for PEM fuel cells, are characterized by a
hydrophobic/hydrophilic nanophase separation. Water is the medium for proton transfer: it plays a
central role, although not yet fully elucidated, in the conduction mechanisms that need to be
optimized for the ongoing development of new efficient fuel cells.
The dynamical properties of the water are severely affected by the confinement in the charged
matrix at the nanometric scale. In order to clarify the structure-to-transport relationship in ionomers,
we have studied by Quasi-elastic Neutron Scattering and Molecular Dynamics Simulations the
behaviour of water in different systems: perfluorinated membranes (Nafion® [1], aged Nafion®,
and short side chain Aquivion TM ) and surfactants [2]. The latter mimic the physico-chemical
properties of the real systems and offer the advantage to self-assemble in well defined organized
phases.
QENS studies were performed on both time-of-flight and backscattering spectrometers at the ILL.
The quasielastic spectra are discussed on the basis of a sophisticated model for confined motion [3].
This unique diffusion model based on Gaussian statistics takes into account both localized
translational motions and long-range diffusion. Comparison of the diffusion mechanisms and
parameters (diffusion coefficients, confinement sizes and characteristic times) obtained in the
various
systems as a function of their hydration bring new insight on the complex molecular
scenario
for proton motion under confinement.
[1] J-C. Perrin, S. Lyonnard and F. Volino; Quasielastic neutron scattering study of water dynamics in hydrated nafion
membranes, Journal of Physical Chemistry C, 111 (2007), 3393-3404.
[2] S. Lyonnard, B-A. Bruening, G. Gebel, A. Guillermo, J. Ollivier and B. Frick; Perfluorinated surfactants as model
charged systems for understanding the effect of confinement on proton transport and water mobility in fuel cells
membranes. A study by QENS. Proceedings of Confit 2010, EPJ, to be published.
[3] F. Volino, J-C. Perrin and S. Lyonnard; Gaussian model for localized translational motion : application to
incoherent neutron scattering, Journal of Physical Chemistry B, 110 (2006), 11217-11223.

O 18 (K)
Tailored Tungsten Oxide Nanoparticles Produced with Hot Wire Chemical
Vapor Deposition for Protonic Electrochromic and Fuel Cell Applications
Anne C. Dillon, See-Hee Lee*, Rohit Deshpande, Katherine E. Hurst, Shyam Kocha, Virginia R.
Anderson* and Steven M. George*
National Renewable Energy Laboratory , 1617 Cole Blvd., Golden , CO 80401, USA
*University of Colorado, Boulder 80309, USA
The majority of the world energy consumption is derived from fossil fuels. The conversion
reactions required for retrieving energy from carbon resources result in the production of green
house gases and subsequent global warming effects. It is therefore necessary to develop “green”
technologies that will reduce fossil fuel consumption. We
have employed hot wire chemical vapor deposition
(HWCVD) for the generation of crystalline WO3
nanostructures at high-density. Furthermore, the
morphology of the nanoparticles is easily tailored by
altering the HWCVD synthesis conditions[1]. A
transmission electron microscope (TEM) image of a WO3
nanorod is provided in Figure 1. Electrochromic (EC)
materials change optical properties (darken / lighten) by
application of small electric potential difference, and are
suitable for energy efficient windows, anti-glare
automobile rearview mirrors and sunroofs that enable
significant energy savings. There are two critical criteria
for selecting an EC material. One is the time constant of
the ion intercalation reaction, which is limited both by the
diffusion coefficient and also by the length of the
diffusion path. While the former depends on the
Figure 1: TEM image of HWCVDgenerated
crystalline WO3 nanorods.
chemical and crystal structure of the metal oxide, the latter is determined by the microstructure. In
the case of a nanoparticle the smallest dimension represents the diffusion path length. Thus
designing a nanostructure with a small radius while also maintaining the proper crystal structure is
key to a material with fast insertion kinetics, enhanced durability and superior performance. Stateof-the–art
amorphous WO3 films that are typically employed for commercial EC applications rely
on Li + insertion rather than H + insertion as cycling in an acidic electrolyte generally results in
significantly faster device degradation. However, the ability to employ protons to change the
optical properties will enable significantly faster switching speeds to be demonstrated. We have
shown that porous films of crystalline WO3 nanorods exhibit vastly superior electrochemical
cycling stability in an acidic electrolyte and higher charge insertion with comparable coloration
efficiency relative to amorphous films[2]. The WO3 nanoparticles are also promising as catalyst
supports in PEM fuel cells. Tungsten oxides have long been known to enhance the oxygen
reduction reaction and to decompose peroxide that attacks the carbon support and ionomer in the
catalyst layer. We are currently employing atomic layer deposition[3] to anchor small Pt clusters to
the WO3 nanorods for the development of an improved hydrogen fuel cell catalyst. The synthesis of
these metal oxide nanoparticles and their application in both EC windows and as fuel cell catalysts
will be presented in detail.
1. A.H. Mahan, P.A. Parilla, K.M. Jones and A.C. Dillon, Chem. Phys. Lett. 413 (2005), p. 88.
2. S.-H. Lee, R. Deshpande, P.A. Parilla, K.M. Jones, B. To, A.H. Mahan and A.C. Dillon,
Adv. Mat. 18 (2006), p. 763.
3. A.C. Dillon, A.W. Ott, J.D. Way and S.M. George, Surf. Sci. 322 (1995) (1-3), p. 230.
- 19 -

O 19 (I)
Uphill gas permeation due to coupled transport in a mixed proton, oxygen
vacancy and hole conducting perovskite membrane
Michael Sanders 1 , Jianhua Tong 1 , Huayang Zhu 2 , Robert Kee 2 , and Ryan O’Hayre 1
1 Metallurgical and Materials Engineering, Colorado School of Mines, 1500 Illinois St., Golden, CO. 80401, USA
2 Mechanical Engineering, Colorado School of Mines, 1500 Illinois St., Golden, CO. 80401, USA
Coupled transport membranes utilize the
flux of one species to help drive the flux
of another species, in some cases even
against its own chemical potential
gradient. These membrane processes are
exploited in both natural systems, (where,
for example, they underpin cellular
membrane signal transduction [1]) and in
man-made systems, (where, for example,
they have been applied to a number of
multi-component solvent or metal
separations processes [2-5]). To date,
however, coupled transport membrane
studies and applications have been almost
exclusively confined to aqueous or liquid
membrane media. While these systems
have provided remarkable insights and
have enabled novel separations
approaches, both scientific understanding
and commercial application have been
Fig. 1 Permeation experiments showing uphill transport. The tilt
of
the arrows signifies whether the transport was “uphill” or
“downhill.”
For case a, steam transported uphill while oxygen
transported downhill; the opposite occurred in case b.
limited because of the challenges associated with liquid membranes. These challenges include
instability of the membrane and/or the carrier chemistry.
Using the coupled defect transport inherent in a proton conducting perovskite ceramic, we have
developed a membrane capable of simultaneously transporting water and oxygen, including the
uphill transport of either chemical species. This is the first known example of a solid-state coupled
transport membrane and is the first of any type to operate at high temperatures. The unique features
of this system alleviate many of the drawbacks associated with liquid membranes and opens up the
possibility of new membrane separation applications, including air separation or natural gas
reforming using waste steam and heat streams, as well as the ability to controllably “pump” or
“gate” the permeation of select gas species using conjugate chemical potential gradients.
1. Schultz, S. & Curran, P. Coupled transport of sodium and organic solutes. Physiological Reviews 50, 637 (1970).
2. Kondepudi, D. K. & Prigogine, I. Modern thermodynamics from heat engines to dissipative structures. Wiley,
(2002).
3. Babcock, W. C., Baker, R. W., Lachapelle, E. D. & Smith, K. L. Coupled transport membranes II: : The
mechanism of uranium transport with a tertiary amine. Journal of Membrane Science 7, 71-87, (1980).
4. Baker, R. W. Membrane technology and applications. (Wiley, 2004).
5.
Baker, R. W., Tuttle, M. E., Kelly, D. J. & Lonsdale, H. K. Coupled transport membranes : I. Copper separations.
Journal
of Membrane Science 2, 213-233, (1977).
- 20 -

O 20
Proton migration at Σ5 (310)/[001] tilt grain boundary in Y-doped BaZrO3
Cheonan Kim
Korea University of Technology and Education
The energy barriers for proton migration in polycrystalline Y-doped BaZrO3 (BZYO) have been
experimentally studied: the energy barrier for bulk was about 0.45 eV [1] and that for grain
boundary was about 0.6 eV [2]. The energy barrier for proton migration in bulk BZYO has been
calculated and compared with the experimentally obtained values [3]. Since the practical proton
conductors are polycrystalline, and therefore protons should migrate across the grain boundaries,
there has been a big demand for the energy barrier calculation about the grain boundaries of BZYO.
We studied the proton migration at Σ5 (310)/[001] tilt grain boundary in BZYO using density
functional theory (DFT), since the tilt grain boundary was commonly observed experimentally. An
optimum Σ5 (310)/[001] tilt grain boundary was first constructed and a preferential site for an Y+3
ion among the Zr sites was calculated. There were one Zr site on the grain boundary and three other
Zr sites near it. The Y+3 ion preferred the first nearest Zr site off the grain boundary among the
three other Zr sites. There were five paths for proton to migrate across the grain boundary with the
energy barriers in the range of 0.18 ~ 1.06 eV. However, the energy barriers for proton to arrive at
the grain boundary were higher than those that needed to migrate across it. Therefore, the overall
energy barrier for the easiest proton migration across the grain boundary was about 0.55 eV that
was well matched with the experimentally obtained one [2].
Reference
[1] A. Braun, et al., J. Appl. Electrochem., 39, 471 (2009).
[2] R. B. Cervera, et al., Solid State Ionics, 179, 236 (2008).
[3] B. Merinov, et al., J. Chem. Phys., 130, 194707 (2009).
- 21 -

O 21 (K)
On the path dependence of the open-cell voltage of a galvanic cell involving
a ternary or higher compound with multiple mobile ionic species under
multiple chemical potential gradients
Han-Ill Yoo a) and Manfred Martin b)
a) WCU Hybrid Materials Program,
Department of Materials Science and Engineering,
Seoul National University, Seoul 151-744, Korea
b) Institute of Physical Chemistry,
RWTH Aachen University, D-52056 Aachen, Germany
It is well known that the open-circuit
voltage (U) of a galvanic cell involving a
binary compound, or a higher compound
with a single kind of mobile ionic species,
is a state property under a gradient of
chemical potential of the mobile
component. It is not so transparent,
however, when involving a ternary or
higher compound with two or more kinds of
mobile ions under multitude chemical
potential gradients of those mobile
components. We clarify this issue with a
proton-oxide ion-hole mixed-conductor
oxide under chemical potential gradients of
both water and oxygen: U is path- and
history-dependent, and manifests itself
along the diffusion paths of the two mobile
components H and O under given boundary
conditions (see Fig. 1).
log( a H2 O )
- 22 -
-2
-3
-4
-5
-6
U II = 5.7 mV
IIa
electrode'
IIb
U(t���) = 11.1 mV
Ia
U I = 16.6 mV
electrode"
-3 -2 -1 0
log( a ) O2
Fig. 1. The open-cell voltage U of an electrochemical
cell, a � , a� SrCe Yb O a �� , a��
is not a
O2 H2O 0.95 0.05 3�� O2 H2O state property, but dependent on paths (I and II)
between the electrode ( ‘) and (“). At the steady state,
the path is chosen to be the diffusion path, leading to a
unique value U(t→∞).
Ib

Development of proton conducting SOFCs based on LaNbO4 electrolytes
– Status in Norway
Anna Magrasó 1 , Marie Laure. Fontaine 2 , Guttorm E. Syvertsen 3 , Yngve Larring 2 , Hilde L. Lein 3 ,
Tor Grande 3 , Reidar Haugsrud 1 and Truls Norby 1
1 Department of Chemistry, University of Oslo, FERMiO, Gaustadalleen 21, NO-0349 Oslo, Norway
2 SINTEF Materials and Chemistry, N-0314 Oslo, Norway
3 NTNU N-7491 Trondheim, Norway
O 22
High temperature Proton-Conducting Solid Oxide Fuel Cells (PC-SOFCs, Fig. 1) have potential
advantages compared to other fuel cell alternatives and are, as such, of interest to future green
energy technologies. Ideally, electrolytes for these types of cells should exhibit pure proton
conductivity as well as long-term stability in acidic atmospheres. Acceptor substituted LaNbO4
exhibit proton conductivity in wet atmospheres in the order of ~10 -3 S/cm, for 1% Ca-doped
LaNbO4. To reach acceptable performances in a PC-SOFC based on this material, the rather modest
conductivity requires an electrolyte thickness in the micron range. However, with a long-term
chemical stability and a proton transference number close to unity, LaNbO4 may still be interesting
for high temperature fuel cell applications - in contrast to the more investigated acceptor-doped
BaCeO3 that shows instability towards acidic atmospheres.
Development of a complete fuel cell system based on LaNbO4 has been underway, with
collaborative efforts between Norwegian partners: SINTEF, Norwegian University of Science and
Technology and the University of Oslo. This comprises identifying materials for the electrodes, the
interconnect and the sealing, optimization of the microstructures of all cell components,
development of shaping processes and, design of the fuel cell stack. We have addressed the crucial
technological issues of building and testing a PC-SOFC stack, as well as to reach a comprehensive
fundamental understanding of the processes involved - from fabrication and behavior of the
individual components to optimization of PC-SOFC fuel cell stacks.
Figure 1. Schematics of the PC-SOFC assembly.
The present contribution will review current developments of these systems generated within a
portfolio of several project financed through internal University funding and by the Research
Council of Norway. The support is gratefully acknowledged.
- 23 -

Charge Transfer Protonation of a Manganese-Doped Strontium Zirconate
Hiroshige Matsumoto, Takaaki Sakai, Yuya Kawasaki, Yasuhiko Sato and Tatsumi Ishihara
O 23
INAMORI Frontier Research Center, Kyushu University, 744 Motooka, Nishiku, Fukuoka 819-0395, JAPAN
Dept. Appl. Chemistry, Faculty of Engineering, Kyushu University, 744 Motooka, Nishiku, Fukuoka 819-0395, JAPAN
The proton conduction in acceptor-doped oxides is resulted from the hydration of the oxide ion
vacancies. The hydration takes place by the following two steps: (i) an ambient water molecule
sprits into two protons and one oxide ion on the surface of the oxide and (ii) the protons and oxide
ion diffuse into the bulk of the oxide in ambipolar manner [1]. Thus, the hydration needs enough
diffusivity of both protons and oxide ions as well as the negative free energy change of the
hydration reaction. The hydration will not occur if the oxide ion has poor diffusivity in the oxide,
and strontium zirconate will be the case [2].
We report in this paper that transition metal dopant, manganese in the present case, can be used
for protonation of an oxide which have poor oxygen diffusivity. We can assume manganese
introduced partially to the zirconium site of SrZrO3, i.e., SrZr0.9Mn0.1O3-δ for example, being
tetravalent after baked in air, corresponding to the value of δ to be zero. When the material is
exposed in reducing atmosphere, e.g. wet hydrogen at a high temperature, manganese thus
introduced will be reduced to the trivalent state. Due to the electrical neutrality, the reduction of the
manganese must be accompanied by either desorption of oxide ion (Eq. 1) or incorporation of
cationic species, i.e., proton (Eq. 2).
� �
��
1
2Mn Zr � OO
� 2Mn�Zr
�V
O � O2
(1)
2
�
�
�
2Mn H � 2O � 2Mn�
� 2OH
(2)
Zr � 2 O
Zr
O
In the latter case, reduction of the manganese results in the incorporation of protons into the oxide.
This will occur preferentially when the diffusivity of oxide ion is small. The protons thus
introduced are thermodynamically stable when the hydration reaction is spontaneous (ΔG

Electronic conduction of Sr-doped Ce-La monazite ceramics
Hannah L. Ray, Lutgard C. De Jonghe
Department of Materials Science and Engineering, University of California, Berkeley, Berkeley, CA 94720, USA
Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
Cerium orthophosphate and lanthanum orthophosphate are
isostructural, but the conduction properties of these two materials
are extremely different. When doped with aliovalent cations
such as Sr, both materials can incorporate and conduct protons
under wet, reducing conditions with conductivities of around 10 -4
S/cm at 600 C , with activation energies of about 1 eV (Figure
1). However, at high oxygen partial pressures, the total
conductivity of CePO4 increases by over an order of magnitude,
whereas that of LaPO4 decreases [1]. This increase in total
conductivity under oxidizing conditions may be due to a change
in the identity of the dominant charge carrier: since the cerium
cation can exist in either the 3+ or the 4+ valence state, the
cerium orthophosphate is thought to conduct electron holes under
oxidizing conditions.
The interaction between protons and electron holes in a mixed
protonic and electronic conductor is interesting because of the
exchange between protons and holes of the type
X
( SrH )
� X
�h�( Srh) �
�H,
where ( ) X
SrH � represents a
3�
3� 3
Ce Ce
Ce
strontium dopant on a cerium site with a charge-compensating
proton bonded nearby, and ( ) represents a strontium dopant
X
Srh
3
Ce �
Log (Conductivity) (S/cm
0
-1
-2
-3
-4
-5
-6
Conductivity of LaPO4 and CePO4
under oxidizing and reducing conditions
O 24
-7
0.9 1 1.1 1.2 1.3 1.4
1000/T (1/K)
2Sr CePO4, oxidizing
2Sr CePO4, reducing
2Sr LaPO4, oxidizing
2Sr LaPO4, reducing
Figure 1.
Compiled total conductivity
measurements of CePO4 and LaPO4 in
oxidizing and wet reducing conditions
from [1].
on a cerium site with a charge-compensating hole. This type of exchange could potentially release
protons from traps created by coulombic attraction to the dopant, and increase the mobility of
protons in a material. However, neither the defect chemistry for the incorporation of these electron
hole carriers, nor the mechanism by which these carriers move through the material, is well
understood.
Since the cerium and lanthanum orthophosphates are isostructural, an orthophosphate incorporating
both cations forms a solid solution. The change in conduction behavior on increasing the Ce
content of a 2% Sr-doped LaPO4 material can clarify the electronic conduction mechanism. One
possibility is a model whereby electron holes hop over a percolative network of cerium sites,
essentially creating itinerant cerium valance states. This mechanism would be disrupted if La 3+ ,
which cannot change valence, interrupted the cerium ion network. The total conductivity of a series
of La-Ce orthophosphate solid solutions is reported under both oxidizing and reducing conditions,
as well as on a step change in atmospheric conditions, and the applicability of a percolation model
is discussed.
1. N. Kitamura, K. Amezawa, Y. Tomii, T. Hanada, N. Yamamoto, T. Omata, and S. Otsuka-Yao-Matsuo, Journal of
the Electrochemical Society, 152 (4) A658-A663 (2005)
- 25 -

O 25 (K)
Interfacial Proton Dynamics in PEM: Theory and Molecular Modeling
A. Roudgar, S. Vartak, and M. Eikerling
Department of Chemistry, Simon Fraser University
8888 University Drive, Burnaby, BC, Canada
The presentation will focus on theoretical studies of proton transport mechanisms in polymer
electrolyte membranes (PEM) for polymer electrolyte fuel cells. The main class of protonconducting
PEM channel protons through random networks of water-filled nanopores. Hydrated
side chains of the ionomer form charged and flexible interfacial layers relative to which protons
move in nanopores; sulfonic acid head groups of the side chains release protons into water-filled
channels. We consider a dense 2D array of flexible protogenic surface groups (SG) as a model for
studying interfacial correlations and molecular mechanisms of proton mobility in polymeric
membranes at minimal hydration. Our quantum mechanical calculations have elucidated hitherto
unknown effects of molecular structure and packing density of SG on spontaneous ordering, acid
dissociation, water binding, flexibility of SG, and proton dynamics. Major discoveries include a
structural transition to a condensed state of the minimally hydrated array at a critical packing
density of SG (1 SG per 40 Å 2 ), which is accompanied by a hydrophilic-to-hydrophobic transition.
Furthermore, we have explored the mechanism of interfacial proton transport at the critical packing
density. Frequency spectra, calculated with Car-Parinello molecular dynamics, suggest that local
concerted tilting-rotation modes of SG trigger the lateral proton move. Adopting the metadynamics
method of Laio and Parrinello, i we explored an elementary proton move at high SG density and
minimal hydration. Concerted or consecutive sequences of elementary proton moves constitute an
ultra-efficient mechanism of interfacial proton transport. This can be demonstrated by using proton
transfer theory and a simple model of PEM with lamellar morphology. Results of calculations will
be discussed in view of the design of membranes that exhibit high proton conductivity at minimal
hydration.
1 B. Ensing et al., J. Phys. Chem. B 109 (2005) 6687; A. Laio et al., PNAS 99 (2002) 12562.
- 26 -

Proton Transport Mechanism and Pathways in Solid Acids from
Experiment and Theory
Boris Merinov
Materials and Process Simulation Center, California Institute of Technology, MC 139-74, Pasadena, California, USA
O 26
The future development of the fuel cell technology relies on production of proton-conducting
materials that will allow fuel cells operate at medium temperature. Such materials should be solid
electrolytes which show high protonic conductivity in the temperature range of ~150–400ºC. Solid
acids, alkali metal hydrogen sulfates, selenates, phosphates and arsenates, can be considered as
promising candidates [1, 2] since they exhibit superprotonic conductivity (>10-2 S/cm) in the
temperature range of ~150– 250ºC [3-5]. Their transport properties are due to the presence of
particularly mobile acid protons and specific structural characteristics that result in formation of a
dynamically disordered hydrogen bond network in the superprotonic phase. The proton diffusion in
solid acids is governed by the two-step Grotthuss-type mechanism involving a proton transfer along
inter-tetrahedral hydrogen bonds (intra-bond motion) and HAO4-group (A=S, Se, P, As)
reorientation [6] at which the existing hydrogen bond is broken and a new one is formed. Four main
processes occurring at different time scales can be distinguished in this mechanism:
1) thermal vibrations of the atoms involved in hydrogen bonding,
2) proton transfer from one potential minimum of the hydrogen bond to the other,
3) thermal librations of the HAO4 groups, and
4) reorientations of the HAO4 groups with breakage of existing hydrogen bonds and formation
of new ones.
Using quantum mechanical (QM) data on the potential energy surfaces, energetics of different
proton motions have been estimated and compared with experimental results obtained. Based on
this analysis, the proton transport mechanism in the superprotonic phase of solid acids is discussed
and detailed proton diffusion pathways are proposed. A concerted motion of the protons is a
characteristic feature of this mechanism.
References
[1] S.M. Haile, D.A. Boysen, C.R.I. Chisholm, R.B. Merle, Nature 410, 910 (2001).
[2] D.A. Boysen, T. Uda T, C.R.I. Chisholm, S.M. Haile, Science 303, 68 (2004).
[3] A.I. Baranov, L.A. Shuvalov, N.M. Schagina, JETP Letters 36, 459 (1982).
[4] A.I. Baranov, I.P. Makarova, L.A. Muradyan, A.V. Tregubchenko, L.A. Shuvalov, V.I. Simonov, Sov. Phys.
Crystallogr. 32, 400 (1987).
[5] A.I. Baranov, B.V. Merinov, A.V. Tregubchenko, V.P. Khiznichenko, L.A. Shuvalov, N.M. Schagina, Solid State
36, 279(1989).
[6] R. Blinc, J. Dolinsek, G. Lahajnar. 1. Zupancic, L.A. Shuvalov, A.I. Baranov. Phys. Status Solidi (b) 123, K83 (
1984).
- 27 -

Adsorption processes related to the surface properties of LaNbO4
K. Hadidi 1 , O.M. Løvvik 1 , T. Norby 2
1 Department of Physics, University of Oslo, P.O. Box 1048, Blindern, NO-0316 Oslo, Norway
2 Department of Chemistry and Centre for Materials Science and Nanotechnology, University of Oslo, P.O. Box 1126,
Blindern, NO-0318 Oslo, Norway
Acceptor-doped lanthanum ortho-niobate (LaNbO4)
based materials are high temperature proton conductors
[1] with a proton conductivity around ~0.001 S cm -1 .
These materials are attractive candidate as an electrolyte
in solid oxide fuel cells (SOFCs) and hydrogen sensors
due to their low interaction with water and carbon
dioxide which exist in the real conditions of operation.
As a proton conductor, the surface properties of
lanthanum niobate related to the adsorption processes are
of great interest.
In this study, density-functional band structure calculations
using the Vienna ab-initio simulation package (VASP) [2]
were utilized to investigate the surface properties of
lanthanum niobate in the monoclinic (low temperature)
phase [3]. From surface energy calculations comparing the
(101), (010), (100) and (001) terminations, the (010) surface
was found to be the most stable surface. The analogy
between the electronic structure of bulk and different
surfaces, presented that the electronic structure of surface is
influenced by the surface instability. Thus, the adsorption
energy calculations demonstrated that the most stable (010)
surface is repulsive towards hydrogen adsorption (Figure 1)
and
oxygen excess whereas these two processes are more
stable
at the (101) surface.
Adsorption energy (eV)
Adsorption energy (ev)
3.2
2.8
2.4
2
1.6
1.2
0.8
0.4
0
‐0.4
3.8
3.4
3
2.6
2.2
1.8
1.4
1
The most stable site
after relaxation.
(101) Surface
0 1 2 3
The most stable site
after relaxation.
[1] R. Haugsrud and T. Norby, Solid State Ionics 177 (2006), 1129.
[2] G. Kresse and J. Furthmüller, Physical Review B 54 (1996), 11169.
[3] L. Jian and C.M. Wayman, Journal of the American Ceramic Society 80 (1997), 803.
- 28 -
0.2 0.7 1.2 1.7 2.2 2.7
Height above surface (Å)
(010) Surface
O 27
O1Nb1
O4Nb1
O3‐top
O3O4
Nb1O3
O8La2
O4‐top
O1‐top
La1Nb1
O2‐top
Nb‐top
re‐O3top
La1‐Nb1‐
La2‐Nb4
Nb1‐O6
Nb1‐Nb2‐
La3
La‐top
O6‐top
La3‐O6
O7‐Nb1
O7‐Nb2
Nb‐top
re‐O6top
Fig. 1 The optimized adsorption energy for
hydrogen at the most stable site of the (101)
surface presents the stability of this surface
related to the hydrogen adsorption. The most
stable (010) surface is repulsive towards
hydrogen adsorption.

O 28 (K)
High temperature protonic conduction in rare earth phosphates and borates
K. Amezawa 1 , H. Takahashi 1 , A. Unemoto 2 , H. Kuwabara 3 , N. Kitamura 4 and T. Kawada 1
1 Grad. Sch. of Environmental Studies, Tohoku Univ., 6-6-01 Aramaki-Aoba, Aoba-ku, Sendai 980-8579, Japan
2 Insti. of Multidisciplinary Res. for Adv. Mat., Tohoku Univ., 2-2-1 Katahira, Aoba-ku, Sendai 980-8577, Japan/
3 Japan Fine Ceramics Center, 2-4-1 Mutsuno, Atsuta-ku, Nagoya 456-8587, Japan
4 Dep. of Pure and Appl. Chem., Faculty of Sci. and Tech., Tokyo Univ. of Sci., 2641 Yamazaki, Noda 278-8510, Japan
Rare earth phosphates such as orthophosphate LnPO4 and metaphosphate LnP3O9 are found
to exhibit protonic conduction at elevated temperatures [1, 2] and thus expected as an electrolyte of
fuel cells, hydrogen activity sensors, and hydrogen separation systems. Similar protonic conduction
has been also demonstrated in rare earth borates [3]. These oxoacid salts-based materials become
protonic conductors under moisturized atmospheres by doping lower valence (divalent) cations into
rare earth sites. High temperature protonic conductors (HTPCs) based on rare earth oxoacid salts, in
general, show relatively dominant protonic conduction and excellent chemical stability against acid
gases, although their conductivities are lower than those of proton-conducting perovskite-type
oxides. In this presentation, our recent researches on high temperature protonic conduction in rare
earth phosphates and borates are reviewed.
Mechanism of proton dissolution processes into the rare earth phosphates and borates has
been examined by means of spectroscopic measurements, e.g. MAS-NMR, FT-Raman, and FT-IR
spectroscopies in addition to conventional electrochemical measurements, e.g. measurements of
electrical conductivity and transport number [2]. Their defect structures were also investigated by
the first principle calculation [4]. Consequently, in the case of rare earth orthophosphates, it was
suggested that substitution of divalent cations for rare earth ions leads to the condensation of
phosphate ions, i.e. formation of P2O7 4- from two PO4 3- . Such condensation of phosphate ions is
regarded as formation of oxygen deficits like formation of oxygen vacancies in conventional
proton-conducting oxides. Protons are considered to be dissolved into phosphates forming hydrogen
phosphate ions through the equilibrium between the condensed phosphate ions and ambient water
vapor.
Electrical conduction in LaP3O9 glass was also investigated [5]. LaP3O9 glass had
considerably lower conductivity than LaP3O9 ceramics, and its charge carrier species were not
protons. However LaP3O9 glass became to exhibit relatively higher and protonic conductivity by
partial
crystallization of the glass. These results indicated that crystalline state is essentially needed
for
high temperature protonic conduction in phosphates.
References
1. T. Norby and N. Christiansen., Solid State Ionics, 77, 240 (1995) .
2. K. Amezawa, et al., Solid State Ionics, 145, 233 (2001); Electrochem. Solid-State Lett., 7, A511 (2004).
3. K. Amezawa, et al. Solid State Ionics, 175, 575 (2004); H. Takahashi, et al., Solid State Ionics, in press.
4. N. Kitamura, et al., 16th Int. Conf. on Solid State Ionics, P594 (2007).
5. K. Amezawa, J. Am. Ceram. Soc., 88, 321 (2005).
Acknowledgements: This work was supported by the Grant-in-Aid for Scientific Research from
the Ministry of Education, Culture, Sports, Science, and Technology (MEXT) of Japan.
- 29 -

Thermodynamics and proton conductivity trends in fluorite-pyrochlore
structures: A study on lanthanum cerate
O 29
Vasileios Besikiotis 1 , Tor S. Bjørheim 1 , Sandrine Ricote 2 , Christian Kjølseth 1 , Reidar Haugsrud 1
and Truls Norby 1
1 Department of Chemistry, University of Oslo, FERMiO, Gaustadallèen 21, NO-0349 Oslo, Norway
2 Fuel Cells and Solid State Chemistry Division, Risø National Laboratory, Technical University of Denmark, P.O. 49,
4000 Roskilde, Denmark
What appears to be mixed conducting Ca-doped La2Ce2O7 has been applied as component in
electrodes of proton ceramic fuel cells [1], and various ternary pyrochlore structured oxides with the
general formula Ln2B2O7 (Ln=La-Lu and B=Ce, Zr, Sn, Ti) are currently being investigated for
their proton conducting properties. We have studied the effect
of A and B-site substitution on the protonic conductivity in the
series La2-yCayCe2-xZrxO7 (y=0, 0.02, 0.1 and x=0, 0.5, 0.75).
DFT calculations have been performed to elucidate trends in
the hydration and mobility enthalpy of protons for the
abovementioned series Ln2B2O7.
AC conductivity of La2-yCayCe2-xZrxO7 (y=0, 0.02, 0.1 and
x=0, 0.5, 0.75) vs. T, pO2, and pH2O shows that the materials
are essentially ionic conductors in the whole temperature range
T

Synthesis of Highly Sr-doped Lanthanum Orthophosphate and
Polyphosphate in Phosphoric Acid Solutions
Naoyuki Hatada, Akiko Kuramitsu, Yoshitaro Nose, and Tetsuya Uda
Department of Materials Science and Engineering, Kyoto University,
Yoshida Honmachi, Sakyo-ku, Kyoto 606-8501, Japan
O 30
In recent years, lanthanum orthophosphate (LaPO4) and lanthanum polyphosphate (LaP3O9)
have received attention because of their potential application as solid electrolytes in fuel cells. They
exhibit relatively high proton conductivities when doped with alkaline earth metals, such as Sr [1].
For practical use, however, further enhancement of the conductivities is necessary. They are
expected to increase with increasing the Sr doping level. But the solubilities of Sr in the phosphates
have been reported to be comparatively low: approx. 2 mol% in LaPO4 [2]; below 5 mol% in
LaP3O9 [3].
To extend the solubility of Sr, we employed a low-temperature synthesis method: Synthesis
from phosphoric acid solutions. In our previous experiments, 13 mol% Sr-doped LaPO4 was
obtained. It was also found that the Sr doping level depended on synthesis conditions, with drastic
variation. Therefore, in this research, a systematic approach was taken to reveal the optimized
condition for obtaining highly Sr-doped lanthanum phosphates.
Lanthanum oxide, strontium carbonate, and phosphoric acid were mixed in a crucible and
held at 190 °C to obtain the initial solution. A typical molar composition of the initial solutions was
La+Sr : P = 1 : 15. Then the temperature and water vapor pressure were changed to precipitate
lanthanum phosphates. After held for a desired period, the precipitates were washed with hot water
and dried in air. Finally, the precipitates were analyzed by X-ray diffraction and ICP-AES. The
compositions of the solutions were also analyzed by ICP-AES.
Ratio of La precipitated as
lanthanum phosphates, namely,
precipitation ratio of La, was found to have
a significant influence on the Sr doping
level in the precipitates. As shown in Fig. 1,
the Sr doping level in LaPO4 increased with
decreasing the precipitation ratio of La.
Meanwhile, the effect of the precipitation
temperature on the Sr doping level was not
significant within the temperature range of
120 – 250 °C.
5
4 %
Initial Sr concentrations
in solutions
0
0 20 40 60 80 100
Precipitation ratio of La (mol%)
[1] T. Norby and N. Christiansen, Solid State Ionics 77 (1995) 240.
[2] K. Amezawa, Y. Tomii, and N. Yamamoto, Solid State Ionics 176 (2005) 143.
[3] K. Amezawa, Y. Uchimoto, and Y. Tomii, Solid State Ionics 177 (2006) 2407.
Sr/(La+Sr) in precipitates (mol%)
15
10
pH 2 O � 1 atm
8 %
Precipitation
temperature (°C)
Initial
Sr
concentration,
Sr
La+Sr
120 ��
250 ��
(mol%)
4 8
Fig. 1. Sr-doping level in LaPO4 precipitates as a function
of precipitation ratio of La.
- 31 -
��
��

O 31 (K)
Characterization of Structural Change in PLD-Fabricated SrZrO3 Thin Films
Noriko SATA 1 , Sho TAMURA 1 , Yuki NAGAO 1 ,
Hiroyuki KAGEYAMA 2 , Katsumi HANDA 3 , Katsuhiro NOMURA 2 ,
Fumitada IGUCHI 1 , Hiroo YUGAMI 1
1 Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan
2 AIST-Kansai, Midorigaoka 1-8-31, Ikeda, Osaka 563-8577, Japan
3 Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611‐0011, Japan
Alkaline earth zirconates based proton-conducting oxides, such as SrZrO3 and BaZrO3, are
promising because of their chemical and mechanical stability and very low electronic conduction
even at low PO 2. One can expect to reduce the resistance of these materials in thin films, however, it
is commonly reported that the conductivity decreases by one or two orders of magnitude and the
activation energy increases in SrZrO3 and BaZrO3 thin films. The origin of this degradation in
proton conductivity is not yet clearly explained.
We have been working on the pulsed laser deposition (PLD) process, which is widely used to
obtain epitaxial oxide thin films. Epitaxial growth is realized on an appropriate single crystalline
substrate at a sufficiently high temperature, so that rearrangement of the deposited atoms is
accelerated. It is found that in a suitable PLD condition, room temperature deposition on a single
crystal substrate can provide epitaxial thin films by post-annealing (LT-PLD). We have found that
the epitaxial thin films obtained by LT-PLD process have different structural and electrical
properties from those of bulk crystals and thin films fabricated by the conventional (hightemperature)
PLD process (HT-PLD). In-situ X-ray diffraction (XRD) measurements of the postannealing
process of SrZrO3(SZO) in the LT-PLD showed that the epitaxial crystallization starts at
560C, which is much lower than that of HT-PLD process. It is also found that 5-mol% Yttrium
doping reduces the crystallization temperature by 20 degree C, which might be due to crystalline
nucleation. Local environmental information in the thin films will be valuable to understand the
crystallization process in LT-PLD and the origin of the difference in electrical conduction. In
addition to the XRD analysis, X-ray absorption fine structure (XAFS) is performed to investigate
the structural difference in the SZO thin films. Fluorescence EXAFS spectra of the Sr and Zr Kedges
were obtained by a Lytle type ionization chamber at BL-9C, Photon Factory, KEK, Japan.
XANES spectra of the Sr K edge indicate that the configuration (CN, bond length) of the oxygen
atoms around Sr is different not only in as-deposited thin film but also in post-annealed SZO thin
films of LT-PLD process compared to the crystalline SZO fabricated by HT-PLD. EXAFS analysis
of those data has confirmed that the as-deposited SZO thin film has no long-range order, which is
correspondent to the results in TEM observation and XRD. Zr-O inter-atomic distances obtained by
the EXAFS analysis are not very different among all specimens. On the contrary, it is found that Sr-
O inter-atomic distances are different from each other. Though one can obtain precise lattice
parameters by XRD, the geometry of the oxygen atoms is not reflected very much. It is not easy to
discuss quantitatively about the structural change in the SZO thin films by the XAFS measurements,
however, the analysis has indicated a possible explanation of those data by the tilt angle change of
the ZrO6 octahedron in LT-PLD thin films on MgO substrates from the other crystalline SZO
specimens.
- 32 -

Water uptake and conduction property of
nano-grained yttria-doped zirconia
Yasuaki Akao a , Shogo Miyoshi a , Naoaki Kuwata b , Junichi Kawamura b ,
Yukiko Oyama a , Shu Yamaguchi a
a: Dep. of Materials Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-8656 Tokyo, JAPAN
b: IMRAM, Tohoku University, 2-1-1 Katahira, Aoba-ku, 980-8577 Sendai, JAPAN
O 32
One of the approaches to development of new ionic conductors would be making use of interfaces
such as grain boundary and surface. The transport properties along the interfaces come to appear as
macroscopic properties, when the materials are fabricated in a nano-grained structure. In our
previous study 1 , protonic conduction at low temperatures has been observed on nano-grained
(Zr,Y)O2 (YSZ) compacts, which have been fabricated via a combination of low-temperature
synthesis of nano-powder and room-temperature high-pressure (4GPa) compaction. Protonic
conduction in nano-YSZ has also been reported by Kim et al. 2 , while the specimens were prepared
by spark plasma sintering. While those observations indicate a good feasibility of developing a
new kind of nano-grained protonic conductors, of which the bulk properties involve negligible
proton solubility or conductivity, the detailed mechanism of such low temperature proton
conductivity has not been well understood. In the present study, considerations are made on
thermal stability of protonic species at and in the vicinity of interfaces in nano-grained YSZ, and
their roles in protonic conduction are discussed.
The microstructure observed with FE-SEM indicates the existence of nano-pores, which are
regarded to originate from condensation of adsorbed H2O molecules on the powder surface during
the room-temperature compaction. Such a microstructure may hold free H2O molecules in its
structure, as well as OH group terminating the surface and H2O molecules hydrogen-bonded to
them. 1H MAS-NMR measurements distinguish three kinds of proton in the materials. The
difference in thermal stability of those protonic species is observed with a thermal desorption
spectroscopy (TDS) and in-situ FT-IR analysis. One of the important observations is that the
species with the high thermal stability, which is regarded as OH group terminating the surface,
undergoes a H/D exchange even at low temperatures. The results of conductivity measurements
including the H/D isotope effect suggest that protonic conduction prevails over oxide ion
conduction bellow ca 873 K. The isotope effect remains prominent even at low temperatures down
to 60C, indicating that the dominant proton migration process is essentially based on the Grotthuss
mechanism. This conduction behavior is consistent with the observations with TDS and in-situ FT-
IR, i.e., significant mobility of protons dissociated from OH group, while the dissociation process
usually seems rather unfavorable at low temperatures. To understand the observed behavior, we
propose that the dissociation of protons from the surface-terminating OH groups is assisted by an
interaction with H2O molecules which adsorb on the OH groups with hydrogen bond.
1.
Y. Akao et al., The 14th International Conference on Solid State Protonic Conductors, (2008).
2.
S. Kim et al., Advanced Materials 20 (2008) 556.
- 33 -

Proton conductivity in acceptor doped LaVO4
Morten Huse, Tor S. Bjørheim, Reidar Haugsrud
Department of Chemistry, University of Oslo, FERMiO, Gaustadallèen 21, NO-0349 Oslo, Norway
O 33
State-of-the-art proton conductors comprise alkaline-earth based perovskites, e.g. BaCeO3, SrCeO3
and BaZrO3. These materials are reactive towards CO2 and other acidic species and/or exhibit high
grain boundary impedances [1, 2], and there is thus an interest in new stable proton conductors. In
this contribution we report on the electrical properties of LaVO4, a new proton conductor.
Electrical characterization of nominally undoped LaVO4, La0.99Ca0.01VO4 and La0.95Ca0.05VO4 was
performed in various partial pressures of oxygen, water vapor and hydrogen isotopes, from 300 to
1100 °C by impedance spectroscopy, AC conductivity measurements (10 kHz) and EMFmeasurements.
Relative permittivity was measured in a custom-made aluminium sample holder.
XRD, SEM and EDS were used for structural, micro structural and compositional analysis.
Generally, acceptor doped LaVO4 was a pure ionic conductor in oxidizing atmospheres in the entire
measured temperature range, dominated by proton conductivity at low temperatures (T

O 34 (I)
Quasielastic neutron scattering (QENS) applied to proton dynamics in
bulk and confinement – the case of phosphoric acid
B. Frick 1 , A. Thomas 2 , S. Lyonnard 3 , L.Vilciauskas 4 , K.D. Kreuer 4
1 Institut Laue-Langevin, F-38042 Grenoble, France; 2 MPI for Colloid Research, Golm, Germany, 3 CEA,
INAC/SPrAM/PCI, Grenoble,France; 4 MPI for Solid State Research, Stuttgart, Germany
Quasielastic neutron scattering (QENS) has been proven to be a powerful tool for studying the local
fast dynamics of materials with high proton conductivity [1, 2]. We review first more generally the
information content of QENS for proton dynamics in bulk and confinement and report on progress
in neutron scattering instrumentation.
In the following we will then discuss recent QENS data on bulk phosphoric acid (PA) and on
geometrically confined PA to get thereby a deeper insight into the proton conduction mechanisms
that are still not elucidated in detail, even though PA is today an important constituent of new
proton conducting membranes [3].
For anhydrous bulk phosphoric acid (PA), the ns- and ps- dynamics is investigated in the
temperature range from 2K to 430K (bulk PA : Tm ~ 315K). We interpret the data by fitting to
different models, e.g. jump diffusion models and by comparing to ab-initio MD-simulations carried
out by one of the authors [4, 5]. Proton conduction in PA is very sensitive towards perturbations,
but it is not clear to which extend these are a consequence of chemical interaction or of geometrical
confinement. For this purpose PA was also confined in nano-porous SiO2 matrices with cylindrical
pores of average diameters of 2.3 nm, 4.9 nm and 9.8 nm and by introducing inert and chemically
interacting molecules into the hydrogen bond network of PA. All samples were investigated on the
backscattering spectrometer IN16 with a sub-µeV energy resolution and also on the time-of-flight
instrument IN5 at 12Å and 5Å with a resolution of 20µeV and 80µeV, thus covering 4 orders of
magnitude in energy transfer from relaxations in the µeV range to vibrations in the several 10meV
energy range. We discuss the differences in the dynamics of confined and bulk PA as well as its
dependence
on pore size. The data evaluation under progress indicates an astonishingly weak
influence
of confinement in pores of 2-10 nm diameter on the dynamics of PA.
1. P. Perrin, Lyonnard and S.M. Volino, Journal of Physical Chemistry C 111, 3393-3404 (2007).
2. Th. Dippel, K. D. Kreuer, J. C. Lassègues, and D. Rodriguez, Solid State Ionics 61, 41–46 (1993).
3. K. D. Kreuer, S.J. Paddison, E. Spohr, M. Schuster, Chemical Reviews 104 (2004) 4637.
4. L. Vilciauskas, S. J. Paddison, and K.-D. Kreuer, J. Phys. Chem. A 113(32), 9193–9201 (2009).
5. L. Vilciauskas et al., work in progress
- 35 -

O 35 (I)
Ambient and high-pressure synchrotron x-ray diffraction studies of
heating-induced structural modifications in phosphate-based solid acids
Cristian E. Botez
Department of Physics, University of Texas at El Paso, 500 W. University Ave., El Paso, TX 79968, USA
We present results from
synchrotron x-ray powder
diffraction demonstrating that
heating CsH2PO4 (CDP) to about
260�C under a pressure of 1 GPa
leads to a polymorphic transition
from its room-tempearture
monoclinic (P21/m) phase to this
compound’s high-tempearture
cubic (Pm3m) modification, while
completely inhibiting CDP’s
dehydration [1]. As CDP becomes
superprotonic at 260�C upon
heating under the same pressure
[2], the above-mentioned finding
adds more unambiguous evidence
to confirm that CDP’s
superprotonic jump is triggered by
a heating induced polymorphic
transition, and not by chemical
modifications. RbH2PO4 (RDP) is
another phosphate-based solid acid
Intensity (arb. units)
80000
60000
40000
20000
0
RbH 2PO 4
T=150 o C
30 40 50
two theta (deg.)
Fig. 1 Rietveld fit (solid line) to x-ray diffraction data (circles), and
refined positions of the non-hydrogen atoms in the crystal structure of
intermediate-temperature RDP. The lower trace is the difference
between the observed and the calculated patterns and the vertical bars
are the Bragg reflection markers. Spacegroup is P 21/m and lattice
parameters are a=7.694Å, b=6.199Å, c=4.774Å and �=109.02 deg.
that exhibits a jump of its proton conductivity on heating [3], but, for RDP, much less is known (or
agreed upon) in terms of the structural changes underlying its superprotonic behavior. We discuss
our temperature-resolved experiments [4] aimed at uncovering the structural details of the transition
from room-temperature tetragonal (I-42d) RDP to an intermediate-tempearture (120�C-200�C)
monoclinic modification, including the determination of the crystal structure of the monoclinic
RDP polymorph, and its isomorphism with room-temperature CDP. We also present results from
high-pressure x-ray diffraction measurements that reveal the structural changes that accompany the
jump in the proton conductivity of RDP at 327°C under 1GPa of pressure. Finally, we report the
crystal structure of an intermediate-temperature (190�C-235�C) monoclinic KH2PO4 (KDP) phase,
and discuss this result in the context of the reported lack of superprotonic behavior of this solid
acid.
1. C. E. Botez, J. D. Hermosillo, J. Zhang, J. Qian, Y. Zhao, J Majzlan, R. R. Chianelli, and C. Pantea, J. Chem. Phys.
127, 194701(2007).
2. D.A. Boysen, S.M. Haile, H. Liu, and R.A. Secco, Chem. Mater. 15, 727(2003).
3. D.A. Boysen, S.M. Haile, H. Liu, and R.A. Secco, Chem. Mater. 16, 693(2004).
4. C. E. Botez, H. Martinez, R. J. Tackett, R. R. Chianelli, J. Zhang, and Y. Zhao, J. Phys: Condens. Matter 21,
325401(2009).
- 36 -

Proton dynamics of CsH2PO4 and related salts containing organic ions
Hideki Maekawa 1,2,3 , Ayumu Ishikawa and Akira Kudo
1 Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan
2 Center for Interdisciplinary Research, Tohoku University, Sendai 980-8578, Japan
3 CREST, Japan Science and Technology Corporation, Kawaguchi 332-0012, Japan
To illuminate ionic conduction behavior of super
protonic phase of CsH2PO4 (CDP), quasi-elastic
neutron scattering (QENS), pulse field gradient
nuclear magnetic resonance (PFG-NMR) and 1 H
NMR spin-lattice relaxation time (T1)
measurements were carried out. 1 Diffusion
coefficient of protons obtained from PFG-NMR
reproduced well the electrical conductivity by using
Nernst-Einstein equation. Comparison of PFG-
NMR and T1 provided a hopping distance of
protons as 2.7 Å, which agreed with the next nearest
proton sites in CDP. On the other hand, QENS data
was fitted well with a jump-diffusion model.
Comparison of the jump diffusion coefficient and
the correlation time obtained by QENS provided a
librational correlation time of protons in the order
of 10 -12 s. The present investigation suggests that
different techniques, QENS and NMR, can observe
O 36 (I)
Fig. 1 Comparison of the diffusion
coefficient of protons in CDP obtained
from various techniques. 1
protonic motions having different time constants including librational and translational motions
within the hydrogen bonding network of CDP.
On the other hand, a series of oxo-acidic salt composites containing organic cations has
been prepared and surveyed by protonic conductivity measurement, XRD, TG-DTA in order to
clarify their applicability for electrolytes at intermediate temperatures. All samples were
composed as AX (A:Cs, NH4, CH3NH3, (CH3)2NH2, (CH3)4N, (C2H5)4N X2: HSO4, H2PO4;
X:HSO4, H2PO4). Decrease in the crystallographic transition temperature of CsHSO4(CHS) and
CDP have been observed in several composites. Also, protonic conductivities increased by about
one order before the transition temperature. TG-DTA and powder XRD suggest some composites
have stoichiometric compounds.
1. A. Ishikawa, H. Maekawa, T. Yamamura, Y. Kawakita, K. Shibata, M. Kawai, Solid State Ionics, 179, 2345-2349
(2008)
- 37 -

Oxygen Reduction Kinetics at Pt | CsHSO4
by Conducting Atomic Force Microscopy
Mary W. Louie † , Adrian Hightower § , and Sossina M. Haile †‡
† Department of Chemical Engineering, ‡ Department of Materials Science, California Institute of Technology, 1200 E.
California Blvd., Pasadena, CA 91125, USA
§ Department of Engineering, Harvey Mudd College, Claremont, CA 91711
O 37
Oxygen reduction kinetics at the nanoscale Pt | CsHSO4 interface at ~150 ºC in humidified air were
characterized using conducting atomic force microscopy (AFM) combined with A.C. impedance
spectroscopy and cyclic voltammetry. Impedance measurements revealed that oxygen reduction at
Pt | CsHSO4 was comprised of two processes, one exponentially dependent and the other weakly
dependent on overpotential. Both processes displayed near-ideal capacitive behavior which
indicates a minimal distribution in their relaxation times. This ideal behavior is taken to be
representative of a nanoscale interface for which spatial averaging effects are minimal and,
moreover, enables the rigorous separation of multiple processes that could otherwise be convoluted
in measurements using macroscale electrode geometries. Measurements of the complete currentvoltage
characteristics of the Pt | CsHSO4 interface at various points across the electrolyte surface
reveal a variation of the oxygen reduction
kinetics with position. The overpotentialactivated
process was interpreted as a
charge transfer reaction, and within the
Butler-Volmer framework, analysis yielded
exchange coefficients (α) for charge
transfer ranging from 0.1 to 0.6 and
exchange currents (i0) spanning five orders
of magnitude. The observed countercorrelation
between i0 and α indicates that
the extent to which the activation barrier
decreases under bias (as indicated by the
value of α) depends on the initial magnitude
of that barrier under open circuit conditions
(as indicated by the value of i0).
Furthermore, the observation of such a
correlation across multiple independent sets
of data demonstrates the suitability of
conducting AFM for comprehensive studies
of electrochemical reactions at electrolytemetal-gas
boundaries.
-i 0 [A]
10 -13
10 -14
10 -15
10 -16
10 -17
10 -18
10 -19
10 -20
No. k [N m -1 Probe Nominal
_________________ ]
(1) 5
(2) 5
(3) 5
(4) 1.8
(5) 3.5
(6) 5
0.1 0.2 0.3 0.4 0.5 0.6
Figure 1. Exchange current for charge transfer plotted as a
function of exchange coefficient, showing a strong countercorrelation.
Parameters were extracted from a Tafel fit to the
current-voltage characteristics of Pt | CsHSO4 at ~150 °C in air.
- 38 -
�

Impact of cation nonstoichiometry on phase behavior, mictrostructure,
water incorporation and proton conductivities in yttrium-doped BaZrO3
Yoshihiro Yamazaki, Chih-Kai Yang, Raul Hernandez-Sanchez, and Sossina M. Haile
Materials Science, California Institute of Technology, 1200 E California Blvd., Pasadena, CA 91125, USA
Barium zirconate, specifically that doped with yttrium, is a
prominent proton conducting electrolyte because of its high
bulk proton conductivity, chemical stability, and mechanical
robustness. The material presents challenges, however,
because of difficulties in attaining reproducible proton
transport properties, and a wide scatter in bulk conductivity
has been reported in the literature (Figure 1). The question
addressed here is the origin of such scatter. In an earlier
work, it was proposed that barium loss during high
temperature sintering is responsible [1]. An alternative
explanation based on the separation of perovskite into
distinct phases has also been proposed [2]. Here, we report
the phase behavior, microstructure, water uptake, and proton
conductivities in 10 and 20 at% yttrium-doped barium
zirconates, in which cation nonstoichiometry (Ba deficiency,
x,
in Ba1-xZr0.9Y0.1O3-δ and Ba1-xZr0.8Y0.2O3-δ) is precisely
controlled
using chemical solution synthesis [3].
X-ray diffraction analysis of the Ba1-xZr0.8Y0.2O3-δ series
reveals the presence of a single perovskite phase up to x =
0.06, and the decrease in cell constant with increasing x
O 38
Fig. 1 Increasing Ba deficiency, x, in
Ba1-xZr0.8Y0.2O3-δ lowers bulk proton
conductivity. Data points indicate
current measurements and solid lines
without data points represent selected
literature results.
indicates that the barium deficiency is accommodated largely by partial incorporation of the yttrium
on the A-site. At greater barium deficiency, yttria-rich phases (Zr-doped Y2O3 and Y-doped ZrO2)
are observed in conjunction with essentially undoped barium zirconate. In combination with the
known binary phase behavior, these results enable construction of the ternary phase diagram BaO-
ZrO2-YO1.5. Proton conductivity is found to decrease monotonically with increasing barium
deficiency. In the single-phase region this attributed to the dopant partitioning, as evidenced by a
decrease in water uptake measured by thermogravimetry in both the Ba1-xZr0.9Y0.1O3-δ and
Ba1-xZr0.8Y0.2O3-δ series. The sharp decrease in conductivity upon traversing the two phase region
reflects the low H2O uptake in fully non-doped barium zirconate. Thus, precise control of the cation
stoichiometry indicates the requirements for obtaining reproducible bulk proton conductivity in
yttrium-doped barium zirconates, while revealing mechanisms by which Ba deficiency lowers the
bulk proton conductivity. The potential for utilizing anomalous X-ray scattering (AXS) to directly
determine the extent of dopant partitioning is discussed.
1. P. Babilo, T. Uda and S.M. Haile, Journal of Materials Research 22 (2007), 1322.
2. A.K. Azad, C. Savaniu, S.W. Tao, S. Duval, P. Holtappels, R.M. Ibberson and J.T.S. Irvine, Journal of Materials
Chemistry 18 (2008), 3414.
3.
Y. Yamazaki, R. Hernandez-Sanchez and S.M. Haile, Chemistry of Materials 21 (2009), 2755.
- 39 -

Cost-effective solid-state reactive sintering method for proton-conducting
ceramics
Jianhua Tong, Daniel Clark, Ryan O’Hayre
Metallurgical & Materials Engineering, Colorado School of Mines, 1500 Illinois Street, Golden, CO 80401, USA
O 39
High-performance proton-conducting yttrium-doped barium zirconates and cerates have been
successfully fabricated from inexpensive raw carbonate and oxide precursor powders using a
recently developed solid-state reactive sintering (SSRS) process. This SSRS process can be briefly
described as follows. With the addition of small amount (less than 2wt%) of a sintering additive to
raw material powders, high-quality phase-pure, dense perovskite ceramics can be produced in a
straightforward process involving a single ball-milling, dry pressing, and high-temperature sintering
procedure. Compared to conventional polymer sol-gel or conventional solid reaction methods, this
modified technique reduces materials costs by a factor of 10 and simplifies fabrication since the
processes of perovskite phase formation, pellet densification, and grain growth all occur in a single
sintering step, greatly decreasing fabrication time and cost. In addition, this technique greatly
enhances the ability to obtain high-quality, dense, large-grain sized ceramics, bringing the
commercialization of proton conducting ceramics closer to reality.
Exemplifying the capabilities of this approach, fully dense, large-grained (~5μm) pellets of
BaZr0.8Y0.2O3-δ (BZY20) have been produced at the remarkably low sintering temperature of
1350 o C. An excellent proton conductivity of 33mS/cm was achieved for 2wt% NiO modified
BZY20 pellets under room temperature water humidified UHP Ar atmosphere at 600 o C. Moreover,
the mechanisms of the formation, ceramic densification, and grain growth were fully explored
through a suite of comprehensive characterization. The second phase of BaY2NiO5 formed from
reaction of the sintering additive and raw materials during the SSRS process is believed to play a
critical role in the densification process. The SSRS technique has also been applied to NiO modified
BaCe0.8Y0.2O3-δ (BCY20), where again BaY2NiO5 second-phase formation was identified and
implicated in the perovskite phase conversion and densification process. In the BCY20 system, the
second-phase BaY2NiO5 was found to preferentially locate in grain boundary regions and nanosized
nickel metal particles were also found to enrich in the grain boundary region after reduction of the
ceramic in H2, leading to a significant commensurate increase in conductivity. The proton
conductivity for a BCY20 pellet modified with 1wt% NiO was determined to be 2.7mmS/cm at
500 o C under room temperature water humidified UHP Ar atmosphere, which was 7 times higher
than the proton conductivity for a control sample obtained from high-quality polymeric sol-gel
powder under identical conditions.
- 40 -

Solid State NMR studies of doped BaSnO3 and BaZrO3 protonic
conductors: Defect trapping and ionic mobility
Lucienne Buannic, 1 Frédéric Blanc, 1 Clare P. Grey 1,2
1 Department of Chemistry, State University of New York, Stony Brook, NY 11794-3400, USA
2 Department of Chemistry, University of Cambridge, Cambridge, UK
One of the key problems that prevent the extensive use
of Solid Oxide Fuel Cells (SOFC) is the high operating
temperatures - 800 to 1000 °C - required to activate the
anionic conduction through the solid electrolyte. New
materials presenting good protonic conductivities could
replace the current electrolytes and lower the operating
temperature from 400 to 200 °C. These protonic
conductors usually adopt a perovskite structure ABO3
where doping of the B 4+ cation by a lower valence
cation like Y 3+ or Sc 3+ creates oxygen vacancies in the
structure. Hydration of these materials occurs through
the reaction of a molecule of water and an oxygen
vacancy in order to form hydroxyl groups. These
protonic defects are responsible for the protonic
conductivity in these perovskites. The cation ordering
following substitution on the B site can account for the
vacancy trapping in the dry material which will in turn
influence the hydration property of the material.
In order to understand the protonic conductivity
exhibited by these materials, the first step is to explain
cation ordering and vacancy trapping in the dry
structure while the second stage includes looking at the
protonic defects and their location in the hydrated
materials. We examined a series of BaZr1-xYxO3-δ and
BaSn1-xYxO3-δ (0.10 ≤ x ≤ 0.50), and BaZr1-xScxO3-δ
(0.05 ≤ x ≤ 0.30) by solid-state NMR, an excellent tool
to observe the different local environments. Study of the
dry structures by 17 O, 91 Zr, 119 Sn, 45 Sc and 89 Y showed a
random distribution of the substituting cations in BaZr1xScxO3-δ
and BaZr1-xYxO3-δ but a clear ordering in
BaSn1-xYxO3-δ. In addition, preliminary results allowed
us to identify some of the protonic conduction pathways
in hydrated BaZr1-xScxO3-δ by 1 H NMR.
O 40
Fig. 1: Variable Temperature 1 H MAS NMR Hahn echo spectra of BaZr1-xScxO3-x/2(OH)y. (a) x = 0.05, y = 0.01;
(b) x = 0.15, y = 0.10; (c) x = 0.30, y = 0.20. Top: spectra obtained at 300 K., bottom: spectra obtained at 110 K.
- 41 -

The thermodynamics and kinetics of the dehydration of CsH2PO4 studied
in the presence of SiO2
Ayako Ikeda and Sossina M. Haile
Materials Science, California Institute of Technology, 1200 E California Blvd., Pasadena, CA 91125, USA
The thermodynamics and kinetics of dehydration and hydration
of CsH2PO4 are investigated by thermogravimetric, differential
scanning calorimetry and X-ray diffraction analysis in the
temperature range 200 ~ 400 ºC and water partial pressure range
0.06 ~ 0.89 atm. Addition of SiO2 powder to CsH2PO4 prevents
coarsening of the solid acid during heat treatment (upper figure)
and accelerates the dehydration and hydration reactions. Despite
the morphological impact, no chemical reaction is observed
between CsH2PO4 and SiO2. Accordingly, use of SiO2 permits
access to thermodynamic behavior on moderate timescales.
The
pH
2O
–T phase diagram determined from this work (lower
figure) confirms the occurrence of a partially dehydrated liquid,
CsH2-2xPO4-x(l), under high-temperature, high-humidity
conditions, in addition to CsH2PO4(s) and CsPO3(s). The phase
boundaries are each determined with good accuracy as a result
of the elimination of kinetic effects. The triple point connecting
the three phases is located at p = 0.35 ± 0.2 atm and T = 267.5
H 2O
± 1.0 °C. The thermodynamic stability of CsH2PO4 and
CsH2-2xPO4-x(l), the latter of which exists over the composition
range x = 0.38 ~ 0.48, were ascertained from hydration studies
carried out under the appropriate temperature and water partial
pressure conditions. The effect of grain size, water partial
pressure and temperature on the kinetics of hydration from
CsPO3 to CsH2PO4 are reported.
O 41
Figure 1. (upper) Morphology of
post-dehydration sample of SiO2 and
(formerly) CsH2PO4; (lower) p – H 2O
T phase diagram representing the
dehydration behavior of CsH2PO4,
compared to earlier literature studies.
1. Y. Taninouchi, T. Uda, Y. Awakura, A. Ikeda, and S. M. Haile, Journal of Materials Chemistry 17 (2007), 3182
2. Y. Taninouchi, T. Uda, and Y. Awakura, Solid State Ionics 178 (2008), 1648.
3. Y. Taninouchi, T. Uda, and Y. Awakura, Journal of The Electrochemical Society 156 (2009), B572
- 42 -

Enhancement of proton conductivity
in highly oriented poly(aspartic acid) thin film
Yuki Nagao, *,† Jun Matsui, ‡ Takashi Abe, §
Hitoshi Yamamoto, || Tokuji Miyashita, ‡ Noriko Sata, † Hiroo Yugami †
† Department of Mechanical Systems and Design, Graduate School of Engineering, Tohoku University, Sendai 980-
8579, Japan, ‡ Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, Sendai
980-8577, Japan, § Department of Mechanical and Production Engineering, Faculty of Engineering, Niigata
University, Niigata 950-2181, Japan, || Department of Macromolecular Science, Graduate School of Science, Osaka
University, 1-1 Yamadaoka Suita, Osaka 565-0871, Japan
The design of highly proton-conductive solid electrolytes is
essential to many applications in the field of solid-state ionics. One
fundamental approach to creating highly proton-conductive material
is chemical modification. Usually, sulfonic acid groups are used as a
proton conductive group because of their excellent proton
conductivity. However, the high acidity of sulfonic groups restricts
the polymer backbone to fluoro or aromatic groups, which result in a
high cost for production. So a new method to produce highly protonconductive
material has been desired since a long time. Ionic
conductivity enhancement in 2D systems has been recognized for
more than 20 years. Recently, we have been reported a several
enhancement phenomena of the proton conductivity in thin
films.[1,2] An application of this phenomenon may show promise of
a new method to produce highly proton-conductive material. In this
study, we investigated the proton transport properties of a partially
protonated poly(aspartic acid)/sodium polyaspartate (P-Asp) thin
Log (� / S cm -1)
-1
-2
-3
-4
-5
-6
60-nm-thick film
Pelletized P-Asp
P 01
-7
298 K
-8
40 50 60 70
RH / %
Fig. 1 The difference of the
proton conductivities of the
pelletized P-Asp and 60-nmthick
film on MgO(100)
substrate at each relative
humidity.
film prepared by spin coating. We also report that the orientation of the amide groups, which act as
a proton conducting channel, induced the enhancement effect.
The difference of the proton conductivities of the pelletized P-Asp and 60-nm-thick film on
MgO(100) substrate at each relative humidity (RH) was shown in Fig. 1. The proton conductivity of
60-nm-thick thin film exhibits 3.4 × 10 -3 at 298 K and 70 % RH. This conductivity is relatively high
for a proton conductor in which the protons of carboxylic acid groups serve as proton sources. The
proton conductivity of 60-nm-thick film is ~10 times higher than that of the pelletized sample at the
same temperature and RH. An enhancement phenomenon of the proton conductivity was also
observed when the 60-nm-thick thin film was prepared on amorphous SiO2 substrate.[2] The
activation energy for proton conduction of 60-nm-thick film is 0.53 eV, which becomes 0.12 eV
smaller than that of the pelletized P-Asp. [2]
The origin for this enhancement of the proton conductivity by the thin film was not due to the
difference in adsorbed water amount in this case, which was determined by quartz crystal
microbalance (QCM) method. Incident-angle dependence of polarized IR absorption spectra was
measured to evaluate the orientation of molecular chains in the 60-nm-thick film of P-Asp on a
MgO substrate. The result suggests that the C=O bonds of the amide groups are oriented mostly
perpendicular to substrate surface in the 60-nm-thick film.
1. Y. Nagao, N. Naito, F. Iguchi, N. Sata and H. Yugami, Solid State Ionics 180 (2009), 589.
2. Y. Nagao, F. Iguchi, N. Sata and H. Yugami, Solid State Ionics 181 (2010), 206.
‐ 43 ‐

P 02
Crystallinity and morphology of PVDF-HFP-based proton-exchange
membranes embedding polytyrenesulfonic acid-grafted silica particles
M. Maréchal, 1,4*
F. Niepceron 2,3
, J. Bigarré 2
, H. Mendil-Jakani 1 , G. Gebel 1
1) Commissariat à l’Energie Atomique, Matter Science Department, Grenoble, France
2) Commissariat à l’Energie Atomique, Department of Materials, Le Ripault, Monts, France
3) Laboratoire des Matériaux Macromoléculaires, INSA Lyon, Villeurbanne, France
4) Laboratoire d’Electrochimie et de Physicochimie des Matériaux et Interfaces, Grenoble, France
Novel proton-exchange membrane (PEM) materials based on a hybrid organic-inorganic
formulation have been investigated [1]. The water retention properties around 100°C is one of their
advantages. In the present contribution, we intend to report on the incorporation of original acidfunctionalized
inorganic nanoparticles, polystyrenesulfonic acid-grafted silica particles [1, 2], in an
inert PVDF-HFP matrix. The proton conductive characteristics relied exclusively on the particle
phase gives promising results. Membranes with different amounts of particles have been prepared
by
evaporation and recasting techniques. These membranes were characterised and their
morphologies
have been investigated.
Intensité / u.a.
1000
100
10
1
0.1
0.01 0.1 1
q / A -1
Figure: A log-log representation of a X-ray scattering curve from a membrane with a 50 wt.%
loading
Finally, the performance of membrane-electrode assemblies (MEAs), using selected hybrid
membranes, was evaluated by single cell fuel cell tests. Remarkably, such hybrid membrane systems
exhibited up to 1.2 W/cm 2
, at 80 °C using non-hydrated gas feeds.
[1] F. Niepceron, B.Lafitte, H. Galiano, J. Bigarré, E. Nicol, J-F Tassin, J. Membr. Sci. 338 (2009) 100.
[2] X. Chen, D. P. Randall, C. Perruchot, J. F. Watts, T. E. Patten, T. V. Werne, S. P. Armes, J. Colloid Interface Sci.
257 (2003) 56.
‐ 44 ‐

Proton mobility in tetragonal and monoclinic LaNbO4
through a second-order phase transition
Kazuaki Toyoura*, Harald Fjeld, Reidar Haugsrud, and Truls Norby
Department of Chemistry, University of Oslo, FERMiO, Gaustadalléen 21, NO-0349 Oslo, Norway
LaNbO4 is an electrolyte candidate for proton conducting
fuel cells. It exists as two polymorphs, the high
temperature tetragonal (t-LaNbO4) and the low temperature
monoclinic (m-LaNbO4) where the transition between the
two is a second-order displacive phase transition. The
crystal structure of m-LaNbO4 changes gradually as a
function of temperature. In this work, the relation between
the structural change and the migration enthalpy of protons
has been investigated by means of first principles
calculations and conductivity measurements.
Protons generally reside around oxide ions in oxides, to
form O-H bonding (~ 1 Å). Therefore, proton migration in
oxides can be considered as a sequence of proton jumps
from one oxide ion to another. Our theoretical study
clarified that protons migrate in similar paths for t- and m-
LaNbO4. Figure 1 shows the trajectory of the ratedetermining
proton jump in the tetragonal phase. In the
first four (0–3) and the last four (5–8) positions, the
distance between the migrating proton and the first nearest
neighbor oxide ion is kept constant, ~ 1 Å. In position 4, in
contrast, the migrating proton resides not around an oxide
ion, but between two oxide ions. This kind of migration,
i.e. rotation and hopping, has been reported in other proton
conducting oxides, such as BaCeO3 and BaZrO3. The
potential barriers are 0.41 eV (39 kJ/mol) in t-LaNbO4 and
0.62 eV (60 kJ/mol) in m-LaNbO4, respectively.
Figure 2 shows the bulk conductivity of Sr-doped LaNbO4
as a function of inverse temperature. The migration
enthalpy of protons is 35 kJ/mol in the tetragonal phase,
which is in good agreement with the computational value,
39 kJ/mol. In the monoclinic region, the experimental
conductivity is gradually approaching the theoretical line
corresponding to the monoclinic phase at 0 K. This is
reasonable because of the displacive phase transition. The
migration enthalpy increases gradually with decreasing
temperature,
from 35 to 57 kJ/mol in the range of 520-205
° C.
* (Current affiliation) Department of Materials Science and Engineering,
Kyoto University, Yoshida, Sakyo, Kyoto 606-8501, Japan
‐ 45 ‐
O
O
O
O
Nb
O
O
7 8
6
5
0
1 2
4
3
Nb
O
O
Fig. 1. The rate-determining path
of proton migration in t-LaNbO4.
Fig. 2. The bulk conductivity of
Sr-doped LaNbO4.
P 03

NMR measurements on proton mobility in nano-crystalline YSZ
Judith Hinterberg a , Alina Adams b , Bernhard Blümich b , Martin Wilkening c , Paul Heitjans c ,
Sangtae Kim d , Zuhair A. Munir d , Roger A. De Souza a , Manfred Martin a
a Institute of Physical Chemistry, RWTH Aachen University (Germany)
b Institute of Macromolecular Chemistry, RWTH Aachen University (Germany)
c Institute of Physical Chemistry and Electrochemistry, Leibniz University of Hannover (Germany)
d Department of Chemical Engineering and Materials Science, University of California (USA)
Nano-crystalline cubic 9.5 mol% YSZ shows proton conductivity at room temperature [1,2]. In this
work we report preliminary Nuclear Magnetic Resonance (NMR) results on water saturated, dense,
nanostructured YSZ samples. Static NMR as well as magic angle spinning NMR spectra show two
distinct signals. Their temperature dependent behaviour and their linewidths suggest that one can be
attributed to (free) water adsorbed on the surface of the sample and the other one to mobile protons
within the sample. This interpretation is supported by comparison with measurements on a single
crystalline sample. Motional narrowing is observed for the signal originating from protons inside the
sample. The analysis of temperature and field dependent T1 relaxation measurements points towards
diffusion
in a confined geometry. This supports our previous experimental results which indicated
conduction
of protons along the grain boundaries [3].
1. S.Kim, U. Anselmi-Tamburini, H. Jung Park, M. Martin, Z.A. Munir, Adv.Mat. 20, 556-559 (2008)
2. H.J. Avila-Paredes, J. Zhao, S. Wang, M. Pietrowski, R.A. De Souza, A. Reinholdt, Z.A.Munir, M. Martin, S. Kim,
J. Mater. Chem. 20, 990-994 (2010)
3. S. Kim, H.J. Avila-Paredes, S. Wang, C-T. Chen, R.A. De Souza, M. Martin, Z.A. Munir, PCCP 11, 3035-3038
(2009)
‐ 46 ‐
P 04

P 05
Determination of the amount of proton in proton conducting alumina by DC
polarization method
Yuji Okuyama 1 , Noriaki Kurita 2 , Daisuke Sato 2 , Hisashi Douhara 2 and Norihiko Fukatsu 2
1 Intellectual property Division, Industry-Academia- Government Collaboration Center,
Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
2 Department of Materials Science and Engineering, Graduate School of Engineering, Omohi College,
Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
Acceptor doped α-alumina exhibits protonic conduction at high temperature. Although the conductivity of
alumina is lower than that of the other proton conducting oxide, the transport number of proton is maintained
higher even at elevated temperature (1073-1673 K). Therefore, this material can be used favorably as the
electrolyte of the galvanic-cell type hydrogen sensor for metal melting processes.
The chemical potential profile in ionic conductor under polarized state is determined by the continuity of ionic
and electronic currents. Internal chemical potential distribution is established uniquely when the chemical
potentials at both electrodes and the applied voltage are given. In this study, the maximum solubility of the
dissolved hydrogen C was determined for commercial polycrystalline alumina at temperature range of 1273-
� �i
H
1573 K by measuring the amount of the desorbed hydrogen when the potential profile of hydrogen in alumina was
changed by changing the applied voltage. The amount of desorbed hydrogen was measured by a hydrogen pump
reported elsewhere [1].
The equilibrium reaction for hydrogen dissolution is represented as follow,
� �
1/2H 2 � h � Hi
(1)
For alumina equilibrated with H2O-H2 atmosphere, the relative charge of acceptor dopant, M� is almost perfectly
�1 � �1/2
compensated with proton, therefore, the concentration of positive hole is given as K C � p . Applying to the
Al
H H
i 2
calculation method by Coudhury and Patterson[2], the distribution of hydrogen potential can be represented as
follow,
�1/
2
�1/
2
x � r � p � � � �
H x�
x / A r p x�L
/ A
� �
2 ( )
H
� �
2 ( )
ln ln
�
(2)
� �1/
2 � � �1/
2
L
�
� r � pH
( x�0)
/ A � � r � pH
( x�0)
/ A
2
2 �
where, r is the ratio of the current of positive hole to that of proton. A can be estimated from the mobility of proton
and positive hole and the equilibrium constant, K, of the reaction represented by Eq. (1).
1 �1
A � m m K
(3)
�
� �
h Hi
The parameter r may be estimated from the applied voltage by using the following relation.
1/
2
RT � p
�
H x�
L � A/
r
� � � 2 ( )
E
�
apply ln (4)
F � 1/
2 �
� pH
( x�
0)
� A/
r
2 �
The value, A, was determined by the emf measurement.
The increment of the concentration of positive hole upon changing the polarization voltage can then be
calculated based on the change of the chemical potential profile of hydrogen, and which must be equal to the small
amount of desorbed hydrogen, �n
� , therefore,
Hi ( E1
�E
2 )
L
L
�1
�
�1
/ 2
�1
/ 2
�n � � K C �S
( ( pH
( ) ( x)
) dx ( pH
( ) ( x)
) dx)
Hi ( E1�E2
)
Hi
�0
2 E �
2 �0
2 E
(5)
1
where S and L are the sectional area and the thickness of the sample, respectively. According to Eq.(5), the
0
concentration of proton, C , was determined employing the equilibrium constant reported in previous study[3].
The value mol cm -3 �7
2. 0 �1.
6�10
was obtained.
H i �
[1]N.Kurita, K.Otsuka, N.Fukatsu and T. Ohashi, Solid State Ionics, 79(1995) 358-365.
[2]N. S. Coudhury and J. W. Patterson, J. Electrochem. Soc.(1970) 1384.
[3]Y. Okuyama et al. Solid State Ionics 180 (2009)175-182.
‐ 47 ‐

1
Dynamic absorption behavior of hydrogen within perfluorosulfonic acid
polymer electrolyte membranes during exposure to water vapor
Bun Tsuchiya 1
, Shinji Nagata 2 , Kesami Saito 2 , Tatsuo Shikama 2
Department of General Education, Faculty of
Science and Technology, Meijo University, 1-501, Shiogamaguchi,
Tempaku-ku, Nagoya 468-8502, Japan
stitute for Materials Research, Tohoku University, 2-1-1, Katahira, Aoba-ku, Sendai 980-8577, Japan
2 In
r of hydrogen
He 2+ Perfluorosulfonic acid (PFSA) polymer electrolyte membranes (PEMs) have potential for use as
hydrogen separators from water (H2O) for hydrogen gas production systems because of having
extremely high protonic proton conductivity on the condition of operating temperature around 373
K and high humidity. The property of water absorption into the polymer electrolyte membranes is
one of the most significant parameters for the development of the hydrogen gas production systems
and greatly contributes to increments of the protonic conductivity and re-combination rate for
hydrogen molecule formation. Therefore, it is essential to understand dynamic behavio
absorbed within the polymer electrolyte membranes during exposure to water vapor.
The PFSA membranes used in the present study were Aciplex-SF-1004® which were ones of
typical proton conducting polymers, fabricated by Asahi Kasei Corporation. The Pt electrodes with
a 0.1 �m thick were deposited on both sides of the PFSA membranes using an electron-beam
sputtering device. The protonic conduction, water absorption characteristics and hydrogen behavior
at the bulk, radical defects, and interface between the membranes and Pt electrode in the membranes,
exposed immediately at several temperatures of 293-393 K from vacuum to air with a relative
humidity of approximately 50 %, were investigated in-situ by direct current (DC) resistance and
alternative current (AC) impedance measurements. In addition, the concentration of hydrogen (H)
retained near the surface (about 400 nm in depth) of the membranes were measured using an elastic
recoil detection (ERD) technique with 2.8 MeV ion probe beams after isochronal annealing for
10 min and exposure to water vapor at 293 K.
The proton conductivities of the water vapor-induced PFSA membranes at 293 K gradually
increased with increasing the air exposure time, and became approximately four orders of
magnitude higher when reached up to saturation at approximately 400 min. The hydrogen content in
the near-surface region of the membranes at the exposure time of 60 min was also observed to
increase to approximately five times that of the initial polymer by means of the ERD technique. In
particular, the presence of some intrinsic defects such as peroxy free radicals and fluorocarbon
radicals
which have been produced in the membranes significantly play an important role for the
increase
of the proton conductivity, and can allow hydrogen to be dissociated
from water, and to
migrate
more smoothly at the interface between the membranes and electrode.
‐ 48 ‐
P 06

P 07
Preparation of Multilayered Thin Film Fuel Cell Using Titanium Oxide as
Anodic Catalyst via Layer-by-Layer Assembly
Hisatoshi Sakamoto 1 , Yusuke Daiko 2 , Hiroyuki Muto 1,3 ,
Mototsugu Sakai 3 , and Atsunori Matsuda 1,3
(1) Department of Environmental and Life Sciences, Toyohashi University of Technology,
Hibarigaoka, Tempaku, Toyohashi, Aichi 441-8580, JAPAN
(2) Department of Materials Science and Chemistry, University of Hyogo,
Shosha, Himeji, Hyogo 670-2101, JAPAN
(3) Department of Electrical and Electronic Information Engineering, Toyohashi University of Technology,
Hibarigaoka, Tempaku, Toyohashi, Aichi 441-8580, JAPAN
Direct methanol fuel cells (DMFCs) have attractive potentials of power source for portable
devices such as cell-phones and laptop computers. However, the poisoning of catalysts by carbon
monoxide and the fuel cross-over are serious problems for the fuel cell property of DMFCs. The Pt-
Ru-supported carbon (C/Pt-Ru) is generally used to anodic catalyst. On the other hand, the
photocatalysts such as anatase titanium oxide (TiO2) and/or noble metal-doped TiO2 were applied to
methanol oxidation and water-splitting for the production of hydrogen gas (H2) [1]. In addition, the
TiO2 photocatalyst was employed in an anodic catalyst with Pt-Ru catalyst to promote the methanol
oxidation by UV excitation [2]. Layer-by-layer (LbL) assembly is a convenient technique to form
the polymeric film with a thickness of nano-meter order, and that is useful to deposit nano-particles.
In this study, membrane-electrode assembly (MEA) using the TiO2 nano-particles as a catalyst was
prepared on porous glass substrates by LbL method.
The illustration of multilayered thin film fuel cell was shown in Fig.1. First, the gold collecting
electrode was sputtered on porous glass substrate, and then anatase TiO2 nano-particles (P-25) were
deposited by the intermediary of primer layer. Continuously, a multilayerd polyelectrolyte film
consisting of anionic poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) and cationic
poly(allylamine hydrochloride) (PAH) was also deposited on the TiO2 layer. A cathodic catalyst of
Pt nano-particles was prepared by photoreduction of hexachloroplatinic acid (H2PtCl6), and then
deposited on the multilayered electrolyte by using the PDDA as a binder. Finally, an electron
conductive polymer of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) was
spin-coated as a cathodic collecting electrode. A
CH3OH aqueous solution was supplied through the
O2 (air) UV light
porous glass substrate, and UV light was irradiated
from the cathodic side to excite the layered TiO2.
Total thickness of MEA was about 650 nm. UV
light at 365 nm of center wavelength was passed
though about 70 % until the TiO2 layer. Electrical
generation was confirmed and fuel cell performance
was enhanced in proportion to the CH3OH
concentration and the irradiation intensity of UV light.
[1] G. Wu et al., Int. J. Hydrogen Energy, 33, (2008) 1243.
[2] K. Drew et al., J. Phys. Chem. B, 109, (2005) 11851.
‐ 49 ‐
Electrode
Cathodic catalyst ; Pt
Multilayered electrolyte
Anodic catalyst ; TiO2 Electrode
Porous glass
Fuel ( CH3OH aq. )
Fig. 1. Diagrammatic illustration of multilayered
thin film fuel cell using the anatase TiO2
nanoparticles as a anodic catalyst.

Hydration kinetics of proton-conducting zirconates upon a change of
temperature in wet atmosphere
Jung In Yeon and Han-Ill Yoo
WCU Hybrid Materials Program,
Department of Materials Science and Engineering
Seoul National University, Seoul 151-744, Korea
It is reported [Kudo et al., Solid State Ionics 179 (2008) 851] that when the temperature of proton
conducting SrZr0.9Y0.1O3-δ is lowered from 700 o C to 600 o C in a wet atmosphere, its electrical
conductivity first decreases with decreasing temperature, followed by “extremely” slow,
monotonic increase to a saturated value. This square-root (√ )-shaped variation with time has been
interpreted as being due to the decrease of mobility of protons with decreasing temperature,
followed by “extremely” slow, single-fold chemical diffusion of H2O. We will demonstrate that it
is not the case: the hydration proceeds by decoupled twofold chemical diffusion of H and O, but
the effect of faster H-diffusion on the conductivity may be overridden by the effect of mobility
change when temperature change is slower. Otherwise, the twofold relaxation would manifest
itself. The twofold isothermal and isoactivity hydration/dehydration relaxations are quantitatively
analyzed to evaluate the two chemical diffusivities for the system of BaZr0.8Y0.2O3-δ in the range
of water activity -4.0≤ log(PH 2O/atm) ≤-2.3 at 700 o C and = -0.67, and in the range of temperature
of 600 o C to 800 o C in the 0 o C-water-saturated air atmosphere.
‐ 50 ‐
P 08

“In-situ” high temperature neutron diffraction study of lanthanum
tungstate: a proton conductor with a fluorite-type structure
Anna Magrasó 1 , Istaq Ahmed 2 , Reidar Haugsrud 1
1 Dept. Chemistry, University of Oslo, SMN/FERMiO, Gaustadalleen 21, NO-0349 Oslo, Norway
2 Dept. Chemical and Biological Engineering, Chalmers University of Technology, SE-412 96, Göteborg, Sweden
Lanthanum tungstate, “La6WO12”, has been reported to
exhibit appreciable proton conductivity at intermediate
temperatures and mixed ionic-electronic conductivities at
higher temperatures [1]. The material cannot be made phasepure
with a nominal atomic ratio between La and W equal to 6,
but a solid-solution of single-phase compositions with La/W
ratios between 5.3 and 5.7 has been reported [2]. The lanthanum
tungstate crystallizes in a fluorite-type structure, and it has
recently been shown that the formula is more correctly
represented as La7-xW1+yO16-δ (x=0.37, y=0.17, δ =2.57 for a
La/W nominal ratio of 5.6: LWO56) [2]. According to this
structure refinement, the oxygen sublattice is inherently
deficient and these positions are suggested to interact with water
vapor dissolving charge compensating protonic and oxygen
defects, yielding the materials conductivity characteristics. A
possible defect model will be presented. In addition to the
influence of protons on its properties, a peculiar effect was
observed when La was sought substituted by Ca [1]; the
presence of Ca seemingly decreased the ionic contribution to the
conductivity relative to the electronic one.
In order to further clarify the structural and functional
properties of this material, in-situ neutron diffraction
experiments at elevated temperatures under both nominally
dried and humidified Ar atmospheres have been performed at
the ISIS facility, Rutherford Appleton Laboratory (UK) on
single-phase undoped and 2% Ca-doped lanthanum
Fig. 1 Structure of LWO56
according to ref [2].
lattice parameter (Å)
11.28
11.26
11.24
11.22
11.2
11.18
11.16
100 300 500 700 900
T ( 0 C)
DRY AR
WET AR
P 09
Fig. 2. Variation of lattice parameter for
undoped LWO56 between 150 and 800
°C in flowing Ar, or wetted (D2O)- Ar.
tungstate. The main focus of the investigation is to locate crystallographic positions of both cations and
anions and correlate their implications on the proton conductivity, for instance, filling of oxygen
positions, cation displacements, or changes in the coordination environment. The role of acceptor
substitution to the behavior of this material will be discussed.
1. R. Haugsrud, Solid State Ionics 178 (2007) 555-560.
2. A. Magrasó, Carlos Frontera, David Marrero-López, Pedro Núñez, Dalton Transactions (2009) 10273 – 10283.
This work was supported by the “N-INNER” project (187160/S30) of the Research Council of Norway.
‐ 51 ‐

Periodic long range proton conduction pathways in
pseudo-cubic and orthorhombic perovskites
Maria A. Gomez a , Dylan Shepardson b , Luong T. Nguyen a,b , Tolu Kehinde b
a Department of Chemistry, Mount Holyoke College, 50 College Street, South Hadley, MA
01075, USA
b Department of Mathematics and Statistics, Mount Holyoke College, 50 College Street,
South Hadley, MA 01075, USA
Earlier, we investigated the effect of doping on N step
periodic proton conductions pathways in pseudo-cubic
BaZr0.875Y0.125O3 [1] and orthorhombic perovskites
SrZr0.875Y0.125O3 and SrZr0.875Al0.125O3 [2]. In the 900-1300K
temperature range, overall average limiting barriers over the
N step periodic pathways considered are 0.3, 0.4, and 0.6 eV
for Y/BaZrO3, Y/SrZrO3, and Al/SrZrO3, respectively, in
good relative agreement with experiment. There are many
contributing pathways for each system. Further, the
simulation box size limits the N step periodic pathways
found. In this paper, we expand the simulation cell
periodically and use vertex and color coding to find probable
pathways through the expanded system. Comparison of these
paths with the smaller simulation box N step periodic paths
provides us with insight on how to interpret pathways found
with different size simulation boxes.
1. M. A. Gomez, M. Chunduru, L. Chigweshe, L. Foster, S. J. Fensin,
K. M. Fletcher, L. E. Fernandez, The effect of yttrium dopant on the
proton conduction pathways of BaZrO3, a cubic perovskite, Journal
of Chemical Physics 132 (2010) 214709.
2. M. A. Gomez, M. Chunduru, L. Chigweshe, K. M. Fletcher, The
effect of dopant at the Zr site on the proton conduction pathways of
SrZrO3, an orthorhombic perovskite, Journal of Chemical Physics, Submitted.
‐ 52 ‐
Zr
Y
O
P 10
Figure 2: (a) shows a 17 step pathway in
Y/BaZrO3and (b) shows a 16 step
pathway in the Al/SrZrO3. The former
stays on doped faces while the latter
stays in undoped regions.
H

Proton Conductivity and Stability of Ba2In2O5 in Hydrogen Containing
Atmospheres
Jasna Jankovic a, b , David P. Wilkinson a, b , Rob S. Hui b
a Department of Chemical and Biological Engineering, University of British Columbia – 2360 East Mall, Vancouver,
BC, Canada, V6T 1Z3
b National Research Council – Institute for Fuel Cell Innovation – 4250 Wesbrook, Vancouver, BC, Canada, V6T 1W5
P 11
Ba2In2O5 is one of the oxygen deficient brownmillerite structured ceramic materials widely
investigated for both oxygen ion conduction and proton conduction in oxidizing atmospheres [1-4].
However, its electrochemical properties have not been studied in hydrogen containing atmospheres,
especially in the intermediate temperature range between 100 o C and 500 o C, a most desirable range
for many practical applications such as fuel cells. In this work the total electrical conductivity of
Ba2In2O5 in hydrogen containing atmospheres (with and without humidification) and contribution of
proton conductivity to the total conductivity were
investigated by AC impedance spectroscopy and
EMF method in the temperature range between
100 o C and 500 o C. A surprisingly high and stable
electrical conductivity of over 0.3 S/cm was
achieved in the temperature range of 300 o C to
480 o C in a 50%vol H2 - 50%vol N2 atmosphere,
as shown in Fig.1. EMF measurements revealed a
proton transport number of one at 100 o C and
200 o C, while 0.84 and 0.74 at 300 o C and 350 o C,
respectively. Ba2In2O5 shows chemical stability in
hydrogen containing atmospheres at temperatures
below 500 o C, while decomposing at above 500 o C.
This previously unreported conductivity in a H2
atmosphere creates an opportunity for use of
Ba2In2O5 as a proton conductive material for a
range
of intermediate temperature electrochemical
devices.
log� (S/cm)
1. G. B. Zhang, D. M. Smyth, Solid State Ionics 82 (1995) 153-160
2. T. Yajima, H. Iwahara, H. Uchida, Solid State Ionics 47 (1991) 117
3. G.B. Zhang, D.M. Smyth, Solid State Ionics 82 (1995) 161 -172
4. N. Bonanos, Solid State Ionics 53-56 (1992) 967-974
‐ 53 ‐
1
0
-1
-2
-3
-4
-5
-6
-7
-8
500 400 300 200 100 o C
Nafion
-9
1.20 1.60 2.00
1000/T(K
2.40 2.80
-1 )
Fig. 1 Comparison of Ba2In2O5 conductivity in different
atmospheres: ● in dry air; △ in dry N2; ◊ in
50%H2/50%N2; ♦ in 48%H2/49%N2/3% steam; □ sample
decomposed.

Proton Solvation and Transport in Hydrated Nafion
Shulu Feng and Gregory A. Voth
Department of Chemistry, James Franck Institute, and Computation Institute, University of Chicago, Chicago,
IL, USA
Proton solvation properties and transport mechanism were studied in hydrated nafion using the selfconsistent
multistate empirical valence bond (SCI-MS-EVB) method. It was found that sulfonate
groups affect proton solvation as well as proton distribution by stabilizing the Zundel-like structure
in their first solvation shells. Diffusion rates, Arrhenius activation energies, and transport pathways
were calculated and analyzed to characterize the nature of proton transport. Similar to experimental
observations, activation energy drops quickly with increasing water content when water loading
level is smaller than ~ 10 H2O/SO3 - . The transport pathway is strongly correlated with sulfonate
groups, which serve as a kind of transit station for the protons.
‐ 54 ‐
P 12

Conductivity study of dense BaZr0.9Y0.1O3-δ obtained by
spark plasma sintering
Sandrine Ricote * , Nikolaos Bonanos * , Hsiang-Jen Wang * and Bernard A. Boukamp **
* Fuel Cells and Solid State Chemistry Division, Risø National Laboratory for Sustainable Energy, Technical University
of Denmark, P.O. 49, 4000 Roskilde. Denmark.
** University of Twente, Faculty of Science and Technology, MESA + Institute for Nanotechnology, P.O. Box 217, 7500
AE Enschede, The Netherlands.
Many studies on proton conductors at intermediate
temperature are conducted on yttrium doped barium zirconate
because of its good stability and satisfactory proton conductivity
at temperatures around 600�C. Two issues, however,
are still under investigation: the fabrication of very dense
samples and the understanding of the high grain boundary
resistivity.
To obtain 95% dense samples requires sintering at
temperature about 1700�C for several hours, resulting in
evaporation of barium. The use of sintering aid has also been
tried, but leads to contamination of the grain boundaries. This
study presents the spark plasma sintering as a powerful
method to get 99.8% dense and transparent BaZr0.9Y0.1O3-δ
(BZY10) samples [1].
The purity of the sample has been investigated by XRD and
microscopy. The cubic lattice parameter of the single phase
compound has been evaluated to a slightly higher value than
the one commonly determined (4.2108Å), and the grain size
has been found to be between 100 and 800 nm. The HRTEM
pictures reveal clean grain boundaries (Figure 1).
Conductivity measurements have been performed in wet
reducing atmosphere to determine the bulk and grain
boundary activation energy of proton diffusion (Figure 2).
The higher value for the grain boundaries seems to be only
explained by a space charge layer, as neither evaporation of
barium nor impurity or second phase have been detected in
the grain boundaries. The activation energy found in this
work falls nicely on a plot of the bulk activation energy
versus the lattice parameter published by Azad et al. [2] on
BZY10 sintered by different processes, showing that a larger
lattice
parameter gives a lower activation energy for proton
transport.
‐ 55 ‐
� (S.cm -2 )
Fig. 1: HRTEM picture of BZY10.
1e-2
1e-3
1e-4
1e-5
1e-6
1e-7
Total
Bulk
GB
Specific GB
o
T ( C)
P 13
1nm
800 600 500 400 300 200
1e-8
0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
1000/T (K -1 )
Fig. 2: Temperature dependence of the
conductivity, N2/H2 (9%), 0.015 atm H2O.
1. S. Ricote, G. Caboche, C. Estournes, N. Bonanos, Journal of Nanomaterials (2008), Article ID 354258.
2. A.K. Azad, C. Savaniu, S.W. Tao, S. Duval, P. Holtappels, R.M. Ibberson and J.T.S. Irvine, Journal of Materials
Chemistry 18 (2008), 3414.

Conductivity study of A- and B-site (co-)doped LaNbO4
Mariya Ivanova 1 , Sandrine Ricote 2 , Wilhelm A. Meulenberg 1 , R. Haugsrud 3 , T. Norby 3
P 14
1 Forschungszentrum Jülich GmbH, Institute of Energy Research 1, D-52425 Jülich, Germany
2 Fuel Cells and Solid State Chemistry Division, Risø National Laboratory for Sustainable Energy, Technical University
of Denmark, P.O. 49, 4000 Roskilde, Denmark
3 University of Oslo, FERMiO, Gaustadalleen 21, NO-0349 Oslo, Norway
Acceptor-doped lanthanum niobate (LaNbO4) represents a
class of ceramic materials that exhibits proton conduction at
elevated temperatures accompanied by a high chemical and
thermal stability under a variety of conditions. Due to their
good mechanical properties, high red-ox stability and
compatibility with NiO and Ni, these niobates are of interest
for application as electrolyte in proton conducting solid
oxide fuel cells (PC-SOFC).
In order to improve the conductivity of these materials,
various doping and co-doping schemes can be implemented.
As shown in the literature, A-site doping for example with
1% Ca improves the proton conductivity of LaNbO4 up to a
value of approximately 1·10 -3 S·cm -1 at 1000 °C [1].
Different doping schemes of LaNbO4 were attempted in the
present study in order to: i) test the influence of doping
elements on both grain interior and grain boundary
conductivities; and ii) correlate the conductivity of doped
materials with both the chemical and structural features of
the host-guest matrix.
Materials developed in this study have a chemical
composition corresponding to the general formula
ln � tot [S.cm -1 ]
-8
-10
-12
-14
-16
-18
T [�C]
1000 800 600 400
LN-Ga
LN-Ge
LN-In
LCN-Ga
LCN-Ge
LCN-In
LBN-Ga
LBN-Ge
LBN-In
0.8 1.0 1.2 1.4 1.6 1.8
1000/T [K -1 ]
La1-xAxNb1-yByO4-δ where A stands for Ca or Ba and B for Ga, Ge or In (x=0 or 0.01; y=0.01). The
investigated compounds were synthesized via the solid state route. Samples with relative densities
higher than 95% were obtained after sintering at 1500°C/10hrs. The impedance spectroscopic study
was carried out in a wet (PH2O=0.015 atm) mixture of 9%H2 and N2 in the temperature range from
300°C to 900°C. Grain boundary and grain interior conductivities were deconvoluted from the
impedance spectra yielding several tendencies in analyzing the conductivity-doping elementcorrelation.
Amongst the developed doped materials, La0.99Ca0.01Nb0.99Ga0.01O4-δ showed the highest
total conductivity of 4·10 -4 S·cm -1 at 900 °C (Figure 1) which is however lower than the reference
value of approximately ~9·10 -4 S·cm -1 measured for La0.99Ca0.01NbO4-δ at 900 °C [1].
1. R. Haugsrud and T. Norby, Solid State Ionics 177 (2006), 1129.
‐ 56 ‐
1E-4
1E-5
1E-6
1E-7
1E-8
Fig. 1: Total conductivity of (co-)doped
LaNbO4 as a function of temperature.
� tot [S.cm -1 ]

Preparation of Nafion 117�-SnO2 Composite Membranes using an
Ion-Exchange Method
C. F. Nørgaard a , U. G. Nielsen b , E. M. Skou a
a
Institute of Chemical Engineering, Biotechnology and Environmental Technology, Faculty of Engineering, University
of Southern Denmark, 5230 Odense M, Denmark
b
Department of Physics and Chemistry, Faculty of Science, University of Southern Denmark, 5230 Odense M, Denmark
Nafion 117�-SnO2 composite membranes were successfully prepared using an ion-exchange
method. SnO2 was incorporated into Nafion 117� membranes by ion-exchange in solutions of
SnCl2 . 2 H2O in methanol, followed by oxidation to SnO2 in air. The content of SnO2 proved
controllable by adjusting the concentration of the ion-exchange solution.
The prepared nanocomposite membranes were characterized by XRD and 119 Sn MAS NMR while
the
in-plane proton conductivity was found to decrease with SnO2 content when evaluated with EIS.
However,
the conductivity was comparable to Nafion� at SnO2 contents below 8 wt%.
‐ 57 ‐
P 15

A study of Pt electrodes on proton conducting Ca-doped LaNbO4
Ragnar Strandbakke, Truls Norby, Reidar Haugsrud
Department of Chemistry, University of Oslo, FERMiO/SMN, NO-0349 Oslo, Norway
The polarization resistance of Pt point electrodes on a La0.995Ca0.005NbO4 (LCNO) proton conductor
has been investigated by electrical impedance spectroscopy in the temperature range 600 – 700 ºC in
wet O2, as a function of pH2O in 2.5 % O2 + 97.5 % Ar, and as a function of pO2 in wet O2 + Ar
mixtures. surface processes are being p
hydroxide ions from ambient water and
adsorbed surface oxygen is suggested as
governing the overall electrode reaction
under oxidizing conditions. H2O / D2O
isotope exchange measurements are in
agreement with the proposed wateroxygen
reaction, suggesting proton
transfer in both surface and interface
reactions.
(1/RS) shows a dependency of roughly
pH2O 1/3 roposed as rate limiting, and the formation of surface
and pO2
Fig. 1: 1/ RS (three‐phase boundary length specific)
as a function of pH2O and pO2 at 700 °C.
1/5 at 700 ºC, see Fig. 1.
The activation energy was 1.09 (± 0.04)
eV in wet O2, and total electrode
resistance at 700 ºC was approximately
3·10
f
4 Ωcm referring to unit triple phase
boundary length.
The surface related part of the
polarization resistance RS could be
fitted to a Langmuir-type adsorption
model, representing surface exchange o oxygen and water, followed by hydroxide formation
reaction.
‐ 58 ‐
P 16

Proton Conductivity in BCY20-Pd Ionic Hybrid Material
Archana Subramaniyan, Jianhua Tong, Ryan O’Hayre and Nigel Sammes
Department of Metallurgical and Materials Engineering, Colorado School of Mines, 1500 Illinois St., Golden, CO
80401, USA
Acceptor doped alkaline earth cerate perovskites
generate hydroxyl-type defects at elevated
temperatures in atmospheres containing water vapor
or hydrogen. The hydroxyl-type defects lead to
protonic conduction in these perovskites. Hence,
they are potential candidates for applications such
as fuel cells, hydrogen sensors and electrochemical
reactors. This work aims to fabricate and
characterize a “super ionic hybrid composite
material” combining proton conducting oxides and
a hydrogen permeable metal. Incorporation of the
hydrogen permeable metal nano-particles in the
proton conducting ceramic matrix at volume
fractions below the electronic percolation threshold
manipulates the space charge layer at the
metal/ceramic interfaces, and is thereby
hypothesized to increase the proton conduction
significantly. The super ionic hybrid composite
pellets are fabricated by mixing 20 mol% yttria
doped barium cerate (BCY20) with palladium
powder. As a first step in this two-step process,
BCY20 pellets were fabricated via powders
synthesized from a polymeric sol-gel route and
characterized by XRD, SEM and Raman
spectroscopy. A new phase, identified to be yttria
P 17
Fig. 1 Conductivities of BCY20 pellets sintered at
1450˚C for 24 h in air with (open symbol) and
without BCY20 powder bath (closed symbol).
doped ceria (Y0.2Ce0.8O1.9) was observed on the surface of the BCY20 pellets when sintered above
1250˚C for 24 hours. On sintering the pellets in a BCY20 powder bath, this phase was eliminated.
From the electrical characterization of BCY20 pellets (figure 1) sintered with and without powder,
the effect of the second phase on ionic conduction was observed. Also, the need for the
elimination of the same is proposed. The synthesis and sintering of BCY20 was thereby optimized
to obtain a phase pure material with the desired density. As a final step, super ionic hybrid pellets
were fabricated by mixing synthesized phase pure BCY20 powders with palladium nano particles.
The structural, microstructural, physical and electrical characterization of these BCY20/Pd
composite ceramics will be discussed in detail.
‐ 59 ‐

Defect chemistry and transport properties of oxide protonic perovskite
materials with transition metals on B-site: BaZr1-xPrxO3-δ
K. E. J. Eurenius, T. Kikuchi, M. Tamaru, S. Miyoshi, and S. Yamaguchi
Department of Materials Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, JAPAN
The development of highly reactive cathode materials for proton conducting fuel cells
(PCFCs) is a necessary component that has so far been missed to date i . Mixed electron and hole
conductors could greatly reduce cathode polarization because of extended 2-dimensional reaction
surface in comparison with a limited reaction area of triple phase boundary for composite cathodes.
One direction for the mixed conductivity is to employ the solid solution phase between AB 3+ xB 4+ 1xO3-(h
● )x and AB 3+ xB 4+ 1-xO3H + x ii,iii . However, this idea has not been successful, since the materials
examined earlier have shown poor or no proton conductivity. An additional route is to investigate
site percolation systems doped with a multivalent transition metal on the B-site, such as AM1-xyB
3+ xB 4+ yO3H. This composition has not yet
been successful due to poor hole and proton
conductivity iv .
The aim of this study is to
illustrate a complete picture based on
defect chemistry by Brouwer diagram
for such a system and hence to analyze
the characteristics of a site-percolation
properties. Further, the possibility of
strong correlation between localized
electrons and both holes and protonic
defects in combination with possible
two-fold percolation of electrons and
protons via the transition metal and
oxygen network is discussed.
Log
[Defect]
P 18
Log (pO2/atm) Log (pH2O/atm)
Fig.1. Illustration of defects under dry (pO2) and wet (pH2O) conditions.
As an example for the examination of the present idea, the experimental results of BaZr1-xPrxO3-δ (x
= 0.1 - 0.9) by electrochemical measurements for transference number, conductivity and Seebeck
coefficient as well as the electron spectroscopy measurements and DFT calculations have been
analyzed based on three-dimensional Brouwer diagram: A complex conduction behavior, where the
material with hole conductivity in O2 atmosphere due to the nature of PrO6 octahedra, turns into a
mixed conductor of protons, oxide ions and holes under reducing atmospheres, is analyzed using the
3D-Brouwer diagram estimated. The moderate range of mixed proton and hole conductivity, which
shows a cubic dependence with dopant concentration, is due to the strong correlation between
localized electrons on Pr ions and both positively charged electron holes and protons on oxide ions
sublattice B.
1
S. M. Haile Actra Materialia 51 (2003) 5981
1
H. Matsumoto, T. Shimura, T. Higuchi, T. Otake, Y. Sasaki, K. Yashiro, A. Kaimai, T. Kawada, J. Mizusaki,
Electrochemistry, 72 (2004) 861
1
H. Matsumoto, T. Shimura, T. Higuchi, H. Tanaka, K. Katahira, T. Otake, T. Kudo, K. Yashiro, A. Kaimai, T. Kawada,
J. Mizusaki, Journal of The Electrochemical Society, 152 (2005) A488
1
S. Mimuro, S. Shibako, Y. Oyama, K. Kobayashi, T. Higuchi, S. Shin, S. Yamaguchi, Solid State Ionics, 178 (2007)
647
‐ 60 ‐

Microstructural analysis of Y doped BaZrO3
Yukiko Oyama a , Takao Tsurui b , Miyoshi Shogo c , and Shu Yamaguchi c
a: Department of Applied Chemistry and Chemical Engineering, Toyama National College of Technology
13 Hongo, Toyama-shi, Toyama, 939-8630, Japan
b: Tohoku University Institute of Materials Research, Tohoku University
2-1-1Katahira, Aoba-ku, Sendai, 980-8577, Japan
c: Department of Materials Engineering, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo,
Bunkyo-ku, Tokyo, 113-8656, Japan
P 19
Yttrium doped BaZrO3 (BZ) is one of the candidate materials for the proton conducting electrolyte
with a superior chemical stability and the highest conductivity among perovskite oxide systems.
Our previous study for the samples synthesized by conventional solid reaction method sintered at
1600 ºC shows the phase separation of two BaZrO3 phased; a simple cubic BaZrO3 and perovskite
phase (BZ(II)) with an ordered super cell structure with structural units of BaZrO3 and BaYO2.5.
The samples with the composition of BaO:ZrO2:YO1.5(=1/2Y2O3)=3:2:1 and 9:4:8 have been
prepared by three different synthetic processes of conventional solid state reaction (SSR) method,
Pechini method, and Sol-Gel method using metal alkoxides as source materials, annealed for
various period of time. Microstructure observation of Ba(Zr1-xYx)O3-d by a transmission electron,
electron beam diffraction (JEM-4000EX, JEOL), and energy dispersive X-ray spectroscopy (JEM-
3000F, JEOL) are carried out to examine the phase formation in the polycrystalline samples
prepared by those preparatory methods.
TEM micrographs of SSR samples annealing at 1600 ˚C for 10h are shown in Fig 1 (a) and (c). The
primitive lattice of simple cubic BaZrO3 (Fig. 1 (a)), and nanocrystal grains (c) are observed. A
nanocrystal grains (Fig. 1 (c)) and the superlattice phase (Fig. 1 (d)) are both observed in addition to
the primitive lattice phase from the most of the samples except for sample. Amorphous phase (Fig.
1 (b)) is observed with supper lattice phase from SSR 100h and 200h samples. The primitive lattice
is only observed from the composition around the solubility limit of about 8 mol% Y in BaZrO3
phase. The compositions of superlattice phase are located between BaO:ZrO2:YO1.5=3:2:1 and
9:4:8 as shown in Fig. 2. The nano-grain crystals with almost the same compositions to the initial
one are observed from samples by Pechini and Sol-Gel method. The existence of stable nano-grain
crystals even after 200h annealing suggests the contribution of liquid phase for the phase formation.
The phase formation process of Y doped BaZrO3 phase based on the phase diagram for BaO-ZrO2-
YO1.5 system is also discussed by taking into account of the presence of liquid phase at the sintering
temperature.
(a)
(c)
2nm
2nm
(b)
(d)
2nm
2nm
Fig.1 TEM micrographs with electron beam diffraction patterns of
Ba 3 Zr 2 YO 8.5 synthesized by solid state reaction method annealed
at 1600°C for (a) and (c) 10h, and (b) and (d) 100h. The electron
diffraction image indicates (a) basic cubic pattern, (b) amorphous,
(c) nano crystal, and (d) super lattice, respectively.
- 61 -
ZrO2
BaO
3:2:1
■ 3:2:1 by SSR
■ 3:2:1 by Pechini
9:4:8 by Sol-Gel
9:4:8
YO1.5
Fig.2 Composition mapping of super lattice phase
about 3;2;1 and 9:4:8 samples annealed at 1600°C
on the BaO-ZrO2-YO1.5 ternary phase diagram.

Site Selectivity of Dopants in BaZr1-yMyO3-δ (M = Dy, Eu, Sm)
and Measurement of Their Water Contents and Conductivities
Donglin HAN a , Yoshitaro NOSE a , Kozo SHINODA b , Tetsuya UDA a
a Department of Materials Science and Engineering, Kyoto University,
Yoshida Honmachi, Sakyo-ku, Kyoto 606-8501, Japan
b Institute of Multidisciplinary Research for Advanced Materials, Tohoku University,
Katahira 2-1-1, Aoba-ku, Sendai 980-8577, Japan
BaZrO3 doped with trivalent rare-earth cations has
relatively high protonic conductivity in humidified
atmosphere. However, it is reported that the rareearth
cations, which are named as amphoteric
dopants, can occupy both A and B sites in crystal
lattice of perovskite oxides, consuming and
generating the oxide ion vacancies, respectively.
Since the protonic conductivity in doped BaZrO3
depends on the concentration of protons formed
by dissolving hydroxide ions into the oxide ion
vacancies, the concentration of oxide ion
P 20
Fig. 1 Lattice volume difference, defined as lattice
volume of the Ba-rich sample minus that of the Bapoor
sample, with reported data of doped BaTiO3 [1].
vacancies is one of the vital factors in the protonic conducting. Therefore, the site selectivity of
trivalent dopants in doped BaZrO3 is important on its protonic conductivity.
First, the lattice volumes of Ba1±0.01Zr0.99M0.01O3-δ (M = Sc, Y, Dy, Eu, Sm) were investigated. As
shown in Fig. 1, when doped with Eu or Sm, the difference of the lattice volume between Ba-rich
and Ba-poor samples was larger than that of nondoped
ones. However, when doped with Sc, Y or
Dy, the lattice volume difference was close to or
smaller than that of the non-doped ones. Therefore,
it is considered that comparing with Sc, Y and Dy, it
is relatively easy for Eu and Sm to occupy the A-site
when doping into BaZrO3. Then, the water contents,
namely concentrations of hydroxide ions, of the
BaZr0.8M0.2O2.9 samples hydrated in the humidified
O2 or Ar atmosphere were measured, as shown in
Fig. 2. The results revealed that when hydrated in Fig. 2 Proton concentration of BaZr0.8M0.2O2.9 (M =
Sc, Y, Dy, Eu, Sm) hydrated in humidified O2 or Ar.
humidified O2 atmosphere, the concentrations of
hydroxide ions of the samples doped with Dy, Eu or Sm were lower than those of the samples doped
with Sc or Y. And when hydrated in humidified Ar atmosphere, comparing with the ones hydrated
in humidified O2 atmosphere, no significant difference in concentration of hydroxide ions was
observed, expect the sample of BaZr0.8Dy0.2O2.9, which exhibited a great elevation in concentration
of hydroxide ions when hydrated in the humidified Ar atmosphere. At last, the measurement of
conductivities was performed. It was observed that for the BaZr0.8M0.2O2.9 (M = Sc, Y) samples,
there was little difference in conductivities measured in the atmosphere of humidified O2 or Ar.
However, by altering the atmosphere from humidified O2 to Ar, a dramatic elevation in the
conductivity of BaZr0.8Dy0.2O2.9 was observed. It is considered to be attributed reasonably to the
higher concentration of hydroxide ions in humidified Ar atmosphere than that in humidified O2
atmosphere, which was confirmed as shown in Fig. 2.
1. Y. Tsur, A. Hitomi, I. Scrymgeour and C.A. Randall, Japan Journal of Applied Physics 40 (2001), 255.
‐ 62 ‐

Proton conductors based on the double perovskite Ba2YNbO6
Xiaoxiang Xu, Elena Konysheva, Shanwen Tao, John T.S. Irvine
School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UK
The potential application of a proton conducting material is mainly dependent upon its magnitude of
conductivity and associated working temperatures. The most desirable working temperatures for
proton conductors, as has been identified by Norby, lie from 200 o C to 700 o C, where electrode
kinetics in fuel cells are fast and insensitive to poisoning [1]. But no satisfactory proton conductors
have been found in this range yet. Y doped BaCeO3 is a potential material as it shows promising
conductivity at a temperature as low as 600 o C. Its poor chemical stability toward CO2 and H2O
however, renders a large restriction on its application as the electrolyte in fuel cells as CO2 and H2O
are normal products during energy conversions. It has been reported that certain types of mixed
perovskites can be protonic conductors. They demonstrate comparable proton conductivity as simple
perovskite with less electronic contributions and much higher stability toward CO2 and H2O. A
typical example is Ba3Ca1.18Nb1.82O9-δ whose activation energy ~0.54 eV is comparable with the
simple perovskite BaCe0.9Y0.1O3-δ [2]. Their chemical formula can be written in general form
A3B’B”2O9 and A2B’B”O6, where A and B” are divalent ions and pentavalent ions, while B’ is
divalent for the formal but trivalent for the latter. It was found that B site disordering as well as Ba 2+
at A sites are favorable for higher proton conductivity [3]. Here we develop a double perovskite
structure material Ba2YNbO6 whose structure and electrical properties were investigated after
doping or introduction of cation non-stoichiometry. Large polarizable cations such as Ba 2+ and Y 3+
tend to form a high symmetry structure. The highest proton conductivity achieved is 1.38×10 -3 S/cm
at 540°C in wet 5% H2/Ar (humidified in water at room temperature) for sample Ba2Y1.08Nb0.88O6-δ,
which is comparable with primitive perovskite proton conductors。
1. T. Norby, Solid State Ionics 125 (1999), 1.
2. K.C. Liang, Y. Du, and A.S. Nowick, Solid State Ionics 69 (1994), 117.
3.
A.S. Nowick, Y. Du, and K.C. Liang, Solid State Ionics 125 (1999), 303.
‐ 63 ‐
P 21

Atmosphere dependent temperature evolution phase transition of
BaCe0.9Y0.1O2.95 - A neutron powder diffraction study
Abul K. Azad 1 , Angela Kruth 2 , John T.S. Irvine 1
1
School of Chemistry, University of St Andrews, Fife KY16 9ST, UK
2
Department of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, UK
P 22
Proton conducting solid electrolytes with high protonic conductivity with high transport number
have a wide range of technological applications in fuel cells, batteries, sensors,
hydration/dehydration of hydrocarbons, electrolysers. Yttrium doped BaCeO3 has been widely
investigated as a proton conducting material [1]. Earlier neutron powder diffraction measurements
probing the influence of water content on structure have started with wet or dry samples and heated
these up in vacuum with gradual loss of
water in conditions that do not quite match
those of the greatest technical relevance
[2,3]. In this study high-resolution neutron
powder diffraction data were collected at
different temperatures under hydrogen or
oxygen under high and low humidities. The
samples were loaded in quartz tubes in dry
or wet conditions, reducing pressure at
ambient to allow measurements in situ at
approximately 1 bar. Rietveld refinement of
neutron diffraction data showed that the
structure changed from orthorhombic (space
group Pbnm) to rhombohedral (R-3c) on
heating from room temperature to 973 K.
Figure 1 shows the Rietveld refinement
Fig. 1. Rietveld refinement profile of the neutron
powder diffraction data of BaCe0.9Y0.1O3-� collected
at room temperature in wet hydrogen atmosphere.
profile of BaCe0.9Y0.1O3-d collected at room temperature in wet hydrogen atmosphere. The unit-cell
volume under oxygen was found to be higher than under hydrogen at the same temperatures.
Oxygen site occupancies were directly determined as functions of temperature for dry and wet
conditions in both oxidising and reducing conditions in order to probe actual oxygen/hydroxyl
contents under the conditions relevant to most fuel cell or transport studies.
[1] K.D. Kreuer, Solid State Ionics, 97 (1997), 1.
[2] K. Knight, Solid State Ionics, 127 (2000), 43.
[3] I. Ahmed, C.S. Knee, M. Karlsson, S.-G. Eriksson, P.F. Henry, A. Matic, D. Engberg and L. Börjesson, Journal of
Alloys and Compounds 450 (2008), 103.
‐ 64 ‐

The effect of cation non-stoichiometry of proton conducting LaNbO4
Guttorm E. Syvertsen 1 , Anna Magrasó 2 , Mari-Ann Einarsrud 1 , and Tor Grande 1
1 Department of Material Science and Engineering, Norwegian University of Science and
Technology, NO-7491 Trondheim, Norway
2 Department of Chemistry, University of Oslo, FERMiO, Gaustadalléen 21, NO-0349 Oslo, Norway
The proton conductivity of LaNbO4 is enhanced by
minor substitution of La with alkaline earth ions [1-2].
The enhanced proton conductivity is rationalised by
hydration of oxygen vacancies, but interfacial space
charges may contribute as well. The solubility of
alkaline earth oxides in LaNbO4 is still under debate,
and possible supersaturation and minor deviations from
the nominal stoichiometric composition, may influence
the electrical conductivity of the bulk materials. Here
the influence of variations in cation non-stoichiometry
of LaNbO4 is reported. LaNbO4 produced by spray
pyrolysis [3] were systematically doped with small
amounts of La 3+ , Nb 5+ and Ca 2+ oxide precursors. The
sintering properties of the doped LaNbO4-powders were
investigated by dilatometry, and 4-point dc-conductivity
measurements were performed at elevated temperatures
in controlled atmosphere. Minor variations in the cation
stoichiometry were shown to have a pronounced effect
on both the sintering properties as well as the electrical
conductivity. The effects of the La-, Nb-, and Caadditions
are discussed with regards to mass transport
during sintering and on the electrical conductivity.
Finally the solubility of La2O3, Nb2O5 and alkaline earth
oxides in LaNbO4 is discussed with respect to possible
formation of secondary phases due to the cation nonstoichiometry.
1. R. Haugsrud and T. Norby, Nature Materials 5 (2006) (3),
193.
2. R. Haugsrud and T. Norby, Solid State Ionics 177 (2006) (13-
14), 1129.
3. T. Mokkelbost, I. Kaus, R. Haugsrud, T. Norby, T. Grande
and M.-A. Einarsrud, J. Am. Ceram. Soc. 91 (2008) (3), 879.
4. A.M. Frolov and A.A. Evdokimov, Russ. J. Inorg. Chem.
(Engl. Transl.), 32 (1987), 1771.
‐ 65 ‐
P 23
Fig. 1 10 kHz total conductivities of selected samples
of LaNbO4 with excess CaO.
Fig. 2 Part of the CaO-La2O3-Nb2O5 phase diagram
showing the investigated compositions. Phase diagram
was redrawn from Frolov and Evdokimov [4].

Solid State NMR Studies of CsH2PO4, a Protonic Conductor for
Intermediate-Temperature Solid Oxide Fuel Cells (IT-SOFCs)
Gunwoo Kim, 1 Frédéric Blanc, 1 and Clare P. Grey 1,2
1 Department of Chemistry, State University of New York, Stony Brook, NY 11794-3400, USA
2 Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK
There are strong demands for clean energy sources
to solve environmental issues. Fuel cells are a
promising alternative to conventional, internal
combustion engines as they are more efficient and
cleaner. Among the various electrolytes used for
IT-SOFCs, solid inorganic acids (e.g. CsH2PO4,
CsHSO4)[1, 2] are drawing significant interest as
they present unusually high protonic conductivity
over the phase transition state, referred to as
superprotonic phase. Although the conduction
mechanism has not yet been completely addressed,
it is generally accepted that the rotation of the
tetrahedral anion, H2PO4 - facilitates proton
conduction.[3] In order to fully understand the
detailed mechanism, solid state NMR spectroscopy
was used to examine the dynamics of the hydrogen
onded protons and the rotational behavior of the
trahedral anion in CsH PO .[4] The motions of
per
at
H line
lysi
O4 -
b
te 2 4
protons were observed using
spin e
measur and H- P double resonance
chniques to provide further insight into the
mechanism of conduction.
1 H and 2 H variabletem
ature (VT) NMR experiments including
relax ion time measurements. Different timescale
for the motion was obtained by simulations of the
2
shape, 2-site exchange of 1 H spectra and
ana s of relaxation times. The motion of the
H2P anion was also investigated by using 31 P
cho VT experiments, relaxation time
1 31
ements
te
P 24
1. Boysen, D.A., et al., High-Performance Solid Acid Fuel
Cells Through Humidity Stabilization. Science, 2004.
303(5654): p. 68-70.
2. Haile, S.M., et al., Solid acids as fuel cell electrolytes. Nature, 2001. 410(6831): p. 910-913.
3. Haile, S.M., et al., Solid acid proton conductors:
from laboratory
curiosities to fuel cell electrolytes. Faraday
Discussions, 2007. 134: p. 17-39.
4. Yamada, K., et al., Superprotonic conductor CsH2PO4
studied by 1H, 31P NMR and X-ray diffraction. Solid
State Ionics, 2004. 175(1-4): p. 557-562.
‐ 66 ‐
Figure 1. Variable-temperature 1 H MAS spectra of
CsH2PO4 at a spinning speed of 14 kHz at 11.4 T,
showing the effect of temperature on the two distinct
environments. The isotropic peaks at room temperature
are labeled.

First-Principles Studies of Proton - Ba tions in LaPO4
Nicole Adelstein
1,4 1,5 2,5
, Jian Feng , Jeffrey A. Reimer , Jeffrey
B. Neaton,
1,3
3
and Lutgard C. De Jonghe
‐ 67 ‐
2+ Interac
1 Materials Sciences Division
2 Energy and Environmental Technology Division
3 Molecular Foundry
Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley CA 94720, USA
4 Department of Material Science and Engineering
5 Department of Chemical Engineering
U. California at Berkeley, Berkeley CA 94720, USA
The
proton‐dopant interaction in Ba‐doped LaPO4 is studied with first‐principles density
functional
theory to explore the role played by dopants in proton conduction. Using large
supercells,
we find that 3% Ba‐doping results in a local effective
negative charge near the
dopant that attracts protons. Protons near Ba dopants bind
to oxygen much more strongly
relative to sites far from the dopant, suggesting the prot
room
temperature. ped La
e .3 Å,
1H{ 137 on should sit near Ba at
Ba NMR double resonance experiments on
a related system, a Ba‐do
metaphosphate glass, support this claim, finding that the av rage proton‐Ba distance is 3
in good agreement with our calculations for Ba‐doped LaPO4.
Fig. 1 The proton sits bounded
to an oxygen. Sites are chosen
based on the distance to the
barium dopant.
P 25

High Temperature Protonic Conduction Properties of
(La,Sr)MO3 – SrZrO3 (M = Cr, Mn and Fe) Solid Solutions
Atsushi Unemoto A , Koji Amezawa B , and Tatsuya Kawada B
A Institute of Multidisciplinary Research for Advanced Materials, Tohoku University
B Graduate School of Environmental Studies, Tohoku University
P 26
To date, although protonic conductivity of the rare-earth doped SrZrO3 is widely
investigated, the number of reports regarding the transition metal-doped one is limited to only a few
reports. In our recent work on the electrical conductivity measurements of SrZr0.99Fe0.01O3-δ, it was
found that the transport number of proton is relatively high even at higher temperatures, for
instance, 0.75 at 1173 K in H2 – 1.9%H2O [1]. Since the solubility of Fe in SrZrO3 is limited to be at
most 2.5 % [2], we additionally doped La in A-site to increase the doping level of Fe in B-site,
aiming to increase the protonic conductivity. However, it resulted in only drastic decrease of the
electrical conductivity and transport number of protons [3]. In this study, we examined the electrical
conductivities of (La,Sr)MO3 – SrZrO3 (M = Cr and Mn) by two-probe ac technique to investigate
the effect of co-doping of La and transition metal M (M = Cr, Mn and Fe) into SrZrO3.
Figure 1 shows the electrical conductivities of (La0.9Sr0.1MO3-δ)0.05(SrZrO3)0.95 for M = Cr
and Mn in H2 – 1.9%H2O and in D2 – 1.9%D2O at 1073 – 1273 K. In the case of M = Mn, the
conductivity degraded gradually with time in lower oxygen partial pressure, suggesting
decomposition of the oxide. Thus, the measurements could be performed only limited oxygen
partial pressure range. Remarkable isotope effect of H and D was observed for both oxides similarly
to the case of M = Fe [3], suggesting remarkable protonic conduction. It was also found that the
total conductivity increased by decreasing oxygen partial pressure, corresponding to decrease of
mean valence of Cr in the oxide.
When major positive defect is oxygen vacancy, the proton concentration is expected to be
12
proportional to pH2O. Thus, by assuming the linear relation between the proton conductivity and the
concentration, the contribution of protonic conductivity could be separated under constant oxygen
o 12
partial pressure by the equation, � � ����
��
�� � pH2O,
at temperature from 1273 – 1073 K. �� H ��is
the
o
conductivities except for protonic one and � � � H
is a constant. Transport number of proton was
found to depend on oxygen partial pressure
similarly to the case of M = Fe [3]. At 1173 K
in log( pH2 O / atm) = 0.019, it varied from 0.63
to 0.73 in the oxygen partial pressure range of
log( p / atm) = -15.58 to -19.57.
O2
1. A. Unemoto, A. Kaimai, K. Sato, N. Kitamura, K.
Yashiro, H. Matsumoto, J. Mizusaki, K. Amezawa,
T. Kawada, Solid State Ionics 181 (2010) 868.
2. A. Unemoto, A. Kaimai, K. Sato, K. Yashiro, H.
Matsumoto, J. Mizusaki, K. Amezawa, T. Kawada,
Solid State Ionics 178 (2008) 1663.
3. A. Unemoto, A. Kaimai, K. Sato, N. Kitamura, K.
Yashiro, H. Matsumoto, J. Mizusaki, K. Amezawa,
T. Kawada (In Preparation).
‐ 68 ‐
Figure 1. Electrical conductivity of (La0.9Sr0.1MO3δ)0.05(SrZrO3)0.95
(M = Cr, Mn and Fe) in humidified hydrogen.
Closed and open symbols are the values in H2 – 1.9%H2O and
D2 – 1.9%D2O, respectively.

Electrical Conductivity and Defect Structure of Sr-Doped Nd3PO7
Atsushi Unemoto A , Koji Amezawa B , and Tatsuya Kawada B
A Institute of Multidisciplinary Research for Advanced Materials, Tohoku University
B Graduate School of Environmental Studies, Tohoku University
P 27
A series of phosphate-based proton conductors is a promising candidate as a solid electrolyte
[1-3] because they are expected to have high tolerance against ambient gases such carbon dioxide
and water vapor contrary to proton conducting cerates [4]. In this study, we chose the rare-earth
oxyphosphate, (Nd,Sr)3PO7, as a phosphate-based proton conductor. Although crystal structure
analysis [5] and luminescent properties [6] of the rare-earth oxyphosphates are revealed so far, the
electrical conduction properties are still unclear.
Powders of the rare earth oxyphosphates, (Nd1-xSrx)3PO7-δ (x = 0 and 0.03), were prepared by
a conventional solid state reaction route. The sintered bodies were obtained by a spark plasma
sintering (SPS) technique. Platinum-paste was painted on both surfaces as electrodes. The electrical
conductivities were evaluated by a two-probe ac technique in oxygen environments.
The electrical conductivity of Sr-doped Nd3PO7 showed higher values than that of non-dope
one by approximately one – half order of magnitude in 1.0%O2 – 1.9%H2O and unhumidified
1.0%O2. This suggests that doping of Sr into Nd3PO7 enhanced the electrical conductivity.
Figure 1 shows the electrical conductivity of (Nd0.97Sr0.03)3PO7-δ as a function of oxygen
partial pressure in unhumidified and humidified environments. It was found from the figure that the
electrical conductivity in humidified oxygen is smaller than that in unhumidified one, obviously at
temperatures below 1073 K and as oxygen partial pressure decreased. When major positive defect is
12 14
oxygen deficit, proton and electron hole concentrations are expected to depend on pH2O and pO2 ,
respectively. Thus, the electrical conductivity positively depends on water vapor pressure in proton
conducting phosphates [3]. On the other hand, when major positive defect is proton, the oxygen
�1 �1 2 14
deficit and electron hole concentrations are expected to depend on pH2O and pH2O pO2 , respectively.
As seen in the figure, the electrical conductivity decreased by increasing the water vapor pressure
under constant oxygen partial pressure at temperatures below 1073 K while it increased as oxygen
partial pressure increased under constant water vapor pressure. Considering the gas partial pressure
dependences of the electrical conductivity, it might be concluded that protonic defect is induced in
oxyphosphates, however, the ceramics does not allow their significant conduction. This means,
major ionic carrier is oxide ion rather than
proton in (Nd0.97Sr0.03)PO7-δ.
1. T. Norby, N. Christiansen, Solid State Ionics 77 (1995)
240.
2. K. Amezawa, S. Kjelstrup, T. Norby, Y. Ito, J.
Electrochem. Soc. 145 (1998) 3313.
3. K. Amezawa, H. Maekawa, Y. Tomii, N. Yamamoto,
Solid State Ionics 145 (2001) 233.
4. H. Matsumoto, S. Okada, S. Hashimoto, K. Sasaki, R.
Yamamoto, M. Enoki, T. Ishihara, Ionics 13 (2007)
93.
5. E. G. Tselebrovskaya, B. F. Dzhurinskii, O. I.
Lyamina, Inorg. Mater. 33 (1997) 52.
6. S. Ku, J. Zhang, J. Lumin. 122-123 (2007) 500.
‐ 69 ‐
Figure 1. Electrical conductivity of (Nd0.97Sr0.03)3PO7-δ as
a function of oxygen partial pressure at 973 – 1273 K.

Mechanochemical Synthesis of Proton Conductive CsHSO4-Azole Composites
for Medium Temperature Dry Fuel Cells
Song-yul Oh 1 , Toshihiro Yoshida 1 , Go Kawamura 2 , Hiroyuki Muto 1,2 , and Atsunori Matsuda 1,2
(1) Department of Environmental and Life Sciences, Toyohashi University of Technology,
Tempaku-cho, Toyohashi, Aichi 441-8580, JAPAN
(2) Department of Electrical and Electronic Information Engineering, Toyohashi University of Technology, Tempakucho,
Toyohashi, Aichi 441-8580, JAPAN
P 28
Inorganic solid acids, such as sulfates and phosphates, have been widely studied because of
their promising proton conductivity for the application to electrochemical devices and unique phasetransition
to super-protonic state. 1,2) However, despite their high proton conductivity in the superprotonic
regions, they show much lower proton conductivity at temperatures lower than the
transition temperature.
On the other hand, we have shown that a solid state reaction involving mechanochemical
treatment using a high-energy ball mill is a promising way to improve the proton conductivity of
inorganic solid acids and to synthesize a new class of solid acid composites. 3,4) In this study,
inorganic-organic composites were synthesized by the solid state mechanochemical method, and
their proton conductivity and structure studies were performed. CsHSO4 (CHS) was chosen as an
inorganic acidic compound to investigate its super-protonic behavior, and three kinds of azoles,
imidazole (Iz, Tm = 89 o C), 1,2,4-triazole (Tz, Tm = 123 o C) and benzimidazole (Bz, Tm = 171 o C),
were examined as organic basic compounds to use their self-dissociation behaviors.
80CHS·20Azole composites (in mol. %) were prepared to improve the proton conductivity,
especially in a temperature range lower than Tc of CHS in a dry atmosphere. According to this
approach, it is expected that newly developed hydrogen bonding and acid-base ionic cluster between
CHS and azoles involve promising proton conductivity in a wide range of temperature under
anhydrous atmosphere.
The azoles such as Iz, Tz and Bz are capable basic components that can act as a proton solvent,
like water, due to its amphoteric (proton donor–acceptor sites) nature, intermolecular hydrogen bond
formation and self-dissociation characteristics. 5) In Fig. 1, the CHS-Azole composites show higher
proton conductivities, especially in
temperature regions lower than the phase
transition temperatures of their raw substances.
Furthermore, the CHS-Iz and CHS-Tz show a
value range close to 4.8×10 -4 to 1.9×10 -3 Scm -
1 with in a wide temperature range of from 50
to 160 o C, in a dry N2 atmosphere. These
results, including their structural studies,
indicate that chemical interactions between
CHS and azoles were newly formed, which
improve proton transfer by protonic hopping.
Detailed results on the structural studies and
proton conductivities of CHS-Azole
composites with various molar ratios will be
presented and discussed.
[1] T. Norby, Solid State Ionics 125 (1999) 1.
[2] S.M. Haile, et al., Nature 410 (2001) 910.
[3] A. Matsuda, et al., Solid State Ionics 176 (2005) 2899.
[4] A. Matsuda, et al., Solid State Ionics 177 (2006) 2421.
[5] K.D. Kreuer, Chem. Mater. 8 (1996) 610
Fig. 1. The temperature dependence of conductivity of
various CHS-Azole composites. CHS, Iz, Tz and Bz
are for CsHSO4, imidazole, 1,2,4-triazole and
benzimidazole, respectively.
‐ 70 ‐

Micro solid oxide fuel cells with perovskite type proton conductive thin
electrolytes
Fumitada Iguchi, Kensuke Kubota, Syuji Tanaka, Noriko Sata,
Masayoshi Esashi and Hiroo Yugami
Graduate School of Engineering, Tohoku University
Aoba 6-6-01, Aramaki, Aoba-ku, Sendai 980-8579, Japan
P 29
We fabricated micro - sized solid oxide fuel cells (m-SOFC), which based on proton conductive
electrolytes, i.e. Y-doped BaZrO3 and Sr-doped LaScO3 on silicon wafers and perform power
generation test of those cells. In this study, modified cell design with flat thin electrolytes and
trapezoid shape flow channels were adopted to resolve the problems of mechanical stability. The
schematic illustration of the cell design is shown in fig.1. As an electrolyte, 15mol% Y-doped
BaZrO3 or 20mol% Sr-doped LaScO3 were used, and at the both sides of the electrolyte, Pt-Pd
porous electrodes were fabricated as electrodes.
As shown in fig.2, free standing m-SOFC cells (300mm) with 15mol% Y-doped BaZrO3 (BZY15)
proton conductive thin electrolyte, were successfully fabricated on the (100) Si wafer. Because
residual stress in the electrolyte was kept at compressive during operation to prevent mechanical
failures, the electrolyte was significantly distorted. But, it is consistence during thermal cycles up to
several times.
The power generation test was performed in the temperature range of 286 o C to 430 o C with
humidified H2 as anode gas and air as cathode gas. Observed open circuit voltage around 400 o C was
over 1000mV. So, it is confirmed that anode and cathode were successfully separated by the
electrolyte as same as conventional SOFC. The maximum power density was obtained at 386 o C and
the value was 0.03 mW /cm 2 . The value is quite lower than leading power density (861mW /cm 2 at
450 o C[1], 150mW /cm 2 [2] at 550 o C) using YSZ a electrolyte. In this study, although m-SOFC can
work well, it is clear that the performance of the m-SOFC should be improved.
Figure 1 schematic illustration of cell design Fig.2 �‐SOFC (□300mm)
‐ 71 ‐
100�m
References
[ 1] P.-C. Su, C.-C. Chao, J.H. Shim, R. Fasching and F.B. Prinz, Nano Letters 8 (2008) (8), p. 2289.
[ 2] Anja Bieberle-Hutter et al, Journal of Power Sources 177 (2008), p.123.

Room-Temperature Protonic conduction in Nanocrystalline films of Yttria-
Stabilized Zirconia
Sangtae Kim, Hugo J. Avila-Paredes, Zuhair A. Munir
Department of Chemical Engineering and Materials Science, University of California, Davis, CA 95616, USA
We have recently reported that doped ZrO2 and CeO2
ceramics conduct protons under wet atmosphere at
relatively low temperatures (< 200�C) when their grain
size becomes smaller than 100 nm [1-3]. The protonic
conductivity increases rapidly with decreasing grain size,
implying that protons indeed migrate along the grain
boundaries under such conditions [2].In this contribution,
we present the results of our investigation on protonic
conduction in 1 �m-thick polycrystalline films of 8 mol%
yttria-stabilized zirconia (YSZ) with an average grain size
of 17 nm prepared on sapphire substrate using a spincoating
process [4]. Protonic conductivity of the films is
found to be higher by over an order of magnitude (at
30�C ) than earlier reported values for nanocrystalline
YSZ bulk ceramics with a similar grain size. This value is
comparable to the oxygen-ionic conductivity of this
material presented at about 400 �C. These results
suggest that, besides grain size, the structural
characteristics of the grain boundaries may also play an
important role in determining protonic transport in this
material, and possibly other nanocrystalline solid
electrolytes
(SEs), and that the protonic conductivity can
further
be enhanced by optimizing such characteristics of
the
grain boundaries. Aa
aa
Acknowledgement
The authors are grateful to Prof. H.U. Anderson for providing the
YZS film samples and also thank Prof. Barrera-Calva for AFM
measurements. The authors appreciate fruitful discussion with Prof.
M. Martin and Dr. R. A. De Souza.
‐ 72 ‐
� t T / (S cm -1 K)
10 0
10 -2
10 -4
10 -6
10 -8
10 -10
600 400
T / °C
200
b
YSZ Film (17 nm)
YSZ Pellet (13 nm)
YSZ Pellet (100 nm)
P 30
P H2O = 2x10 -2 bar
0.8 1.2 1.6 2.0 2.4 2.8 3.2 3.6
1000T -1 /K -1
Fig. 1 A SEM image of 1-�m thick YSZ
film with a grain size of ~17 nm on a
sapphire substrate (a); the conductivities
measured form nano-structured samples
indicated under wet air in the temperature
range of 30 – 600 �C (b).
1. S. Kim, U. Anselmi-Tamburini, H. J.Park, M. Martin and Z. A. Munir, ,Adv. Materi., 2008, 20, 556.
2. H. J. Avila-Paredes, J. Zhao, S. Wang, M. Pietrowski, A. Reinholdt, Z. A. Munir, M. Martin, and S. Kim, J. Mater.
Chem., 2010, 90, 990.
3. S. Kim, H. J. Avila-Paredes, S. Wang, C. T. Chen, R. A. De Souza, M. Martin, Z. A. Munir, Phys. Chem. Chem.
Phys., 2009, 11, 3035.
4. Hugo J. Avila-Paredes, Enrique Barrera-Calva, Harlan U. Anderson, Roger A. De Souza, Manfred Martin, Zuhair
A. Munir and Sangtae Kim, J. Mater. Chem., 2010, DOI: 10.1039/c0jm00051e.

P 31
Fabrication of BaCe0.9Y0.1O3-� thin film on Pd substrate by UV-MOD
Koichi Asano a , Yoshihiro Kozawa b , Yoshihiro Mugikura a,b , and Takao Watanabe a,b
a Central Research Institute of Electric Power Industry, 2-6-1 Nagasaka, Yokosuka 240-0196, JAPAN
b Yokohama National University, 79-7 Tokiwadai, Hodogaya, Yokohama 240-8501, JAPAN
Introduction – Solid oxide fuel cell (SOFC) has been focused on the development of intermediate
temperature (IT) range of 873-1073 K considering a long-term operating and low material cost. We
have applied accepter-doped BaCeO3 to an electrolyte for IT-SOFC because it shows relatively-high
proton conductivity and the cell performance of proton conductor is expected higher than that of
oxide ion conductor around IT region. However, in a CO2-containg atmosphere as a reformed
natural gas, BaCeO3 doesn’t always posses sufficient chemical stability and loses its proton
conduction. We have overcome that BaCeO3 is covered with a dense Pd 1) . Pd protected BaCeO3
from the reformed gas, and function at the same time as an anode. On the other hand, the reduction
in operating temperature of SOFC leads to rapid increase in the bulk resistance of the electrolyte.
Therefore, thin films as an electrolyte are generally considered. However, thermal resistances of Pd
and cathode materials are normally lower than the sintering temperature of BCYO. In this study, the
thin film to achieve the IT-SOFC that applied BaCe0.9Y0.1O3-� (BCYO) as the proton conductor was
fabricated on dense Pd substrate at low sintering temperature by metal organic deposition (MOD)
method.
Experimental – The metal organic acid salt solutions
(Kojundo Chemical Laboratory Co. Ltd., Japan) as
precursor materials were applied to Pd substrate
(Pd/Ag=75/25%, φ18 mm, 0.2 mm t ) by a spin-coating
technique and were pyrolyzed at 523 K. This process
was repeated 8 times and it was then sintered at 1123
K, 0.5h in air.
Result and discussion – BCYO film layer was
fabricated on Pd substrate with good adhesion. The
thickness of thin film is about 0.8 �m. However, the
BCYO thin film had low density as an electrolyte as
shown in Fig.1(a). The UV-MOD as a new process,
which was added with ultraviolet lamp irradiation
(254 nm) after spin-coating at room temperature, was
applied. The thickness of thin film is about 0.45 �m as
shown in Fig.1(b). It was found that the BCYO thinfilm
fabricated by UV-MOD method was achieved
high density compared with the MOD method. The
XRD pattern of BCYO is shown in Fig.2. BCYO and
Pd are mainly identified and BCYO single phase was
formed on Pd substrate. But it seems that the
conductivity of BCYO was rather low, 10 -4 Scm -1 at
873 K in wet hydrogen atmosphere because the small
amount of PdO was formed by sintering process.
Reference – [1] K. Asano, M. Kawakami, Y. Mugikura, and T. Watanabe, ECS Trans., 7, (1), 993 (2007).
‐ 73 ‐
(a)
Cover layer
BCYO
(b)
Cover layer
BCYO
Pd substrate Pd substrate
Fig.1 Cross-sectional SEM images of BCYO thin
film on Pd substrate milled by FIB.
(a) MOD, (b)UV-MOD.
Fig.2 XRD pattern of BCYO thin film on
Pd substrate.

First principles calculations of defect equilibria in BaZrO3
Akihide Kuwabara 1 , Craig A. J. Fisher 1 , Hiroki Moriwake 1 ,
Fumiyasu Oba 2 , Katsuyuki Matsunaga 2 , Isao Tanaka 1,2
Nanostructures Research Laboratory, Japan Fine Ceramics Center, 2-4-1 Mutsuno, Nagoya, 456-8587, Japan
Department of Materials Science, Kyoto University, Yoshida, Kyoto, 594-8587, Japan
P 32
Acceptor-doped BaZrO3 exhibits high proton conductivity at elevated temperatures in wet
atmospheres [1]. It may thus be a candidate for the electrolyte in a proton conducting solid oxide
fuel cell. Acceptor doping of BaZrO3 forms oxide ion vacancies in order to maintain electrical
neutrality. In wet atmospheres, the vacancies react with water vapor, whereby the vacancies are
filled and protons are introduced into the lattice. Theoretical calculations based on density functional
theory have been systematically performed to evaluate the defect energetics of BaZrO3 [2-3].
However, defect equilibria involving cation defects are not
yet well understood. The aim of the present study is to
clarify defect formation behavior.
Total energy calculations were carried out using
VASP code [4]. Electron-ion interactions were represented
by the projector augmented wave (PAW) method, and the
generalized gradient approximation (GGA) was chosen for
the exchange-correlation potential. Plane waves up to an
energy cut-off of 400 eV were used as the basis set for wave
functions. First, a primitive cell of BaZrO3 was fully
optimized, and then supercells containing 320 atoms (4 � 4
� 4 unit cells) were constructed for calculations of defective
systems. In this study, we focused on defects in pure
BaZrO3. Only the Γ point was adopted as k-point sampling
for the supercells. All atomic positions in defective systems
were fully relaxed until all residual forces were less than
0.02 eV/Å. Details of the calculation methodologies of
point defect formation energy are available elsewhere [5-6].
As shown in Figure 1, native defects of BaZrO3,
��
oxygen vacancies ( VO ) and Ba vacancies ( V� � Ba ), are likely
to form under both Zr-rich and Ba-rich conditions at 1900 K.
From the point of view of electrical neutrality, the major
��
defects are partial Schottky pairs of V ��Ba � VO
. Under the Zr-
��
rich condition, anti-site defects of Zr ions on Ba sites ( ZrBa
)
can also be formed.
Figure 1. Dependence of calculated defect
formation energy on Fermi energy under (a)
Ba-rich and (b) Zr-rich conditions at T =
1900 K, pO2 = 0.1 atm and pH2O = 0.02
atm. In the horizontal axis, the valence band
top is set to be 0 eV. Conduction band
bottom is 5.4 eV [7].
1. S. Imashuku, T. Uda, Y. Nose, G. Taniguchi, Y. Ito, and Y.
Awakura, Journal
of The Electrochemical Society, 156 (2009) B1.
2. M. E. Björketun, P. G. Sundell and G. Wahnström, Physical Review B, 76 (2007) 054307.
3. M. E. Björketun, P. G. Sundell and G. Wahnström, Faraday Discussions, 134 (2007) 247.
4. G. Kresse and J. Furthmüller, Physical Revew B, 54 (1996) 11169.
5. A. Kuwabara and I. Tanaka, Journal of Physical Chemistry B, 108 (2004) 9168.
6. A. Kuwabara, R. Haugsrud, S Stølen and T. Norby, Physical Chemistry Chemical Physics, 11 (2009) 5550.
7. G. Łupina, J. Dąbrowski, P. Dudek, G. Kozłowski, P. Zaumseil, G. Lippert, O. Fursenko, J. Bauer, C. Baristiran, I.
Costina, H.-J. Müssig, L. Oberbeck, and U. Schröder, Applied Physics Letters, 94 (2009) 152903.
‐ 74 ‐

On the symmetry of defects in perovskite-type protonic conductors:
A Sc-45 NMR study
Itaru Oikawa 1 , Mariko Ando 1 , Hajime Kiyono 2 , Masataka Tansho 3 , Tadashi Shimizu 3 ,
and Hideki Maekawa 1
1 Graduate School of Engineering, Tohoku University, Aramaki Aoba 6-6-02, Sendai, 980-8579, Japan
2 Graduate School of Engineering, Hokkaido University, N13, W8, Kita-ku, Sapporo, 060-8628, Japan
3 National Institute for Materials Science, Sakura 3-13, Tsukuba, 305-0003, Japan
Introduction
Perovskite-type protonic conductors AB1-xMxO3-� (M: rare-earth elements) are a candidate
for electrolytes of intermediate temperature solid oxide fuel cells due to high protonic conductivity.
Protonic conductivity varies with A and B site cations as well as dopant cations. Nuclear magnetic
resonance (NMR) can provide local structural information around specific ions in oxide materials.
In the present study, defects around dopant cations in perovskite-type protonic conductors were
investigated
by Sc-45 NMR.
Experimental
Samples of AB1-xScxO3-� (A = Ba, Ca and Sr, B = Ce and Zr) were prepared by solid state
reaction. Raw materials were mixed, pelletized and calcined at 1473 K in air. Calcined pellets were
ground, mixed by a ball mill and sintered at 1723-1873 K in air. Sintered samples were vacuum
dried at 1173 K. Sc-45 magic-angle spinning (MAS)-NMR were carried out at JNM-ECA930
spectrometer (21.8 T) with Sc-45 resonance frequency 225.78 MHz. NMR spectra were collected by
single pulse experiment with pulse length of 1 �s at spinning speed 22 kHz.
Results and discussion
Sc-45 MAS-NMR spectra of vacuum dried II: ScO ScO6-H I: ScO
6-H I: ScO 6
AB0.90Sc0.10O3-� (A = Ba, Ca and Sr, B = Ce and Zr) III: ScO BaZrO
5
3
showed obvious compositional dependence, as shown in *
* *
Fig. 1. Peaks I, II and III were assigned to sixcoordinated
Sc (ScO6), six-coordinated Sc with protons
III II I BaCeO 3
*
*
reside vicinity (ScO6-H) and five-coordinated Sc with
one oxygen vacancy (ScO5), respectively. The second-
III II SrCeO 3 I
order quadrupole coupling alters the line shape with its
*
*
constants CQ. The line shape change of ScO5 (hatched
III I CaZrO 3
peaks in Fig. 1) was interpreted as a result of symmetry
change of ScO5. CQ of peak III obtained from the peak
300 250 200 150 100 50 0
simulation decreased in the order of BaZrO3, BaCeO3,
chemical shift / ppm
SrCeO3 and CaZrO3. We found that ScO5 polyhedra
Fig. 1 Sc-45 MAS-NMR spectra of vacuum
change its symmetry with A and B site cations for the dried AB0.90Sc0.10O3-� (A = Ba, Ca and Sr, B
first time, and it will open a new paradigm to defect = Ce and Zr). Asterisks indicate spinning
engineering based on the symmetry of oxygen polyhedra. sidebands.
Acknowledgements
H.M. wishes to express his sincere gratitude for the financial support provided by CREST,
JST under “Novel Measuring and Analytical Technology Contributions to the Elucidation and
Application of Materials.” and by KAKENHI “(Grant No. 21360314)” MEXT, Japan.
‐ 75 ‐
P 33

Performances of Reversible SOFCs with BaZr0.6Co0.4O3-δ as air electrode
Fei He, Ranran Peng, Changrong Xia
Department of Material Science and Engineering,
University of Science and Technology of China, Hefei, 230026, P.R.China
Introduction: Reversible solid oxide fuel cells with proton
conducting electrolyte (H-RSOFC) have attracted much
attention because of its special characteristics[1]. In H-
RSOFCs, major part of polarization resistances comes from
air electrodes due to their low catalytic activities. In this
paper, BaZr0.6Co0.4O3-δ were prepared by citric method, and
applied as single phase air electrode for H-RSOFCs. The
electro-performance of such H-RSOFCs was investigated
with BaCe0.5Zr0.3Y0.2O3-δ as electrolyte. The Reversible
solid oxide fuel cells with structure of Ni-BZCY|| BZCY||
BZCO were fabricated and tested in a home-developed-celltesting
system with 30%H2O-air and H2 introduced into air
electrode and hydrogen electrode, respectively.
Results and Disscussion: The performances of RSOFC
were investigated in both SOFC mode and SOEC mode at
600, 650 and 700 o C, as shown in Fig. 1. The open circuit
voltages (OCV) of cells are 0.99, 0.97, 0.95V at 600, 650
and 700 o C, respectively, indicate the electrolyte is very
dense. At SOFC mode (the right part of Fig.1), the current
densities increase with temperature, is about 300mAcm -2 at
0.7V and 700 o C. On the other hand, the performance of cells
in the SOEC mode also increases with temperature (see the
left panel of Fig. 1), and the electrolysis current densities at
cell voltage of 1.3V is -530 mAcm -2 at 700 o C. In Fig. 2. the
impedance spectra of the H-RSOFCs with BZCO single
phase electrode and BCZY/ Sm0.5Sr0.5O3-δ(SSC) composite
electrode were compared at 700 o C, as shown in Fig. 2. The
bulk resistance of the cell with BZCO electrode is bigger
than which with BCZY/SSC electrode, however, the
interfacial polarization resistance of the cell with BZCO
lectrode is 0.2Ωcm 2 e
, about half of that with BCZY/SSC
electrode.
1. M. Ni, M. K. H. Leung, D. Y. Leung, International Journal of
Hydrogen Eneryg 33(2008) 4040-4047
‐ 76 ‐
P 34
Fig. 1 I-V curves of RSOFCs measured at
various temperatures.
Fig. 2 The impedance spectra of the H-RSOFCs
with BZCO and BCZY/SSC electrode were
compared at 700 o C.

Space charge effect and dopant segregation in acceptor-doped BaZrO3
proton conductors
Mona Shirpour 1) , Behnaz Rahmati 2) , Wilfried Sigle 2) ,
Peter A. van Aken 2) , Rotraut Merkle 1) , and Joachim Maier 1)
1) Max Planck Institute for Solid State Research, Heisenbergstr. 1, D-70569 Stuttgart, Germany
2) Max Planck Institute for Metals Research, Heisenbergstr. 3, D-70569 Stuttgart, Germany
While the bulk proton conductivity is high, the grain
boundaries of acceptor-doped BaZrO3 are highly
resistive, resulting in a low total conductivity in
polycrystalline samples [1-4]. One possible
explanation for this blocking character is the presence
of an excess positive charge in the grain boundary
core and depletion of protons, holes and oxygen
vacancies in the adjacent space charge zone. To gain
evidence for this space charge model, Y-doped
BaZrO3 (sintered by SPS “Spark Plasma Sintering”:
1600°C, 5 min, 50 MPa) was reduced using a layer of
metallic zirconium (Fig. 1). The absence of blocking
grain boundaries in the reduced (Fig. 2), nconducting
ceramic is an evidence for a positively
charged core (electron accumulation in the space
charge zone).
The grain boundary properties depend strongly on
processing conditions. The grain boundary
conductivity of Sc- or Y- doped BaZrO3 sintered by
SPS increases by a factor of 10 to 1000 at 300°C with
additional high-temperature annealing (1700°C for 20
h). Quantitative energy-dispersive X-ray
spectroscopy in the TEM showed a significant
segregation of negatively charged dopants to the
grain boundary region (core and/or to the space
charge layers). The detected dopant segregation is
more pronounced for the grain boundaries with
higher conductivity increase. In addition, different
contributions
of segregation driving forces in Y-
doped
and Sc-doped BaZrO3 are considered.
P 35
Fig. 1 SPS-6at%Y-BaZrO3 (a) before reduction (b)
after reduction and removing the oxidized Zr layer
1.
2.
K. D. Kreuer, Annual Review of Materials Research 33
(2003), 333.
F. Iguchi, T. Yamada, N. Sata, T. Tsurui, and H. Yugami,
Solid State Ionics 177 (2006), 2381.
Fig. 2 (a) Blocking grain boundaries in 6at%Ydoped
BaZrO3 in dry N2 and at 24 °C (b) absence of
blocking grain boundaries in reduced sample
3. Y. Yamazaki, R. Hernandez-Sanchez, and S. M. Haile,
Chemistry of Materials 21 (2009), 2755.
4. C. Kjolseth, H. Fjeld, O. Prytz, P. I. Dahl, C. Estournes, R. Haugsrud, and T. Norby, Solid State Ionics 181 (2010),
268.
‐ 77 ‐

Synthesis and characterization of BaCe0.7Zr0.1Y0.1Yb0.1O3-δ proton
conducting ceramic
Siwei Wang, Fei Zhao, Lingling Zhang, and Fanglin Chen*
Department of Mechanical Engineering, University of South Carolina, Columbia, SC 29208, USA
BaCe0.7Zr0.1Y0.1Yb0.1O3-δ proton conducting material
for intermediate temperature solid oxide fuel cells
(IT SOFCs) applications has been prepared by a
modified pechini method [1]. Pure perovskite
structured materials were obtained with calcination
temperatures T≥1000 o C. The thermal expansion
coefficient (TEC) for BaCe0.7Zr0.1Y0.1Yb0.1O3-δ is
9.1-9.7×10 -6 K -1 from 25 to 1100 o C, which is
favorably matched with that of Pr based cathode
materials [2]. The microstructures of the samples
sintered at different temperatures from 1350 to
1550 o C were analyzed, revealing denser
microstructure with higher sintering temperatures.
The correlation between the microstructure and the
conductivity was investigated. The sample sintered at
1400 o C showed the highest conductivity (Figure 1),
indicating that the beneficial effects on conductivity
from denser samples was counteracted by the
segregation of secondary phases in the grain
boundaries
at higher sintering temperatures [3].
1. F. Zhao, Q. Liu, S. Wang, K. Brinkman and F. Chen,
International Journal of Hydrogen Energy 35 (9) 4258.
2. F. Tietz, Ionics 5 (1999) (1) 129.
3. J. Lv, L. Wang, D. Lei, H. Guo and R.V. Kumar, Journal of
Alloys and Compounds 467 (2009) (1-2) 376.
[*] Corresponding Author: (Tel.) 803-777-4875; (E-mail):
chenfa@cec.sc.edu
‐ 78 ‐
ln(��) (S.K/cm)
ln(��) (S.K/cm)
4.0
3.5
3.0
2.5
2.0
1.5
1.0
3.5
3.0
2.5
2.0
1.5
P 36
Temperature (
800 750 700 650 600 550 500 450
o C)
(a) Wet Air
sample A
sample B
sample C
sample D
sample E
0.9 1.0 1.1 1.2 1.3 1.4
1000/ T (1/K)
Temperature (
800 750 700 650 600 550 500 450
o C)
(b)
Wet H 2
sample A
sample B
sample C
sample D
sample E
1.0
0.9 1.0 1.1 1.2
1000/ T (1/K)
1.3 1.4
Fig. 1 Arrhenius plots of conductivity for
BaCe0.7Zr0.1Y0.1Yb0.1O3-δ samples
sintered at different temperatures in (a)
wet air and (b) wet H2, sample A-E
indicating sintering temperatures from
1350-1550 o C, at 50 o C intervals.

High flux ND-study of the structural phase transition in LaNbO4
Christopher S. Knee 1 , Morten Huse 2 , Truls Norby 2 , Sten G. Eriksson 3 , Reidar Haugsrud 2
1 Department of Chemistry, University of Gothenburg, SE-412 96 Göteborg, Sweden
2 Department of Chemistry, University of Oslo, FERMiO, Gaustadalléen 21, NO-0349 Oslo, Norway
3 Department of Environmental Inorganic Chemistry, Chalmers Univ. of Technology, SE-412 96 Göteborg, Sweden
P 37
In the last decade renewed interest in LaNbO4 has emerged due to reports of appreciable proton
conductivity and high proton transference number [1] as well as expected high stability in CO2 and
CO2-H2O atmospheres. Consequently, LaNbO4 has been proposed as a candidate electrolyte
material for proton conducting SOFCs. LaNbO4 exhibits a second order phase transition at ≈ 520 °C
from a monoclinic structure (� ≈ 94 ° at RT) to a tetragonal
cell (�� = 90 °). This has a strong impact on the material’s
conductivity (Fig. 1). The figure suggests that the enthalpy of
proton mobility is significantly higher in the low temperature
monoclinic phase. This is supported by a recent computational
study on LaNbO4 [2] which also identifies an inter-tetrahedral
pathway as the rate limiting step for proton migration. Here,
we use data collected on the high flux neutron diffractometer
D20 at the Institut Laue Langevin to accurately map the
changes in the La-O and NbO4 environments through the
second order phase transition. We find that the oxygen to
oxygen distance between neighboring NbO4 tetrahedra, which
is suggested as the rate limiting step for proton migration,
decreases with increasing temperature up to the transition
temperature, from where this separation was constant. To
explain the difference in proton mobility in the two
polymorphs we suggest that as the oxygen-oxygen distance
decreases the proton jump distance decreases and
consequently the activation barrier for inter-tetrahedral proton
transfer decreases.
Fig. 1 a) Conductivity vs. 1/T in various
atmospheres [1]
This investigation was supported by the Research Council of Norway (grant number 187160) within the N-INNER
program.
1.
R. Haugsrud, T. Norby, Solid State Ionics 177 (2006), p. 1129.
2.
H. Fjeld, K. Toyoura, R. Haugsrud, T. Norby, Phys. Chem. Chem. Phys., (2010) DOI:10.1039/c002851g.
‐ 79 ‐

Performance of SOFC with proton-conductor BaCe0.7In0.2Yb0.1O3-δ
electrolyte
Fei Zhao, Latoya Dixon and Fanglin Chen *
Department of Mechanical Engineering, University of South Carolina, Columbia, SC 29208, USA
Recently significant efforts have been focused on
the development of electrolyte materials for protonconducting
SOFCs. The strategy of co-doping has
been successfully applied to BaCeO3 with M
(M=Ta, Ti, In, Nb and Sn) and Y as the co-dopants
and proved to maintain both high conductivity and
good stability [1, 2]. In this work, the proton
conductor BaCe0.7In0.2Yb0.1O3-δ (BCIYb) was
fabricated by co-doping In and Yb at the Ce-site of
BaCeO3. Pure perovskite structure was obtained
with calcination temperatures T≥1000 o C. The
conductivities of BCIYb pellets sintered at 1450 o C
for 5h were obtained in different atmospheres
(shown in Fig. 1). The performance of the single
cell with BCIYb as electrolyte was also
investigated. As shown in Fig. 2, the cell showed
aximum power outputs of 0.170, 0.238 and 0.303
cm -2 at 600, 650 and 700 o m
W
C, respectively.
1. K. Xie, R. Q. Yan and X. Q. Liu, Journal of Alloys and
Compounds 479 (2009) L40.
2.
F. Zhao, Q. Liu, S.W. Wang, K. Brinkman and F. Chen,
International Journal of Hydrogen Energy 35 (2010), 4258.
[*] Corresponding Author: (Tel.) 803-777-4875;
(E-mail): chenfa@cec.sc.edu
‐ 80 ‐
Fig. 1 Temperature (T) dependence of total
conductivity (σ) of BaCe0.7In0.2Yb0.1O3-δ in
different atmospheres.
P 38
Fig. 2 Performance of the single cell under
humidified hydrogen atmosphere at different
temperatures.

Ionic conduction in Mg–Al and Zn-Al layered double hydroxide
intercalated with inorganic anions
Kiyoharu Tadanaga, Yoshihiro Furukawa, Akitoshi Hayashi, and Masahiro Tatsumisago
Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University,
Sakai, Osaka 599-8531, Japan
Layered double hydroxides (LDHs) are inorganic
layered materials consisting of positively charged
metal hydroxide layers and interlayer anions as
well as water molecules. LDHs have been widely
studied as ion-exchangers and trapping agents for
anionic contaminants owing to their anionexchangeable
property. In this study, the ionic
conductivity of Mg-Al LDHs and Zn-Al LDHs
intercalated with various inorganic anions such as
CO3 2- , Cl - , Br - , NO3 - and SO4 2- was evaluated.
The ionic conductivity of LDHs was found to be
affected by interlayer anions, but the effects of
anions were different between Mg-Al and Zn-Al
LDH systems. Figure 1 shows temperature
dependence of conductivities of Mg-Al LDH
intercalated with CO3 2- , Cl - , Br - , NO3 - and SO4 2-
under 80% relative humidity. In Mg–Al LDH
system, Mg-Al LDH intercalated with Br -
exhibited the highest ionic conductivity, and the
conductivity decreased in the order of Br - >Cl -
=NO3 - = CO3 2- > SO4 2- [1]. The ionic conductivity
of Mg-Al LDH intercalated with Br - was 1.1 ×
10 - 2 S cm -1 at 80°C under 80% relative humidity.
Figure 2 shows conductivities of Zn-Al LDH
intercalated with CO3 2- , Cl - , Br - , NO3 - and SO4 2-
under 80% relative humidity. In the Zn-Al LDHs,
the ionic conductivity is rather low compared with
that of Mg-Al LDHs. Zn-Al LDH intercalated
with NO3 - exhibited the highest ionic conductivity,
and the conductivity decreased in the order of
NO3 - > Cl - > Br - = SO4 2- > CO3 2- . The
electromotive force for the water vapor
concentration cell using Mg–Al and Zn-Al LDHs
showed the same behavior with that using an anion
exchange
membrane, indicating that these LDHs
are
a hydroxide ion conductor.
1. Y. Furukawa, K. Tadanaga, A. Hayashi, and M.
Tatsumisago, Solid State Ionics (2010),
DOI: 10.1016/j.ssi.2010.05.032 .
‐ 81 ‐
Conductivity / S cm -1
Conductivity / S cm -1
10 -1
10 -2
10 -3
10 -4
2.8 2.9 3 3.1 3.2 3.3
1000/T / K -1
10 -3
10 -4
10 -5
10 -6
Mg3-Al CO3 2�� Mg3-Al Cl
LDH
�� LDH
Mg3-Al SO4 2�� Mg3-Al NO3
LDH
�� Mg3-Al Br
LDH
�� LDH
2.8 2.9 3 3.1 3.2 3.3
1000/T / K -1
P 39
Fig. 1. Temperature dependence of conductivities of
Mg-Al LDH intercalated with CO3 2- , Cl - , Br - ,
NO3 - and SO4 2- under 80% relative humidity
Zn2-Al CO3 2�� Zn2-Al Cl
LDH
�� Zn2-Al NO3
LDH
�� LDH
Zn2-Al SO4 2��LDH Zn2-Al Br �� LDH
Fig. 2. Temperature dependence of conductivities of
Zn-Al LDH intercalated with CO3 2- , Cl - , Br - , NO3 -
and SO4 2- under 80% relative humidity

Determination of the enthalpy of hydration of
oxygen vacancies by TG-DSC
Christian Kjølseth 1 , Andreas Løken 1 , Lin-Yung Wang 2 , Reidar Haugsrud 1 and Truls Norby 1
1 Department of Chemistry, University of Oslo, FERMiO, Gaustadallèen 21, NO-0349 Oslo, Norway
2 Department of Chemistry, National Taiwan University, No.1, Lane 4, Roosevelt Rd., Taipei, Taiwan (R.O.C.)
P 40
Accurate determination of the hydration thermodynamics is vital for the fundamental understanding
and further progression towards application of high temperature proton conductors. Hydration
thermodynamics have traditionally been determined indirectly, based on modeling of experimental
data from the water up-take in thermogravimetry or from partial and total conductivity
measurements - relying on defect chemical models and often resulting in unreliable and correlated
values (see e.g. [1,2]). In this contribution we report on combined thermogravimetry (TG) and
Differential Scanning Calorimetry (DSC), TG-DSC, as a novel experimental approach to measure
directly the standard molar hydration enthalpies of high temperature proton conductors. The
technique is demonstrated for several high temperature proton conductors, e.g. two of the most
studied proton conducting perovskite, BaZr0.9Y0.1O3-δ (BZY10) and BaCe0.9Y0.1O3-δ (BCY10). The
measurements were conducted isothermally by parallel recording of the weight and heat exchanges
associated with step changes in the water vapor pressure.
Heat exchange / mW mg -1
0,05
0,00
-0,05
-0,10
-0,15
-0,20
BaZr 0.9 Y 0.1 O 3-�
45 50 55 60 65 70
Time/min
100,2
100,1
100,0
99,9
99,8
99,7
Weight change / %
Heat exchange / mW mg -1
‐ 82 ‐
0,12
0,10
0,08
0,06
0,04
0,02
0,00
-0,02
-0,04
-0,06
BaCe 0.9 Y 0.1 O 3-�
45 50 55 60 65 70
Time/min
Fig. 1 TG‐DSC signals recording hydration of BaZr0.9Y0.1O3‐δ and BaCe0.9Y0.1O3‐δ
at 600 °C.
Fig. 1 shows the typical response in the TG-DSC signals following a shift in the gas from 1 atm N2
to 1 atm H2O for BZY10 and BCY10 at 600 °C. The relative weight of the specimen increases
abruptly as a consequence of the interaction with the water vapour. Simultaneously, we experience a
peak in the DSC signal representing an exothermic process. The obtained molar hydration enthalpy
of BZY10 was investigated at 300 - 900 °C and was found constant at -81±4 kJ mol -1 (per mole of
H2O) over this range. The molar hydration enthalpy of BCY10 was investigated at 600 °C and found
to be -170±6 kJ mol -1 . Both values are in good agreement with the majority of literature data for the
two materials obtained more indirectly by equilibrium methods.
1. R. Haugsrud and T. Norby, Nature Materials 5 (2006) (3), p. 193.
2. K.D. Kreuer et al., Solid State Ionics 145 (2001) (1-4), p. 295.
100,1
100,0
99,9
99,8
99,7
Weight change / %

Proton Transfer and Hydration in 3M Ionomers with Different Protogenic
Groups
Jeffrey K. Clark, and Stephen J. Paddison
Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, TN 37996, USA
P 41
Proton exchange membranes (PEMs) are the electrolyte in current hydrogen fuel cells and function
as not only the separator of the electrodes and reactant gases but importantly as the internal ion
conductor. Efficient operation of these energy conversion devices in diverse applications (vehicular,
portable, and stationary) places demands on the PEM which include: long-time thermal and
chemical stability (including resistance to oxidation and degradation by reactive species) at
temperatures as high as 120°C, and high proton conductivity (≈ 10 -1 Scm -1 ) under low humidity
conditions (25-50% relative humidity). Although a large number of strategies have been devised in
the
pursuit to design membrane materials that meet these requirements current PEM fuel cells still
utilize perfluorosulfonic acid (PFSA) ionomers such as Nafion®.
We present a molecular modeling study on the
role of local hydration, side‐chain connectivity, and
protogenic group separation in effecting proton
dissociation in oligomeric fragments of 3M
ionomers at minimal hydration. Two types of
ionomers, each consisting of a polytetrafluoro‐
ethylene (PTFE) backbone, were considered in this
study. These are: (1) perfluorosulfonic acid (PFSA)
membranes at different equivalent weights with
two pendant side‐chains of distinct separation
(with chemical formula CF3CF(‐O(CF2)4SO3H)(CF2‐
CF2)nCF(‐O(CF2)4SO3H)CF3, with n = 1 and 2) and
(2) imide fragments of structural isomers with
multiple and distinct pendant acid groups (with
chemical formula CF3CF2CF(‐
O(CF2)4SO2(NH)SO2C6H4SO3H)CF3 with the
sulfonic acid group located in either the meta or the ortho position). The initial ‘dry’
optimizations of these structures are shown in Figure 1. Fully optimized structures of these
fragments with and without the addition of water molecules at the B3LYP/6‐311G** level
revealed that both side‐chain connectivity and protogenic group separation, along with local
hydration, are key contributors to proton dissociation in these membranes. Specifically,
interaction between protogenic groups via hydrogen‐bonding networks proved to be
necessary for proton dissociation at low levels of hydration.
Figure 1. Fully optimized ‘dry’ 3M oligomeric fragments: (a) EW 590 g/mol PFSA where n=1, (b) EW 690 g/mol
PFSA where n=2, (c) meta bis acid, and (d) ortho bis acid. Atom color in the structures: grey–carbon, red–oxygen,
yellow–fluorine, orange –sulfur, blue–nitrogen, and white–hydrogen.
‐ 83 ‐

Electrical Conductivity and Defect Structure of Y-doped BaZrO3
Ho-Il Ji, Jong-Ho Lee * , Hae-Ryoung Kim, Ji-Won Son,
Hae-Weon Lee and Byung-Kook Kim
High Temperature Energy Materials Center, Korea Institute of Science and Technology, Seoul 136-791, Korea
Rare earth doped BaZrO3 is one of the promising proton conducting oxides due to its high proton
conductivity and fair chemical stability. However, poor sinterability of doped BaZrO3 has been a
critical barrier to be employed as a solid electrolyte of fuel cell. For this reason there have been
many efforts to improve the sinterability of doped BaZrO3 by adopting sintering aids such as CuO,
ZnO.
In this study, we measured the electrical conductivity of Y doped BaZrO3 (BZY) with- and without
a sintering aid, (Cu, Zn) as a function of temperature, oxygen partial pressure and water vapor
pressure and investigated the influence of sintering aids on its electrical property and defect
structure. For a more quantitative defect structural analysis, proton concentrations were precisely
measured by a Thermo-Gravimetric Analysis (TGA). On the basis of conductivity and TGA results,
equilibrium concentrations of each ionic and electronic charge carrier was calculated and presented
in a three dimensional space (X axis: oxygen partial pressure, Y axis: water vapor pressure, Z axis:
ionic & electronic conductivity or concentration of ionic & electronic charge carriers).
‐ 84 ‐
P 42

Enhanced Sinterability of Y-doped BaZrO3 Powder Synthesized with CuO,
ZnO Addition as a Sintering Aid
Jong-Ho Lee, Seong-Jeong Hong, Ho-Il Ji, Jong-Sung Park, Hae-Ryoung Kim,
Ji-Won Son, Hae-Weon Lee, and Byung-Kook Kim *
High Temperature Energy Materials Center, Korea Institute of Science and Technology, Seoul 136-791, Korea
Rare earth doped BaZrO3 is known to be very difficult to sinter (for example, ρ < 0.95ρth when it is
sintered at 1700 o C for 10h) even though it is one of promising proton conducting oxides with high
proton conductivity and good chemical stability. Such low sinterability of BaZrO3 has given many
technical challenges for fuel cell application such as difficulty in thin and dense film formation
under moderate sintering temperature without any chemical interaction with other cell components.
Recently, it was reported that the addition of ZnO significantly enhanced the sinterability of Ydoped
BaZrO3 (BZY) which might give proper processing accessibility to use it as a solid
electrolyte of fuel cells. However it is still not well understood how this sintering aid influences on
the physico-chemical properties of BZY. In the present study, we report the effects of Zn and Cu
addition on the sinterability and the proton conductivity of BZY. The possible sintering mechanism
as well as the defect structural changes of BZY due to the addition of sintering aids will be also
discussed.
‐ 85 ‐
P 43

Intermediate temperature solid oxide fuel cells based
on a thin BaZr1-xYxO3-δ proton conductor electrolyte
Daniele Pergolesi, Emiliana Fabbri, and Enrico Traversa
International Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science
(NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044 Japan
P 44
High temperature proton conductors have been the subject of extensive investigation because of
their potential application as electrolytes in intermediate temperature solid oxide fuel cells (IT-
SOFCs). Among this class of materials, Y-doped BaZrO3 (BZY) exhibit excellent chemical
stability, but BZY total proton conductivity is too low for practical use.
The low conductivity of BZY derives from its poor sinterability, which leads to the presence of a
large amount of resistive grain boundaries. The possibility of overcoming low sinterability and high
grain boundary resistance, may lead to the development of an excellent electrolyte for IT-SOFCs.
Pulsed laser deposition (PLD) allows growing thin films with high density and an excellent degree
of structural quality.
Using PLD, anode-supported solid oxide fuel cells (SOFCs) based on thin BaZr0.8Y0.2O3-δ (BZY)
electrolyte films were fabricated on sintered NiO-BZY composite anodes (Figure 1). After in-situ
reduction of NiO to Ni, the anode substrates became porous, while retaining good adhesion with the
electrolyte. A slurry-coated composite cathode
made of La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) and
cathode
BaCe0.9Yb0.1O3-δ (BCYb), specifically developed
for proton conducting electrolytes, was used to
assemble fuel cell prototypes. Depositing by PLD
100 nm thick LSCF porous films onto the BZY
thin films was essential to improve the
BZY electrolyte
cathode/electrolyte adhesion.
The fuel cell performance of the developed
anode
device was examined in the IT range by means of
I-V
tests and electrochemical impedance
spectroscopy,
showing promising results.
‐ 86 ‐
Fig. 1 Ba deficiency, x, lowers bulk proton
conductivity in yttrium-doped barium zirconates.

Does the Increase in Y-Dopant Concentration Improve the Proton
Conductivity of BaZr1-xYxO3-δ Fuel Cell Electrolytes?
Fabbri Emiliana 1 , Daniele Pergolesi 1 , Silvia Licoccia 2 and Enrico Traversa 1
P 45
International Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science
(NIMS)1-1 Namiki, Tsukuba, Ibaraki 305-0044 Japan
Department of Chemical Science and Technology, University of Rome Tor Vergata, Via della Ricerca Scientifica, 00133
Rome, Italy
Among high temperature proton conductors, BaZrO3-based oxides offer excellent chemical stability
against reaction with CO2 and H2O. Yttrium acts as an ideal dopant for barium zirconate. Although
its substitution in the B site of the perovskite structure causes local lattice distortions, it almost does
not change the acid/base properties of the coordinating oxygen. This results in the highest
conductivity among doped barium zirconate oxides [1].
The strategy that we have followed to
improve the electrical properties of
barium zirconate is the optimization of
doping conditions, in terms of proper
selection of the dopant concentration. In
this study we investigated single phase
BaZr1-xYxO3-δ (BZYx) oxides, with x
ranging between 0.2 and 0.5, produced
by means of wet-chemical synthesis
procedures. Such high Yttrium dopant
concentrations (x larger than 0.4) have
never been explored before to the best of
our knowledge. Proton uptake, sintering
behavior, phase stability and electrical
properties of BZYx were studied as
function of Y concentration, providing a
comprehensive understanding of the
effect of high dopant concentrations on
the
properties of Y-doped barium
zirconate
proton conductor electrolyte.
1.
K.D. Kreuer, Annu. Rev. Mater. Res. 33 (2003), 333.
Fig. 1 Proton concentration and electrical conductivity as a
function of Y concentration for BaZr1‐xYxO3‐δ
‐ 87 ‐

Computational Modeling of Transport Phenomena in Polymer Electrolyte
Membranes, Nafion and Hydrocarbon Membrane
Yoong-Kee Choe
National Institute of Advanced Industrial Science & Technology (AIST), Umezono 1-1-1, Tsukuba, Japan
P 46
Results of the first-principles molecular dynamics (MD) simulations carried out to investigate
various transport properties in polymer electrolyte
membranes (PEMs) are presented. As is well known,
polymer electrolyte membrane fuel cells have attracted a
lot of interest because of their potential application for
automobile and mobile devices. Since transport properties
arising from proton and water diffusion affects the
performance of fuel cells, full comprehension of chemistry
and physics of these phenomena at an atomistic level is
necessary. To probe the nature of the transport properties,
we applied the techniques of the first-principles MD to
Nafion, a representative perfluorosulfonic acid based
membrane, and other hydrocarbon membranes. We found
that difference in the value of proton diffusion coefficient
with respect to water content inside PEMs is related to the
different character of proton hopping occurring in water
hydrogen bond network. Moreover, the results of the
first‐principles simulations allow us to explain the
relationship between the proton dynamics and electro‐
osmosis (co‐transport of water as a result of proton
conduction) at an atomistic level. Our first‐principles
MD study also shows that a hydrophillic functional
group found in various hydrocarbon membranes makes
a negative influence on the proton transport under low
hydration condition. The results of the simulation
indicate that such a functional group hinders effective
Fig. 1 Snapshots of the first-principles
hydration
around the sulfonic group in PEM and show tsimulation ha t it causes of Nafion Grötthuss with transport high water of
proton
to be ineffective.
content
1. Y. -K Choe, E. Tsuchida, T. Ikeshoji, S. Yamakawa and S. Hyodo, Journal of Physical Chemistry (B) 112 (2008),
11586.
2. Y. -K Choe, E. Tsuchida, T. Ikeshoji, S. Yamakawa and S. Hyodo, Physical Chemistry Chemical Physics 11
(2009), 3892.
3.
Y. -K Choe, E. Tsuchida, T. Ikeshoji, A. Ohira and K. Kidena, Journal of Physical Chemistry (B) 114 (2010), 2411.
‐ 88 ‐

Study of Proton Transport using Reactive Molecular Dynamics
Myvizhi Esai Selvan, David J. Keffer, Shengting Cui, Stephen J. Paddison
Department of Chemical and Biomolecular Engineering, University of Tennessee, 327 Dougherty Engineering,
Knoxville, TN 37996, USA
We have developed a new reactive molecular dynamics algorithm (RMD) to model the structural
diffusion of proton as a chemical reaction with input from both quantum mechanical and
macroscopic models. Structural diffusion is incorporated in a classical MD simulation via three
steps: (i) trigger satisfaction; (ii) instantaneous reaction; and (iii) local equilibration. We have
applied it to study proton transport in several systems including: bulk water, aqueous HCl, and
hydrated polymer electrolyte membranes (PEMs).
Proton transport in hydrated PEMs is influenced by the confinement into regions or domains that are
only a few nanometers in dimension and by the acidity of the sulfonic acid groups. The independent
effect of acidity and confinement on proton transport has been examined by studying the aqueous
HCl systems (0.22 – 0.83 M) and water filled carbon nanotubes (radius from 5.42 – 10.85 Å)
respectively. The presence of the chloride ion in aqueous HCl solutions disrupts the environment of
a proton both structurally and energetically leading to a reduced probability for proton transfer. We
determined that structural diffusion of a proton decreases with an increase in HCl concentration.
When the algorithm was implemented to study the proton diffusion through water filled carbon
nanotubes, the model showed that enhanced confinement drastically reduces structural diffusion by
disrupting the energetic ‘balance’ around the Zundel (H5O2 + ) cation.
Structural diffusion of a proton in a hydrated PEM can be categorized into three chemical reactions
based on the degree of hydration of the membrane and location of the hydrated protons. Proton
transport along the center of the aqueous channel is similar to that of bulk water (in terms of the
transition state) while it is different at the hydrophobic/hydrophilic interfacial regions as observed at
low hydration levels. We are currently trying to understand the individual contribution of these
reactions to the total charge diffusion and the correlation between structural and vehicular
components.
‐ 89 ‐
P 47

Hydrogen transport in LaNbO4-LaNb3O9 composites
Wen Xing 1 , Guttorm E. Syvertsen 2 , and Reidar Haugsrud 1
1 Department of Chemistry, University of Oslo, FERMiO, Gaustadalleen 21, NO-0349 Oslo, Norway
2 NTNU N-7491 Trondheim, Norway
P 48
Mixed protonic and electronic conductors have potentials for serving as membranes in hydrogen
separation technology. However, state-of-the-art materials possessing these functional properties
suffer from low chemical stability under operating conditions. The electrical properties of some of
the phases in the La2O3-Nb2O5 system have been subject to intensive characterization. During these
studies, it has been realized that small amounts of excess Nb in the proton conductor LaNbO4 leads
to segregation of the n-type electronic conductor LaNb3O9 along the grain boundaries. Combination
of the transport properties of these two materials may yield an interesting behavior with respect to
the ambipolar proton-electron conductivities, and as such be a potential candidate system for
hydrogen gas separation membranes.
Disc specimens of LaNbO4-LaNb3O9 composites (10 and
30 vol% LaNb3O9) were fabricated by spark plasma
sintering. The composition and microstructure have been
characterized by SEM-EDS and HRTEM. The electrical
conductivity and the hydrogen flux were characterized as
a function of the temperature, oxygen and water vapor
partial pressures. H/D isotope exchange was utilized to
verify transport of protons.
Figure 1 shows that the hydrogen flux varies with the
feed side hydrogen pressure with a (pH2) 1/2 dependency.
The temperature dependency of the flux density
corresponds to an activation energy of ~140 kJ/mol,
similarly to the activation energy for electronic
conduction in LaNbO4 phase, indicating that the hydrogen
permeation might be limited by electron transport at
measurement conditions. Moreover, the amount of
hydrogen in the permeate increases when changing
permeate gas from dry to wet Ar indicating that also
water splitting and oxide ion conductivity are at play.
Ln(J ,�mol/cm H2 2 Ln(J ,�mol/cm s)
H2 2 s)
-8.5 1000°C
960°C
940°C
-9.0 900°C
-9.5
-10.0
-10.5
-5 -4 -3 -2 -1 0
Ln(p H Ln(p 2
feed H2 feed
, atm)
1/2
Figure 1. Hydrogen flux as a function of the
hydrogen partial pressure at the feed side
In this contribution we will discuss the results from these measurements in view of ambipolar
transport theory to compare the measured flux values with estimates made from the conductivity
data of the composites and the individual material.
This work was initiated through the Big CO2 consortium, GES acknowledges funding through the
NanoPCFC project financed by the Research Council of Norway (182090/S10)
‐ 90 ‐

Poly(p-phenylene sulfone)s with High Ion Exchange Capacity: Ionomers with
Unique Microstructural and Transport Features
C. C. de Araujo 1 , K. D. Kreuer 1 , M. Schuster 2 , G. Portale 3 , and J. Maier 1
1. Max-Planck-Institut für Festkörperforschung, Heisenbergstraβe 1, D-70590 Stuttgart, Germany
2. FuMATech, Am Grubenstollen 11, D-66386 St. Ingbert, Germany
2.DUBBLE, BM26 at ESRF, 6 rue Jules Horowitz, BP220, F- 38043 Grenoble, Cedex, France
c.araujo@fkf.mpg.de
Current attempts to increase the operation temperature of PEM fuel cells are also driving the
development of membranes with high proton conductivity and stability at high temperature and low
humidification [1,2]. Poly(phenylene) ionomers which contain merely sulfone units (-SO2-)
connecting the phenyl rings and in which each phenyl ring is sulfonated (-SO3H) have been
showing to be an important advance in this direction [3-5]. The high degree of sulfonation of this
polymer leads to the development of a microstructure characterized by very narrow hydrated,
hydrophilic domains which are well connected on longer scales. These features together with high
absolute water uptakes at given relative humidities and the high charge carrier concentration
corresponding to the high ion exchange capacity (IEC ~ 4.5 meq./g) result in very high proton
conductivities but also low water transport coefficients (water diffusion and presumably also
electroosmotic drag and permeation). Compared to the transport properties of Nafion, these trends
increase with increasing water content and with increasing temperature. For a relative humidity of
RH = 30 % and a temperature of T = 135 °C, the proton conductivity is found to be seven times
higher than the conductivity of Nafion under the same conditions.
Understanding the properties of this highly sulfonated polymer with very high ion-exchange
capacity is of great interest considering that this is a potential material for applications in block
copolymer and polymer blend synthesis. A complete transport study in this new class of sulfonated
polymer will be presented including: proton conductivity measured by ac impedance spectroscopy,
diffusion coefficients and electroosmotic drag determined by PFG-NMR and Electrophoretic-NMR,
respectively, and microstructure studies by SAXS.
1. K.-D. Kreuer, S. J. Paddison, E. Spohr, and M. Schuster, Chem. Rev. 104, 4637–4678 (2004)
2. K. D. Kreuer, M. Schuster, B. Obliers, O. Diat, U. Traub, A. Fuchs, U. Klock, S. J. Paddison, and J. Maier, J. Power
Sources 178, 499–509 (2008).
3. M. Schuster, K.-D. Kreuer, H. T. Andersen, and J. Maier, Macromolecules 40, 598–607 (2007).
4. M. Schuster, C. C. de Araujo, V. Atanasov, H. T. Andersen, K.-D. Kreuer, and J. Maier, Macromolecules 42, 3129–
3137 (2009).
5. C. C. de Araujo, K. D. Kreuer, M. Schuster, G. Portale, H. Mendil-Jakani, G. Gebel, and J. Maier, Phys. Chem. Chem.
Phys. 11, 3305–3312 (2009).
‐ 91 ‐
P 49

Rule of superprotonic phase transition in CsxRb1-xH2PO4
Yasumitsu Matsuo 1) , Junko Hatori 1) , Yukihiko Yoshida 2) and Seiichiro Ikehata 2)
1) Faculty of Science and Engineering, Setsunan University, 17-8 Ikeda-Nakamachi, Neyagawa, Osaka 572-8508, Japan
2) Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjyuku-ku, Tokyo 162-8601, Japan
‐ 92 ‐
P 50
It is well known that the hydrogen-bonded material, CsH2PO4 (CDP), undergoes a superprotonic
phase transition from the low-temperature ferroelastic phase to the high-temperature paraelastic
phase at around 501 K. It is also known that the mixed crystals CsxRb1-xH2PO4 (x=0~1) also exhibit
the superprotonic conductivity. In these mixed crystals, the temperature of superprotonic phase
transition increases by the increase of x. Furthermore, we have indicated that the precursor effect in
proton conductivity in CDP is closely related to the component d of a spontaneous strain tensor,
which is calculated from the following equation using the lattice constants at ferroelastic phase.
1
tan( / 2 2arctan(
m /
2
a b
d � � �
In the present work, we have prepared with the mixed crystals and investigated the rule of the
superprotonic phase transition in the CDP-type compounds.
Figure 1 shows the relation between the superprotonic phase transition temperature Tc and the
component d. It is evident that Tc linearly increases with the decrease of the component d 2 . This
result indicates that the strain is an important
factor for the appearance of superprotonic
conductivity in the CDP-type compounds. In
addition, by the thermodynamic analyses, it was
found that the relation between the strain
component d and transition temperature Tc is
described with the terms of the changes in the
proton kinetic energy ΔK and entropy ΔS by the
superprotonic phase transition as follows;
1
�K
�Tc
�S
� kd
2
(2)
From these results, it is deduced that the
transition temperature Tc in CDP-type compounds
is determined by the interrelation between the
increase in the kinetic energy of proton, the
2
d 2
1.160
1.150
1.140
m
))
×10 –2
(1)
x = 1
x = 0.9 x = 0.8
x = 0.75
x = 0.6
x = 0.5
x = 0.4
220 240 260
T s ( o C)
Cs xRb 1–xH 2PO 4
x = 0.2
x = 0.25
increase in entropy and the release of strain energy. Fig. 1 Relation between Tc and d 2
i
S. M. Haile Actra Materialia 51 (2003) 5981
ii
H. Matsumoto, T. Shimura, T. Higuchi, T. Otake, Y. Sasaki, K. Yashiro, A. Kaimai, T. Kawada, J. Mizusaki,
Electrochemistry, 72 (2004) 861
iii
H. Matsumoto, T. Shimura, T. Higuchi, H. Tanaka, K. Katahira, T. Otake, T. Kudo, K. Yashiro, A. Kaimai, T.
Kawada, J. Mizusaki, Journal of The 152 (2005) A488
iv
S. Mimuro, S. Shibako, Y. Oyama, K. Kobayashi, T. Higuchi, S. Shin, S. Yamaguchi, Solid State Ionics, 178 (2007)
647

Hydration and protonic conductivity in LaAsO4 based ceramics
Tor S. Bjørheim, Truls Norby and Reidar Haugsrud
Department of Chemistry, University of Oslo, FERMiO, Gaustadallèen 21, NO-0349 Oslo, Norway
Significant proton conduction has been
reported for a variety of rare-earth orthophosphates
[1-3], -vanadates [4], -niobates
[5] and -tantalates [6]. A natural
continuation along similar lines of
compounds is the rare-earth ortho-arsenates,
LnAsO4.
Incorporation and transport of protonic
defects has been studied in nominally
undoped and 1 and 3 mol% Sr-doped
LaAsO4 ceramics. The AC impedance of the
materials was measured as a function of
temperature (1150 - 400 °C), (1 - 1·10 -
5
atm) and (0.025 – 3·10 -5 p H 2O
atm).
p 2
H O
The bulk conductivity decreases with
decreasing p H within the whole
2O
temperature range, and with decreasing pO2
at the highest temperatures. A significant
isotope effect shows that protons contribute
to the total conductivity at all temperatures
under wet conditions and completely
dominate at temperatures below ~850 °C.
The remaining contributions are attributed to
oxide ions, and also electron holes at the
highest temperatures (see Fig. 1).
Based on the results, the defect structure of
Sr-doped LaAsO4 was concluded to be
dominated by oxide ion vacancies in the
4-
form of pyro-arsenate ions, As2O7
, in dry
atmospheres at high temperatures, and by
protonic defects in the form of hydrogen
-
arsenate groups, HAsO 4 , in wet
atmospheres. Hydration thermodynamics
extracted by modeling of the conductivity
data are comparable to those determined for
other LnXO4 (X=P,V,Nb) compounds.
- 93 -
P 51
Fig. 1: Measured total and modeled partial
conductivities of 3 mol% Sr-doped LaAsO4
Activation energies for the mobility of
protons are slightly lower than those
determined for LaPO4. However, the partial
proton conductivities of 4·10 -6 to 5·10 -5
S/cm between 500 and 925 °C for 3 mol%
Sr-doped LaAsO4 are lower than those
determined for acceptor doped LaPO4.
The
authors gratefully acknowledge the Norwegian
Chemical
Society for financial support
1. T. Norby and N. Christiansen, Solid State
Ionics 77 (1995), p. 240.
2. K. Amezawa, Y. Tomii and N. Yamamoto,
Solid State Ionics 176 (2005) (1-2), p. 135.
3. K. Amezawa, H. Maekawa, Y. Tomii and N.
Yamamoto, Solid State Ionics 145 (2001) (1-
4), p. 233.
4. M. Huse, T. Norby and R. Haugsrud, in
preparation, 2010.
5. R. Haugsrud and T. Norby, Nat. Mater. 5
(2006) (3), p. 193.
6.
R. Haugsrud and T. Norby, J. Am. Ceram.
Soc. 90 (2007) (4), p. 1116.

Investigation of hydrogen permeation in mixed conductor LaWOX
(La/W = 5.6)
Skjalg Erdal and Reidar Haugsrud
Department of Chemistry, University of Oslo, Centre for Material Science and Nanotechnology, FERMiO,
Gaustadallèen 21, NO-0349 Oslo, Norway
To date, no known material combines
sufficiently high ambipolar proton-electron
conductivity with chemical and thermal
stability to be used as H2 separation
membranes under typical conditions for
methane steam reforming or coal gasification.
In an effort to uncover materials with sufficient
hydrogen uptake and transport to possibly
serve in hydrogen separation membranes, the
hydrogen permeation through mixed conductor
lanthanum tungstate (LWO) has been
investigated.
LWO was synthesized via a wet chemical
gelling and combustion method. The nominal
La to W ratio (5.6/1) was chosen to ensure we
stay within the compositional window of single
phase LWO, as identified by Magrasó et. al
[1].
Figure 1a presents the hydrogen permeativity
in LWO as a function of temperature, from
1000 to 700 °C, for various feeds. The
hydrogen flux increases with increasing
temperature and feed side pH2 in the entire
temperature range. Above about 850 °C, the
flux is higher for a feed consisting of wet
H2/He than for dry H2/He, but this picture is
reversed as we go below 850 °C, presumably
due to the more reducing conditions needed to
maintain the n-type conductivity at lower
temperatures. The results further support
earlier speculations that the lanthanide
tungstates (in [2]: Er, Gd) have the ability to
incorporate protons through a partial reduction
of the oxide in contact with hydrogen gas [2].
Acknowledgements: This work was supported by the
FRINAT project 171157/V30 “Hydrogen in oxides
(HYDROX)” of the Research Council of Norway.
Permeativity H 2 (mL/min cm)
10 -3
10 -4
10 -5
0.0008 0.0009 0.0010
1/T (K -1 Feed side:
Wet H2 Dry H /He 2
Wet H /He 2
a)
)
Permeativity H 2 (mL/min cm)
10 -3
10 -4
10 -5
10 -3
1000 °C
900 °C
800 °C
10 -2
10 -1
�pH2 (atm)
P 52
10 0
b)
Fig. 1 a) Hydrogen permeativity in lanthanum tungstate as
a function of inverse absolute temperature. Three different
feed side gas compositions are shown. b) Double
logarithmic plot of hydrogen permeativity in lanthanum
tungstate as a function of hydrogen partial pressure
gradient over membrane. Conducted at 1000, 900 and 800
°C. Dry Ar supplied to permeate side in both graphs.
Figure 1b shows the H2 permeativity as a
function of the difference in hydrogen partial
pressure over the membrane, at 1000-800 °C.
For a given temperature, the hydrogen
permeativity increases with increasing ΔpH2,
and this dependency is steeper towards the lower
partial pressure gradients.
Effects of water vapor in the permeate side Ar
have also been determined. At T > 800 °C, the
detected hydrogen concentration in the permeate
increases with increasing pH2O on the permeate
side. This can be understood in a context of
water splitting as a consequence of oxygen ion
conductivity - being negligible below 800 °C,
and rapidly increasing with increasing
temperature.
1. Magrasó, A.; Frontera, C.; Marrero-López,
D.;
Núñez,
P. Dalton Transactions, 2009.
2. R. Haugsrud Solid State Ionics, 178 (2007) 555–
560.
-94

Fabrication of Ca-doped Lanthanum Niobate electrolyte film by
Electrophoretic Deposition for PCFC applications
Francesco Bozza and Nikolaos Bonanos
Fuel Cells and Solid State Chemistry Division, Risø National Laboratory for Sustainable Energy, Technical University
of Denmark, P.O. Box 49, 4000 Roskilde, Denmark
Electrophoretic Deposition (EPD) has been applied to the preparation
of a dense calcium-doped lanthanum niobate electrolyte
film. The EPD technique consists of charging the particles to be
deposited by a suitable suspending medium. When an electric
field is applied to the suspension, the particles migrate to one of
the electrodes and deposit [1, 2]. Powder of La0.995Ca0.005NbO4,
a high temperature proton conductor [3], was suspended in a
solution of acetylacetone and iodine. The effects of suspension
composition and deposition conditions were analyzed in order to
identify a suitable set of EPD process parameters. The powders
were deposited on a composite substrate of La0.995Ca0.005NbO4,
NiO, binder and graphite. With this technique, a dense 8 µm film
of lanthanum niobate supported on a porous La0.995Ca0.005NbO4
/NiO substrate was obtained after sintering at 1200°C (Figure 1).
Moreover the technique was found to be effective for a mixture
of NiO and La0.995Ca0.005NbO4 which, after sintering, would
form a supporter of La0.995Ca0.005NbO4/NiO anode functional
layer. The morphology and gas tightness of the film are
investigated.
This work has been funded by the EU within the FP7 project Efficient
and robust fuel cell with novel ceramic proton conducting electrolyte
(EFFIPRO), grant agreement 227560.
1. P. Sarkar, P. S. Nicholson, J. Am. Ceram. Soc. 79 (1996), 1987.
2. F. Bozza, R. Polini, E. Traversa, J. Am. Ceram. Soc. 92 (2009), 1999.
3. R. Haugsrud, T. Norby, Nature Materials 5 (2006), 193.
- 95 -
P 53
Fig. 1 Cross sectional SEM of a dense
layer of La0.995Ca0.005NbO4 deposited on
a porous substrate of La0.995Ca0.005NbO4/
NiO and sintered in air at 1200°C.

Ab initio Molecular Dynamics study of proton dynamics and mobility in
phosphoric acid
Linas Vilciauskas a , Gabriel Bester a , Klaus-Dieter Kreuer a , Mark E. Tuckerman b
and Stephen J. Paddison c
a Max-Planck-Institut fü̈ r Festkö̈ rperforschung, Heisenbergstraße 1, D-70569 Stuttgart, Germany
b Department of Chemistry and Courant Institute of Mathematical Sciences, New York University, New York, New York
10003, USA
c Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, Tennessee 37996, USA
P 54
Proton transport is one of the most fundamental and crucial processes for all living creatures as
well as in a multitude of phenomena in chemistry and physics such as the function of many devices
like proton exchange membrane fuel cells [1]. Phosphoric acid above its melting point is probably
the best intrinsic proton conductor, having exceptionally high proton conductivity due to a high
degree of self-dissociation (~7 %) and, despite its extremely high viscosity (~120 cP), proton
mobility only comparable to that of aqueous systems. The development of new water-free PEM fuel
cell materials calls for a fundamental understanding of these systems. It is clear that the proton
conduction mechanism is dominated by the structure diffusion however the exact details on how
many molecules [2] are involved in the elementary processes as well as what is its rate limiting step
must still be elucidated. The limited availability of experimental tools capable of probing the
corresponding time and length scales makes the molecular modeling techniques indispensable. The
ab initio molecular dynamics (AIMD) techniques were exceptionally successful in studying the
proton transport processes in diverse media. We performed a set of Car-Parrinello 3 molecular
dynamics simulations, employing a popular BLYP exchange-correlation functional and norm
conserving Troullier-Martins pseudopotentials to treat the core electrons. The kinetic energy cut-off
of 100 Ry was used to expand the electronic wavefunctions around the �-point and the time step of
0.1 a.u. was used to propagate the dynamics. The calculated radial distribution functions and
diffusion constants show a very good agreement with the available experimental data [3,4]. The
D H /D P ratio is ~5 showing that the intermolecular proton transfer is dominating over the vehicular
transport. The rotational dynamics of the phosphate groups in H3PO4 is clearly much more
constrained that in the case of similar systems with fast proton transport such as CsHSO4, CsH2PO4
and probably H3PO3 as well. Most of this effect might be attributed to the high concentration of
protons and the ‘frustrated’ H-bond network (3 proton donors vs. just 1 proton acceptor), but
interestingly, this doesn't hinder the proton dynamics clearly showing that the full rotational
reorientation or ‘tumbling’ of the PO4 group is not necessary for the successful proton transfer (PT)
event. In addition, the strong presence of Grotthuss-like PT events as evident from the simulation
indicates a strong Coulombic coupling between the protons over the O-P-O bonds, which is also
accelerating the overall dynamics. The calculated PT free energy barrier is just 1.8 kcal/mol,
confirming the fact that PT is completely governed by the solvent dynamics. The protons show a
fast hopping between the donor and acceptor on a time scale of 440 fs and only a little angular
rotation on a much slower time scale of 3.6 ps is necessary for the successful event. Moreover, there
are still a lot of very interesting open questions left to answer when dealing with this and similar
systems
such as what is the role of equilibrium water, which is even present in the nominally dry
acid
or how is everything affected by changing the ratio of proton donor/ acceptor sites (e.g. H3PO3).
1. Kreuer, K.D.; Paddison, S.J.; Spohr, E.; Shuster, M.; Chem. Rev. 2004, 104, 4637.
2. Vilciauskas, L.; Paddison, S. J.; Kreuer, K. D.; J. Phys. Chem. A 2009, 113, 9193.
3. Car, R.; Parrinello, M.; Phys. Rev. Lett. 1985, 55, 2471.
4. Dippel, Th.; Kreuer, K.D.; Lassègues, J.C.; Rodriguez, D.; Solid State Ionics 1993, 61, 41.
5. Aihara, Y.; Sonai, A.; Hattori, M.; Hayamizu, J. Phys Chem. B 2006, 110, 24999.
- 96 -

CsH2PO4 nanoparticle synthesis via electrohydrodynamic atomization –
aerosol size measurements
Áron Varga † , Andrew J. Downard ‡ , Hyung Wan Do § , Richard C. Flagan ‡ , Sossina M. Haile †‡
† Department of Materials Science, ‡ Department of Chemical Engineering, § Department of Electrical Engineering,
California Institute of Technology, 1200 E. California Blvd., Pasadena, CA 91125, USA
P 55
It has been shown that solid acid fuel cells based on CsH2PO4 (CDP) are performance limited by the
oxygen electroreduction reaction. 1 Increasing the length of the electrocatalytically active triple
phase boundaries by creating a 3-dimensional, interconnected, porous structure of CDP and Pt
nanoparticles is thought to improve the utilization of Pt catalyst and hence increase fuel cell
performance. 2 Electrohydrodynamic atomization (EHA), a process where an aqueous solution of
CDP is sprayed under high voltage, has emerged as a suitable method of generating CDP
nanoparticles and directly depositing them onto the substrate of choice. 3
The EHA method has an extremely large parameter space, which includes solution properties such
as conductivity and surface tension, spray parameters, such as voltage, flow rate, and geometrical
aspects. To optimize the process relative
to these parameters, an aerosol particle
sizing system, consisting of a 210 Po
neutralizer, a tubular differential mobility
analyzer (TDMA), and a condensation
particle counter (CPC) has been
constructed. The highly charged,
polydisperse aerosol generated by EHA is
introduced into the neutralizer, reducing
the charge per particle to a uniform value.
Based on the electrophoretic mobility of
the particles, the TDMA selects a narrow
size range to pass through to the CPC,
where the concentration is counted. Fine-
tuning the parameters has lead to the
generation of 41 nm diameter CDP
particles – a value approached that of the
Figure 1 CsH2PO4 (CDP) particle size distribution as generated
via electrohydrodynamic atomization and measured with a
differential mobility analyzer
Pt catalyst particles. The result holds promise for increases in Pt utilization and hence solid acid fuel
cell performance.
1 S. M. Haile, C. R. I. Chisholm, K. Sasaki, D. A. Boysen and T. Uda, Faraday Discussions (2007) 134, 17-39.
2 C. R. I Chisholm, D. A Boysen, A. B. Papandrew, S. Zecevic, S. Cha, K. Sasaki, A. Varga, K. P. Giapis and S. M.
Haile, Interface Magazine (2009) 18, 53-59.
3 A. Varga, N. A. Brunelli, K. P. Giapis, S. M. Haile, Journal of Materials Chemistry (2010) 20, 6309 – 6315.
-97-

Cobalt and yttrium doped barium zirconates as mixed conducting
cathodes for SOFC
Björn Björnsson, Juan C. Lucio-Vega, Yoshihiro Yamazaki, and Sossina M. Haile
Materials Science, California Institute of Technology, 1200 E California Blvd., Pasadena, CA 91125, USA
P 56
Mixed ionic and electronic conductors have been shown to be highly effective as cathode materials
in solid oxide fuel cells based on oxide-ion conducting electrolytes [1, 2]. The mixed transport
relaxes the restriction that electrochemical reactions occur at the triple-phase boundary between the
gas phase, the electrolyte, and the cathode electrocatalyst. Instead, reactions over the entirety of the
cathode electrocatalyst surface can be supported. By analogy, it is anticipated that mixed proton–
electronic hole conductors will be suitable for the oxygen electroreduction reaction [3].
over the entire oxide-gas interface. As the first step to test such
a hypothesis, we introduced cobalt into 20 at% yttrium-doped barium zirconate, a well-known
proton conducting oxide. Cobalt addition has been found to enhance electronic hole conduction
under oxidizing atmospheres and at temperatures relevant to intermediate temperature solid oxide
fuel cells (400-500 °C) [4]. Single phase-perovskite phase is observed here in BaZr0.8-xCoxY0.2O3-δ
up to x = 0.3 (at 1300 °C), for materials prepared by chemical solution methods. The results of
transport measurements and thermogravimetric analysis are presented.
2H � � 1/2O (g) � 2h 2 � � H O(g) 2
1. S.B. Adler, Chemical Reviews 104 (2004) (10), p. 4791.
2. Z.P. Shao and S.M. Haile, Nature 431 (2004) (7005), p. 170.
3. R. Peng, T. Wu, W. Liu, X. Liu and G. Meng, Journal of Materials Chemistry 20 (2010), p. 6218.
4. M.A. Azimova and S. McIntosh, Solid State Ionics 180 (2009) (2-3), p. 160.
- 98 -

High-temperature phase behavior in the Rb3H(SO4)2-RbHSO4
pseudo-binary system
Chatr Panithipongwut, Sossina M. Haile
Materials Science, California Institute of Technology, 1200 E California Blvd., Pasadena, CA 91125 USA
P 57
Many solid acids in the M3H(XO4)2 family (M = Cs, Rb, NH4, X = S, Se) transform from a
monoclinic phase at room temperature to a superprotonic, trigonal phase at elevated temperatures.
Previous studies of the conductivity of Rb3H(SO4)2 revealed a sharp increase at 205 °C [1,2], as is
typically observed for polymorphic, superprotonic transitions. In contrast to other M3H(XO4)2
compounds, however, Rb3H(SO4)2 undergoes a disproportionation reaction at this temperature to
Rb2SO4 and an unknown phase with composition intermediate between Rb3H(SO4)2 and RbHSO4
[2]. A comprehensive study using in situ high-temperature X-ray powder diffraction, thermal
analysis (simultaneous thermogravimetric and calorimetric analysis) and electrical impedance
measurements of the pseudo-binary system Rb3H(SO4)2 - RbHSO4 has been carried out here to
determine the composition and characteristics of the intermediate phase and the overall phase
behavior.
In combination, these studies indicate that the intermediate phase, formerly described as
RbmHn(SO4)p(s) with p = (m+n)/2, is Rb5H3(SO4)4. Solid state mixtures of Rb3H(SO4)2 and RbHSO4
with 66.7 % RbHSO4 (corresponding to the stoichiometry of Rb5H3(SO4)4) show the formation of
the new compound at temperatures as low as 130 °C. At 185 °C, Rb5H3(SO4)4 apparently undergoes
a transformation to a higher conductivity phase. Solid state mixtures of Rb3H(SO4)2 and RbHSO4
rich in Rb3H(SO4)2 reveal a conductivity anomaly at 185 °C, attributed to the polymorphic
transition of Rb5H3(SO4)4 and a second anomaly at 205 °C, corresponding to the disproportionation
of the remaining Rb3H(SO4)2, consistent with the previous studies. Mixtures rich in RbHSO4
display an anomaly at 170 °C, tentatively attributed to a polymorphic transition in RbHSO4,
followed by a second anomaly at 185 °C, corresponding to the polymorphic transition in the new
compound. Rb5H3(SO4)4 is not stable at ambient temperatures and eventually disproportionates into
the end-members Rb3H(SO4)2(s) and RbHSO4(s). Neither the high temperature (> 185 °C) nor low
temperature (~ 125 to 185 °C) forms of Rb5H3(SO4)4 are isostructural with any known M5H3(XO4)4
compound.
1. A.I. Baranov, V.V. Dolbinina, E.D. Yakushkin, V.Y. Vinnichenko, V.H. Schmidt and S. Lanceros-Mendez,
Ferroelectrics 217 (1998), 285.
2. L.A. Cowan, R.M. Morcos, N. Hatada, A. Navrotsky and S.M. Haile, Solid State Ionics 179 (2008), 305.
-99-

The superprotonic phase transition and hysteresis behavior of
Cs1-xKxH2PO4
Daniil Kitchaev, Ayako Ikeda, and Sossina M. Haile
Materials Science, California Institute of Technology, 1200 E California Blvd., Pasadena, CA 91125, USA
CsH2PO4 (CDP) as a fuel cell electrolyte suffers
from a large hysteresis and cell volume change at its
superprotonic transition – it is predicted that by
modifying its lattice parameters via doping these
difficulties can be avoided. CDP was doped with
KH2PO4 (KDP) and the properties of the resulting
doped electrolyte were studied over a range of
compositions. The solubility of potassium in CDP
was determined by XRD and EDS measurements
and found to be ~20% near superprotonic
temperatures. The superprotonic transition
temperature and reverse transition of CKDP (Cs1xKxH2PO4)
were evaluated in this solubility range
by DSC. It was found that the superprotonic
transition temperature decreases with increased
potassium content. This behavior contrasts that in
the CRDP (Cs1-xRbxH2PO4) system, in which the
superprotonic transition temperature increases with
rubidium content. (Figure 1)[1][2] Furthermore, the
hysteresis of the superprotonic transition has been
found to decrease with potassium incorporation
(Figure 2), from 13.6 o C for pure CDP [2], to 9.2 o C
for Cs0.7K0.3H2PO4, yet again deviating from
recorded CRDP behavior.
[1] Y. K. Taninouchi, T. Uda, Y. Awakura, A. Ikeda and S. M. Haile,
“Dehydration Behavior of the Superprotonic Conductor CsH 2PO 4 at
Moderate Temperatures: 230 to 260°C,” J. Mater. Chem. 17, 3182-
3189 (2007). (Invited)
[2] Louie, Mary W., Kislitsyn, Mikhail. Bhattacharya, Kaushik.
Haile, Sossina M., “Phase Transformation and Hysteresis Behavior in
Cs 1-xRb xH 2PO 4”. Solid State Ionics 181 (2010) 173-179. Elsevier.
-100-
P 58
Figure 1: Cs1-xKxH2PO4 and Cs1-xRbxH2PO4
superprotonic transition temperatures
Figure 2: Superprotonic phase transition
hysteresis in Cs0.7K0.3H2PO4 observed by DSC
with varying humidification.

Authors Index
Author Program No. …Page
Underline: Presenting Author
[A]
Abe, T. P01...43
Adams, A. P04...46
Adelstein, N. P25...67
Ahmed, I. O09...10 O10...11
P09...51
Akao, Y. O32...33
Amezawa, K. O28K...29 P26...68
P27...69
Anderson, V. O18K...19
Ando, M. P33...75
Argun, A. O02I...3
Asano, K. P31...73
Avila-Paredes, H. P30...72
Azad, A. O09...10 P22...64
[B]
Baranek, P. O13...14
Besikiotis, V. O29...30
Bester, G. P54...96
Bigarré, J. P02...44
Bjørheim, T. O29...30 O33...34
P51...93
Björnsson, B. P56...98
Blanc, F. O05K...6 O40...41
P24...66
Blümich, B. P04...46
Bonanos, N. P13...55 P53...95
Botez, C. O35I...36
Boucher, F. O13...14
Boukamp, B. P13...55
Bozza, F. P53...95
Buannic, L. O05K...6 O40...41
[C]
Cailleteau, C. O16K...17
Chen, C. O11...12
Chen, F. P36...78 P38...80
Chisholm, C. O06I...7
Choe, Y. P46...88
Clark, D. O39...40
Clark, J. P41...83
Cui, S. P47...89
[D]
Daiko, Y. P07...49
Danel, C. O11...12
De Araujo, C. O03...4 P49...91
De Jonghe, L. O24...25 P25...67
De Souza, R. P04...46
Deshpande, R. O18K...19
Dillon, A. O18K...19
Dixon, L. P38...80
Do, H. P55...97
Douhara, H. P05...47
Downard, A. P55...97
[E]
Eikerling, M. O25K...26
Einarsrud, M. P23...65
Emiliana, F. P45...87
Erdal, S. P52...94
Eriksson, S. O09...10 O10...11
P37...79
Esai Selvan, M. P47...89
Esashi, M. P29...71
Eurenius, K. P18...60
[F]
Fabbri, E. P44...86
Feng, J. P25...67
Feng, S. P12...54
Fisher, C. P32...74
Fjeld, H. P03...45
Flagan, R. P55...97
Fontaine, M. O22...23
Frick, B. O16K...17 O34I...35
Fukatsu, N. P05...47
Furukawa, Y. P39...81
[G]
Gebel, G. O16K...17 P02...44
George, S. O18K...19
Gomez, M. P10...52
Grande, T. O22...23 P23...65
Grey, C. O05K...6 O40...41
P24...66
Guillermo, A. O16K...17

[H]
Habenicht, B. O17...18
Hadidi, K. O27...28
Haile, S. O37...38 O38...39
O41...42 P55...97
P56...98 P57...99
P58...100
Hammond, T. O02I...3
Han, D. P20...62
Hatada, N. O30...31
Hatakeyama, A. O07...8
Hatori, J. P50...92
Haugsrud, R. O33...34 O22...23
O29...30 P03...45
P09...51 P14...56
P16...58 P37...79
P40...82 P48...90
P51...93 P52...94
Hayashi, A. P39...81
He, F. P34...76
Heitjans, P. P04...46
Hernandez-Sanchez, R. O38...39
Hightower, A. O37...38
Hinterberg, J. P04...46
Hong, S. P43...85
Hui, R. P11...53
Hurst, K. O18K...19
Huse, M. O33...34 P37...79
[I]
Iguchi, F. O31K...32 P29...71
Ikeda, A. O41...42 P58...100
Ikehata, S. P50...92
Irvine, J. O09...10 P21...63
P22...64
Ishihara, T. O23...24
Ishikawa, A. O36I...37
Islam, M. O12K...13
Ivanova, M. P14...56
[J]
Jankovic, J. P11...53
Ji, H. P42...84 P43...85
Joubert, O. O13...14
[K]
Karlsson, M. O10...11
Kawada, T. O28K...29 P26...68
P27...69
Kawamura, J. O32...33
Kawamura, G. P28...70
Kawasaki, Y. O23...24
Kee, R. O19I...20
Keffer, D. P47...89
Kehinde, T. P10...52
Kikuchi, T. P18...60
Kim, B. P42...84 P43...85
Kim, C. O20...21
Kim, G. P24...66
Kim, H. P42...84 P43...85
Kim, S. O11...12 P04...46
P30...72
Kitamura, N. O28K...29
Kitchaev, D. P58...100
Kiyono, H. P33...75
Kjølseth, C. O29...30 P40...82
Klock, U. O03...4
Knee, C. O10...11 P37...79
Kocha, S. O18K...19
Konysheva, E. P21...63
Kozawa, Y. P31...73
Kreuer, K. O03...4 O34I...35
P49...91 P54...96
Kruth, A. P22...64
Kubota, K. P29...71
Kudo, A. O36I...37
Kuramitsu, A. O30...31
Kurita, N. P05...47
Kurosu, K. O07...8
Kuwabara, A. P32...74
Kuwabara, H. O28K...29
Kuwata, N. O32...33
[L]
Larring, Y. O22...23
Lee, H. P42...84 P43...85
Lee, J. P42...84 P43...85
Lee, S. O18K...19
Lein, H. O22...23
Licoccia, S. P45...87
Løken, A. P40...82
Louie, M. O37...38
Løvvik, O. O27...28
Lucio-Vega, J. P56...98
Lyonnard, S. O16K...17 O34I...35

[M]
Maekawa, H. O07...8 O36I...37
P33...75
Magrasó, A. O22...23 P09...51
P23...65
Maier, J. O03...4 P35...77
P49...91
Maréchal, M. P02...44
Marrony, M. O13...14
Martin, M. O21K...22 P04...46
Matic, A. O10...11
Matsuda, A. P07...49 P28...70
Matsui, J. P01...43
Matsumoto, H. O23...24
Matsunaga, K. P32...74
Matsuo, Y. P50...92
Mendil-Jakani, H. O16K...17 P02...44
Merinov, B. O26...27
Merkle, R. P35...77
Meulenberg, W. P14...56
Middlemiss, D. O05K...6
Miyashita, T. P01...43
Miyoshi, S. O32...33 P18...60
Moriwake, H. P32...74
Mossa, S. O16K...17
Mugikura, Y. P31...73
Munir, Z. P04...46 P30...72
Muto, H. P07...49 P28...70
[N]
Nagao, Y. P01...43 O31K...32
Nagata, S. P06...48
Neaton, J. P25...67
Nguyen, L. P10...52
Nielsen, U. P15...57
Niepceron, F. P02...44
Norby, T. P51...93 O22...23
O27...28 O29...30
P03...45 P14...56
P16...58 P37...79
P40...82
Nørgaard, C. P15...57
Nose, Y. O30...31 P20...62
[O]
O’Hayre, R. O19I...20 O39...40
P17...59
Oba, F. P32...74
Oh, S. P28...70
Oikawa, I. P33...75
Okuyama, Y. P05...47
Ollivier, J. O16K...17
Oyama, Y. O32...33 P19...61
[P]
Paddison, S. O17...18 P41...83
P47...89 P54...96
Panithipongwut, C. P57...99
Park, J. P43...85
Peng, R. P34...76
Pergolesi, D. P44...86 P45...87
Portale, G. O03...4 P49...91
[Q]
[R]
Rahmati, B. P35...77
Rasim, K. O13...14
Ray, H. O24...25
Reimer, J. P25...67
Reiter, G. O04...5
Ricote, S. O29...30 P13...55
P14...56
Rossman, G. O15I...16
Roudgar, A. O25K...26
[S]
Saito, K. P06...48
Sakai, M. P07...49
Sakai, T. O23...24
Sakamoto, H. P07...49
Sammes, N. P17...59
Sanders, M. O19I...20
Sata, N. O31K...32 P01...43
P29...71
Sato, Y. O23...24
Sato, D. P05...47
Schuster, M. P49...91
Shepardson, D. P10...52
Shikama, T. P06...48
Shimizu, T. P33...75
Shinoda, K. P20...62
Shirpour, M. P35...77
Shogo, M. P19...61
Sigle, W. P35...77
Skou, E. P15...57
Son, J. P42...84 P43...85
Strandbakke, R. P16...58

Subramaniyan, A. P17...59
Syvertsen, G. O22...23 P23...65
P48...90
[T]
Tadanaga, K. P39...81
Takahashi, H. O28K...29
Takamura, H. O07...8
Tamaru, M. P18...60
Tanaka, I. P32...74
Tanaka, S. P29...71
Tansho, M. P33...75
Tao, S. P21...63
Tatsumisago, M. P39...81
Thomas, A. O34I...35
Tong, J. O19I...20
P17...59
O39...40
Toyoura, K. P03...45
Traversa, E. O08K...9
P45...87
P44...86
Tsuchiya, B. P06...48
Tsurui, T. P19...61
Tuckerman, M. O01K...2 P54...96
[U]
Uda, T. O30...31 P20...62
Unemoto, A. O28K...29 P26...68
P27...69
[V]
Van Aken, P. P35...77
Varga, Á. P55...97
Vartak, S. O25K...26
Verbraeken, M. O09...10
Viana, H. O09...10
Vilciauskas, L. P54...96 O34I...35
Virkar, A. O14K...15
Voth, G. P12...54
[W]
Wang, H. P13...55
Wang, L. P40...82
Wang, S. P36...78
Watanabe, T. P31...73
Wilkening, M. P04...46
Wilkinson, D. P11...53
[X]
Xia, C. P34...76
Xing, W. P48...90
Xu, X. P21...63
[Y]
Yamaguchi, S. Plenary ...1 O32...33
P18...60 P19...61
Yamamoto, H. P01...43
Yamazaki, Y. O38...39 P56...98
Yang, C. O38...39
Yeon, J. P08...50
Yoo, H. O21K...22 P08...50
Yoshida, T. P28...70
Yoshida, Y. P50...92
Yugami, H. P01...43 P29...71
[Z]
Zhang, L. P36...78
Zhao, F. P36...78 P38...80
Zhu, H. O19I...20