Invited Talks: Transition Metal Oxides - University Blog Service - The ...

The John B. Goodenough Symposium in Materials Science & Engineering – 

In Honor of His 90 th Birthday 

The University of Texas at Austin, Austin, Texas 

October 26-27, 2012 

Invited Talks: Transition Metal Oxides




October 26-27, 2012 

The explicit role of O 2p states in high oxidation state transition metal oxides 

George A. Sawatzky 

University of British Columbia 

Email: Website: 

Abstract Body in Space Below: 

(Please use single space, Times New Roman or similar font, size 12, and limit to 250 Words. Please DO NOT exceed the space 

below.) 

For late 3d transition metal oxide with formally high oxidation states like Cu3+,Ni3+, Co4+, Fe4+,5+, 

Mn 4+ the charge transfer energy for transferring electrons from O to the transition metal may be negative 

resulting in a formally more correct starting point in which the oxidation state is lowered and holes in the 

O 2p orbitals are introduced. In this talk we present experimental evidence for this in several systems and 

discuss the consequences in terms of magnetic properties and issues such as potential charge 

disproportionation. We use x ray spectrosocpies and model cluster like calculations to demonstrate the 

importance of considering the hole occupation of the O 2p states explicitly and discuss some popular 

materials like the Cuprates Nicalates and Cobaltates from this rather different starting point.




October 26-27, 2012 

The Verwey phase of magnetite - an old(ish) mystery in transition metal oxides 

J. Paul Attfield 

Centre for Science at Extreme Conditions and School of Chemistry, University of Edinburgh, West Mains Road, 

Email: j.p.attfield@ed.ac.uk 

Edinburgh, EH9 3JJ, UK. 

Website: http://www.chem.ed.ac.uk/staff/academic/attfield.html 



below.) 

Magnetite (Fe 3 O 4 ) is the eponymous magnetic substance. Its properties have guided the evolution of 

magnetoceptive organisms, and of human science and technology over 3000 years. During the twentieth 

century magnetite was found to be a ferrimagnetic, inverse spinel-type oxide with applications in magnetic 

recording and, more recently, spintronic and multiferroic devices. Spin-spin couplings between 

tetrahedrally and octahedrally coordinated Fe-sites follow the Goodenough-Kanamori rules. Magnetite 

undergoes a complex structural and electronic transition below 125 K. In 1939, Verwey proposed that this 

is driven by a charge ordering of Fe 2+ and Fe 3+ ions, but the low temperature state remained unknown and 

contentious, with a variety of models proposed over 70 years of study. The full low temperature 

superstructure of magnetite was recently solved from high energy x-ray microcrystal diffraction data. 1 

Verwey’s hypothesis was found to be approximately correct but an unexpected localization of electrons in 

three-Fe ‘trimeron’ units (highly structured small polarons) was discovered – this description is supported 

by band structure calculations. 2 Trimerons are proposed to be a type of ‘orbital molecule’; these may be 

important quasiparticles in magnetic oxides. 

1. M.S. Senn, J.P. Wright and J.P. Attfield, Nature 481, 173 (2012). 

2. M.S. Senn, I. Loa, J.P. Wright and J.P. Attfield, Phys. Rev. B (2012).




October 26-27, 2012 

New Iron Oxides by Soft Chemistry 

Mikio Takano 

Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University, Kyoto 606-8501, Japan 

takano@icems.kyoto-u.ac.jp http://www.icems.kyoto-u.ac.jp/ 



below.) 

1: BaFe 4+ O 3 (BFO) A small class of oxides containing iron in a high valence state of Fe 4+ (d 4 ) have 

been known. The most representative phase is SrFeO 3 (SFO) which crystallizes in the cubic perovskite 

structure (a = 3.850 Å). All the Fe 2+ - and Fe 3+ -oxides are antiferromagnetic insulators in their ground 

states, while SFO and related Fe 4+ -oxides commonly exhibit shift toward metallicity and ferromagnetism. 

We succeeded in obtaining BaFeO 3 (BFO) crystallizing in the cubic perovskite structure (a = 3.971 Å), 

not in the known hexagonal perovskite structure, by flowing ozone over BaFeO 2.5 powder at a low 

temperature of 200°C. It has been found that BFO has a spiral spin structure of the A-type below 111 K 

but turns ferromagnetic with a large moment of 3.5 μ B /Fe on application of a small external field of ~0.3 T 

at 5 K (0.2 T at 77 K). BFO is the very first Fe-oxide that shows ferromagnetism at ambient pressure (N. 

Hayashi et al., Angew. Chem. Int. Ed., 43, 12547, 2011). The ferromagnetic transition temperature 

exceeds 300K as external pressure is increased up to 40 GPa as examined by in-situ Mössbauer 

measurements. The P-T phase diagram of BFO will be compared with that of SFO which shows pressureinduced 

ferromagnetism. 

2: Biogenous Iron Oxides (BIOX) Prof. J. Takada’s group (Okayama Univ.) has found that the Fe 3+ - 

based microtubular deposit produced by a species of water-habitant bacteria, Leptothrix ochracea, shows 

interesting unexpected functionalities as a catalyst support, as a starting materials for beautiful red 

pigments, and so on. Results of recent studies in which I have been involved will be presented.




October 26-27, 2012 

Transiton Metal Oxides: Superconductors, Multiferroics, 

and Catalysts for Water Splitting 

Martha Greenblatt 

Department of Chemistry and Chemical Biology, Rutgers University 

martha@rutchem.rutgers.edu: 



below.) 

Combined experimental and DFT theoretical results on low-dimensional new Ni + /Ni 2+ (d 9 /d 8 ) homologous 

series, Ln n+1 Ni n O 2n+2 with n =2 and 3 layered oxides with Ruddlesden-Popper (RP)-related structures and 

isostructural and isoelectronic with the high temperature superconducting cuprates are presented. 

Temperature variation of magnetization, transport, specific heat and 139 La NMR data in La 4 Ni 3 O 8 evidence 

the presence of a transition near ~105 K. DFT calculations suggest similarity of the band structure with that 

of the cuprate superconductors and relate the transition at 105 K to a spin density wave nesting instability 

of the Fermi surface. More recent experimental and theoretical studies suggest that the transition seen at 

105 K could be a high spin-to-low spin transition of Ni 2+ (d8). A quaternary perovskite, PbMn 3 Mn 4 O 12 

prepared at high pressure and high temperature, undergoes a structural phase transition at ~380 K from the 

room temperature rhombohedral-to-a high temperature cubic phase. Temperature dependence of magnetic 

susceptibility, electronic transport and dielectric constant show a transition at ~68 K, which suggest 

coupling of a ferroelectric-like and magnetic behavior that is potentially multiferroic. Cheaper efficient 

catalysts made from earth abundant (not noble metals) and environmentally green materials are 

indispensible for extracting hydrogen from water, the essential precursor to all globally sustainable fuels. 

Achieving this goal and the reduction of CO 2 to liquid fuels are necessary to replace fossil fuels. We have 

synthesized different polymorphs of LiCoO 2 and compared their catalytic activity in water oxidation. Our 

results show that LiCoO 2 is active exclusively in the low-temperature cubic “spinel-like” structure, while 

inactive as the high-temperature layered phase, which is thermodynamically more stable. The related spinel 

LiMn 2 O 4 is transformed from an inactive to a highly efficient water oxidation catalyst (λ-MnO 2 ) upon the 

topotactic removal Li + . These spinel phases contain cubical metal-oxo (M 4 O 4 ) subunits (absent in the 

layered LiCoO 2 analog) that appear to be the key to catalytic activity. The biological basis of the 

mechanism for the high activity of the M 4 O 4 -cubical topology of spinels in water oxidation will be 

discussed.

The John B. Goodenough Symposium in Materials Science & Engineering– 



October 26-27, 2012 

Perovskites of p-block elements: influence of the lone electron pair 

José-Antonio Alonso 

Instituto de ciencia de Materiales de Madrid, C.S.I.C., Cantoblanco, 28049 Madrid 

Email: ja.alonso@icmm.csic.es Website: http://www.icmm.csic.es/matfuelcells/ 

Perovskite oxides containing p-block elements at the A positions provide the possibility of investigating 

the stereochemical effect of the lone electron pair on the crystal structure and properties of these materials. 

In this work we will address the singular features of two families of perovskites: Se(Te)MO 3 (M= 

Mn,Co,Ni) and Pb 2 (M,Sb)O 6 (M= rare earths). The former oxides are only accesses via high-pressure 

synthesis, given the small size of Se 4+ (Te 4+ ) and the extremely distorted MO 6 octahedral framework. The 

irregular oxygen environment around Se(Te) is the result of the presence of the Se 4+ (Te 4+ ) non-bonded 

lone 4s 2 electron pair, which is thought to be directed towards the apex of each trigonal pyramid. 

Additionally, three short Se-O bond lengths, implying very covalent Se-O bonds in a trigonal pyramidal 

configuration, are an important ingredient for the stability of this family of SeMO 3 perovskites. The highpressure 

structural evolution also provides with clues to understand the nature of the chemical bond in 

these materials. The family of Pb 2 (M,Sb)O 6 oxides, typified by Pb 2 TmSbO 6 , exhibit a room-temperature 

structure never observed in double perovskites, and an original sequence of phase transitions with 

temperature; in the different structures an asymmetrical distribution of the chemical bonds driven by the 

strong interaction between the Pb 2+ non-bonded 6s 2 electron pair and the oxygen p states is observed, 

which has been visualized from the electron localization function obtained from DFT calculations by 

using accurate structural data for the room temperature crystal structure. Moreover, the presence of an 

unexpected hybridization between Y and oxygen has been observed in Pb 2 YSbO 6 . This behavior involves 

the oxygen atoms that form the PbO 4 polyhedron, suggesting a strong effect of the chemical pressure of 

the non-bonded electron pair of lead in the whole structure of these compounds.




October 26-27, 2012 

Invited Talks: Energy Storage Materials




October 26-27, 2012 

Lessons from the early days of Li-ion 

Jeff Dahn 

Dalhousie University 

Email: Website: 



below.) 

Most early Li‐ion cells used LiCoO2 as the positive electrode material, even though John Goodenough and coworkers 

showed that LiNiO2 was also an intercalation electrode. At Moli Energy Ltd, where I was Director of 

Research, we "bet the farm" on LiNiO2 around 1988 due to the lower cost of Ni compared to Co. Our early scale 

up experiments led to surprises regarding the reactivity of Li(x)NiO2 with electrolyte at elevated temperature. 

Using my old research report records, I will describe our successes and ultimate failure using LiNiO2 in Li‐ion cells. 

Characterizing charged positive electrode reactivity with electrolyte turns out to be one of the first (not the last!) 

experiments one should do when evaluating new electrode materials. These lessons are critical for young (and 

old!) researchers moving into Na‐ion and Mg‐ion systems.




October 26-27, 2012 

Towards the design of new Fe-based polyanionic compounds 

from inductive effect guidance. 

J-M. Tarascon et al … , 

Laboratoire de Réactivité et Chimie des Solides, 

Université de Picardie Jules Verne, UMR-CNRS 6007, 

33, rue Saint Leu, Amiens Cedex, 80039, France. 

jean-marie.tarascon@u-picardie.fr 



below.) 

Li-ion batteries are strongly considered for electric transportation or for making the use of 

renewable energy the easiest, provided that improvements can be achieved in terms of cost, safety, energy 

density and sustainability. This drastically limits the choice of periodic table elements that can be used. 

Polyanionic compounds based on either SiO 4 4- , PO 4 3- , or BO 3 3- are being the subject of very intensive 

research as they markedly present some of the above benefits we are looking for. Therefore to increase 

their energy density, we have explored, based on the inductive effect concept, the synthesis of compounds 

containing both Li and Fe cations together with highly electronegative polyanions with or without the 

presence of the most electronegative element, namely fluor. 

Combining this strategy with the development of novel low temperature synthesis routes, we have 

discovered a new class of Li-based fluorosulphate materials of formulae AMSO 4 F (A=Li, Na, K; M=3d 

metals). Among them, LiFeSO 4 F, which presents polymorphism, shows a redox voltage of 3.6 V vs. 

Li+/Li° when crystallized in the tavorite form as compared to 3.9 V for the triplite one. This is the highest 

potential ever reported for a Fe 3+ /Fe 2+ inorganic compound so far, and simple structural/inductive effect 

arguments will be proposed to explain such results. 

By mastering the sulphate chemistry we could also prepare new phases such as Li 2 M(SO 4 ) 2 

(M=Fe/Co) or new ones whose structure and electrochemical performances will be reported as well. 

Within the context of this symposium, the magnetic properties of these phases, which are 

antiferromagnetic, will be recapped and the variation of Neel transition temperatures explained in terms of 

superexchange interactions.




October 26-27, 2012 

Lithium Batteries: What Are the Adjusting Screws 

Joachim Maier 

Max Planck Institute for Solid State Research, Heisenbergstr. 1, D-70569 Stuttgart, Germany 

Email: s.weiglein@fkf.mpg.de Website: http://www2.fkf.mpg.de/maier/ 

The contribution focuses on the dominant processes in Li-based batteries and the adjusting screws to 

improve the relevant materials. Special emphasis is laid on the significance of point defect chemistry. One 

major control parameter that became available in the context of nanotechnology and the exploitation of 

which is one of the major drivers in the field, is size. The contribution systematically explores the 

implication of size on kinetic and thermodynamic issues (nanoionics). These issues refer to improved 

electrolytes, improved electrodes, varied cell-voltages and electrochemical performances.




October 26-27, 2012 

The Rechargeable Aprotic Li-O 2 Battery 

Peter G. Bruce 

School of Chemistry, University of St Andrews, St Andrews, Scotland, UK 

Email: pgb1@st-andrews.ac.uk Website: chemistry.st-andrews.ac.uk/staff/pgb/ 



below.) 

John Goodenough’s immense contribution to lithium battery research has always been characterized by 

thinking beyond the current horizon of the technology. He harnesses science in pursuit of next generation 

lithium batteries. John investigated oxide-based cathodes at a time when much of the focus was on 

sulfides. In this spirit, the talk will consider the rechargeable aprotic lithium-air (O 2 ) battery; a potentially 

transformational technology but one that will require scientific advances, even to permit a realistic 

assessment of the potential practicality of such an energy storage device. 

Aqueous and non-aqueous (aprotic) Li-O 2 batteries are under intense investigation. The latter presents us 

with scientific challenges associated with the anode, electrolyte and cathode. After summarizing a number 

of these challenges, the problem of the electrolyte will be considered in greater depth. Early aprotic Li-O 2 

cells employed organic carbonate electrolytes, which have since been shown to exhibit such instability 

towards reduced oxygen species at the cathode that there is little or no Li 2 O 2 formation. As a result, the 

ability to cycle such a cell is not associated with the reversible electrochemistry of Li 2 O 2 

formation/decomposition, as previously thought. Other electrolytes have been investigated and will be 

discussed in terms of their ability to support truly reversible Li 2 O 2 electrochemistry at the positive 

electrode; something that is essential if the aprotic Li-O 2 cell is ever to succeed as an energy storage 

device.




October 26-27, 2012 

Posters




October 26-27, 2012 

Phase Transformation from Vanadium Sulfide to Oxides via a New Chemical Route for the Synthesis 

of β-Li x V 2 O 5 as a High Performance Cathode 

Nina Mahootcheian Asl, Wen Chao Lee, Youngsik Kim * 

a 

Richard Lugar Center for Renewable Energy, Department of Mechanical Engineering, 

Indiana University Purdue University Indianapolis, Indianapolis, Indiana, USA 

*Corresponding Author, Email: yk35@iupui.edu (Y. Kim) 



below.) 

High temperature vanadium pentoxide phase, β-Li x V 2 O 5 , was synthesized by a new chemical 

route synthesis method, which involved phase transformation from the pure LiVS 2 by heat treatment at 

600 °C in atmospheric air. When using this method, well crystalized rod-shaped particles with 20 – 30 

µm in length and 3 – 6 µm in width were found. Moreover, the surface of β-Li x V 2 O 5 particles was 

found to be coated by an amorphous vanadium oxysulfide film (~20 nm in thickness). In contrast to a low 

temperature vanadium pentoxide phase, Li x V 2 O 5 , the electrochemical intercalation of lithium into the high 

temperature vanadium pentoxide phase, β-Li x V 2 O 5 , was fully reversible in the range of 0.0 < x < 2.0 and 

had a capacity up to 310 mAh/g at 0.07 C between 1.5 V and 4 V. A good capacity retention of more 

than 88% was also observed after 50 cycles even at the higher current rate of 2 C. The observed 

electrochemical performance of the heat-prepared sample was quite surprising when considering its 

particle size and comparing it to other vanadium pentoxides prepared using a different synthesis method.




October 26-27, 2012 

High-Voltage Spinel Cathodes for Lithium-Ion Batteries 

Katharine Chemelewski, Eun Sung Lee, Zach Moorhead-Rosenberg, Il Tae Kim, and Arumugam Manthiram 

Materials Science and Engineering Program, The University of Texas at Austin 

Email: manth@austin.utexas.edu Website: http://www.me.utexas.edu/~manthiram 



below.) 

The high-voltage spinel cathode LiMn 1.5 Ni 0.5 O 4 is a promising candidate for large-scale energy storage solutions of 

the future. With fast, 3D lithium-ion diffusion pathways and a robust crystal structure, this cathode material is well 

suited for implementation in vehicle and grid storage applications. However, widespread adoption has been 

hampered by capacity fade particularly at elevated temperatures, which has been attributed to many factors 

including aggressive solid-electrolyte interphase (SEI) reaction, cation ordering, site defects resulting in the 

formation of Mn 3+ , and the orientation of the crystal planes facing the surface. We present here investigations to 

develop a fundamental understanding of the factors that govern the electrochemical properties of LiMn 1.5 Ni 0.5 O 4 , as 

well as novel techniques to characterize the materials quantitatively and surface modification to suppress unwanted 

side reactions. The solubility of Ni in LiMn 1.5 Ni 0.5 O 4 is dependent on temperature and increases with decreasing 

annealing temperature (e.g., 700 o C), eliminating the Li x Ni 1-x O impurity. Additionally, precursor synthesis 

conditions including temperature, pH, stir speed, pressure, and annealing conditions affect the morphology and 

electrochemical properties of the final cathode material, and the orientation of the crystal planes facing the 

electrolyte interface is a critical factor for stabilizing the cathode during high-voltage operation. Also, it is known 

that the performance of the undoped LiMn 1.5 Ni 0.5 O 4 spinel is influenced by the Mn 3+ content, and a magnetic method 

has been developed, for the first time, to determine quantitatively the Mn 3+ content that agrees closely with the 

electrochemical data. Furthermore, the degree of cation ordering could be compared by examining the lithium 

insertion reaction below 3 V into the empty 16c sites, which is consistent with the FTIR and electrochemical data. 

Finally, surface modification with graphene and AlPO 4 is shown to improve the cyclability and rate capability of 

high-voltage spinel cathodes.




October 26-27, 2012 

Direct Methanol Fuel Cells: New Materials and Stack Development 

Thom Cochell, Wei Li, Xinsheng Zhao, Zhongqing Jiang, Zincheng & Arumugam Manthiram 

Materials Science and Engineering Program and Texas Material Institute, 

The University of Texas at Austin, Austin, TX 78712, United States 

Email: rmanth@mail.utexas.edu; Website: http://www.me.utexas.edu/~manthiram/index.htm 

Direct Methanol Fuel Cells (DMFCs) are promising electrochemical energy conversion devices for mobile 

and portable applications. However, several technical barriers must be overcome including sluggish 

methanol oxidation and oxygen reduction reactions, methanol fuel crossover through the proton exchange 

membrane from the anode to the cathode, and dissolution of the anode PtRu catalyst. To overcome these 

barriers of DMFC commercialization, we have developed new materials and implemented novel 

manufacturing processes. The new anode catalyst PtRuSnCe/C was shown to have superior durability 

compared to the commercial PtRu/C anode catalyst. An optimized low-cost cathode catalyst Pd 4 Co/C was 

found to exhibit better performance than Pt/C in DMFC. The blend membrane SPEEK + PSf-NBlm shows 

lower methanol crossover than Nafion 115, and the home-made graphite bipolar plates show superior 

single cell performance to commercial graphite plates. Additionally, novel PtPdCu-based catalysts have 

been designed that show enhanced oxygen reduction activity, and several different SPEEK-based 

membranes have been tailored to lower methanol crossover and increase proton conductivity. Inkjet 

printing and autospray processing methods were used for fabrication of uniform catalyst layers. Together 

these novel materials and processing techniques were utilized to prepare an 18 W 20-cell and an 11 W 10- 

cell DMFC stack.




October 26-27, 2012 

Materials and Interfacial Chemistry for Next Generation Electrical Energy Storage 

S. Dai, 1 M. P. Paranthaman, 1 C. A. Bridges, 1 R. R. Unocic, 1 X. G. Sun, 1 D.-E. Jiang, 1 G. M. Veith, 1 

J. B. Goodenough, 2 and A. Manthiram 2 

1 Oak Ridge National Laboratory, Oak Ridge, TN 37831 

2 The University of Texas at Austin, Austin, TX 78712 

Email: dais@ornl.gov 

Abstract: 

The overarching goal is to investigate fundamental principles governing energy storage through 

integrated synthesis and advanced characterization. Our current research is focused on fundamental 

investigation of electrolytes based on ionic liquids and rational synthesis of novel electrode architectures 

through Fermi level engineering of anode and cathode redox levels by employing porous structures and 

surface modifications as well as advanced operando characterization techniques including neutron 

diffraction and scattering. The key scientific question concerns the relationship between chemical 

structures and their energy-storage efficacies. A novel approach based on small angle neutron scattering 

(SANS) enables the observation of electrochemical processes during the cycling of high capacity lithium 

ion batteries. Changes in neutron scattering intensity associated with mesopore ordering show the 

processes of solid-electrolyte interphase (SEI) formation and lithium intercalation. Using a lithium-ion 

half-cell and different solvent deuteration levels, our results demonstrate that SANS can be employed to 

better understand complicated electrochemical processes occurring in rechargeable batteries. We will also 

report our recent results on ionic liquid electrolytes, and mesoporous architectures for high performance 

lithium ion batteries. 

Research Sponsored by the U.S. Department of Energy, Basic Energy Sciences, Materials Sciences and 

Engineering Division. Research supported by Oak Ridge National Laboratory’s SHaRE User Facility and 

Spallation Neutron Source, which are sponsored by the Scientific User Facility Division, Office of Basic 

Energy Sciences, U.S. Department of Energy.




October 26-27, 2012 

Molecular Concepts of Inorganic Structures with Emphasis on Noncentrosymmetry 

and Local Geometry. 

Martin D. Donakowski*, Romain Gautier, Anastasiya I. Vinokur, Kenneth R. Poeppelmeier 

Northwestern University; 2145 Sheridan Rd; Evanston, IL; 60208 

*Email: martindonakowski@u.northwestern.edu Website: http://chemgroups.northwestern.edu/poeppelmeier/ 



below.) 

This poster describes coordination environments of vanadium oxyfluoride (VOFs) materials; specifically, 

the structural implications of the variable nucleophilicities of VOF anions. The VOF basic building unit 

(BBU) [VOF 5 ] 2- has been noted for its low nucleophilicity in comparison to the similar anion [NbOF 5 ] 2- . 

To examine the coordination of VOF we present the compounds I) CuMOF 5 (H 2 O) 4 (pyz) 2 and 

CuMOF 5 (H 2 O)(pyz) 3 (M = V V , Nb V ), II) MVOF 4 (H 2 O) 7 (M II = Co, Ni, Cu, Zn), and III) 

Na 2 (M(H 2 O) 2 )(V 2 F 6 O 4 ) (M II = Co, Ni, Cu). Compounds (I) present order or disorder of the oxide and 

fluoride ligands owing to the nucleophilicity of the VOF BBU [VOF 5 ] 2- and the use of an organic 

molecule present (pyrazine). Compounds (II) display an interesting phenomenon: the anion 

[VOF 4 (H 2 O)] 2- is only able to coordinate to the cation [M(H 2 O) 6 ] 2+ when M II = Cu. This results in the 

hydrated compound CuVOF 4 (H 2 O) 7 comprised of lambda (Λ)-shaped BBUs that crystallize in a 

noncentrosymmetric space group for reasons that will be described. Compounds (III) exhibit a rarely 

ordered dioxo vanadium fluoride [VO 2 F 4 ] 3- that dimerizes into the new BBU [V 2 O 4 F 6 ] 4- . In comparison to 

[VOF 5 ] 2- This dioxo vanadium fluoride has increased nucleophilicity of the oxide ligands owing to the 

division of the pi-bonding orbitals of the V V cation amongst two oxide ligands and the geometry of the 

dimeric VOF BBU. Implications of the nucleophilicity of the VOF will be explained in terms of synthetic 

strategies to create materials for purposes of nonlinear optical (NLO) activity with analogies to organic 

chemistry methodology.




October 26-27, 2012 

Electrodeposition of Amorphous Silicon Anode for Lithium Ion Batteries 

Rigved Epur a , Madhumati Ramanathan b , Faith R. Beck a,c , 

A. Manivannan c and Prashant N. Kumta a,b,d,† 

aDepartment of Mechanical Engineering and Materials Science, University of Pittsburgh, 

Pittsburgh, PA 15261, USA 

bDepartment of Bioengineering, University of Pittsburgh, Pittsburgh, PA 15261, USA 

cUS Department of Energy, National Energy Technology Laboratory, Morgantown, WV 26507, USA 

dDepartment of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261, 

USA 

Email: pkumta@pitt.edu, manivana@netl.doe.gov 

Amorphous silicon has been successfully electrodeposited on copper using a SiCl4 based organic 

electrolyte under galvanostatic conditions. The electrodeposited silicon films were characterized for their 

composition, morphology and structural characteristics using glancing angle x-ray diffraction (GAXRD), 

scanning electron microscopy (SEM), and Raman spectroscopy. GAXRD and Raman analyses clearly 

confirm the amorphous state of the deposited silicon film. The deposited films were tested for possible 

application as anodes for Li-ion battery. The results indicate that this binder less amorphous silicon anode 

exhibits a reversible capacity of ~1300 mAh g -1 with a columbic efficiency of > 99.5% up to 100 cycles. 

Impedance measurements at the end of each charge cycle show a non-variable charge transfer resistance 

which contributes to the excellent cyclability over 100 cycles observed for the films. This approach of 

developing thin amorphous silicon films directly on copper eliminates the use of binders and conducting 

additives, rendering the process simple, facile and easily amenable for large scale manufacturing.




October 26-27, 2012 

Electronic structure effects in platinum/valve-metal thin film alloys, 

that exhibit enhanced oxygen reduction reaction rates 

Charles C. Hays 

4800 Oak Grove Drive 

Jet Propulsion Laboratory 

California Institute of Technology, Pasadena, CA 91109 

Email: cchays@jpl.nasa.gov 



below.) 

In an effort to reduce the platinum group metal (PGM) loading for the cathode in hydrogen-air fuel cells, 

we have examined the electrochemical performance of Pt-based alloys, in the form of crystallographically 

oriented (111) thin films. Using a multi-electrode technique developed at JPL, we have examined the 

electrochemical performance of Pt alloyed with valve metals (Ti, V, and Zr) and the late transition metals 

(Co, Ni). Our results indicate that alloys with as little as 30 atomic % Pt, are stable in perchloric and 

sulfuric acid electrolytes. The alloys are electrochemically active for the major reactions; e.g., the 

hydrogen-oxidation-reaction (HOR), hydrogen-evolution-reaction (HER), oxygen-reduction-reaction 

(ORR), and oxygen-evolution-reaction (OER). In this contribution, we will focus on results, which show 

that significantly enhanced ORR rates are exhibited in the Pt-Co-Zr and Pt-Ni-V composition manifolds, 

where the measured ORR rates exceed those of Pt (111) thin films tested in the same cell, by factors as 

large as 86X. In each system, a strong dependence on the Pt content is displayed; with peaks in the ORR 

current density exhibited, when the Pt-metal content is near 90 atomic % and 30 atomic %. We will 

discuss the physical origins of this improved ORR performance, and relate it to the composition dependent 

variation in Pt 5d-band filling. 

Acknowledgements: The research described in this presentation was carried out at the Jet Propulsion 

Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space 

Administration. We acknowledge support from the Department of Energy (DE-PS36-08GO98101).




October 26-27, 2012 

Novel Energy Storage with Solid Oxide Rechargeable Metal-Air Batteries 

Kevin Huang 

Department of Mechanical Engineering, University of South Carolina 

300 Main Street, Columbia, SC29201 

Email: kevin.huang@sc.edu Website: www.sofccenter.com 

Cost effective and large scale energy storage is critical to renewable energy integration and smart-grid 

energy infrastructure. Rechargeable batteries have a great potential to become a class of cost effective 

technology suited for large scale energy storage. In this presentation we report our recent progress in 

understanding the energy storage characteristics of a newly developed solid oxide rechargeable iron-air 

battery. Investigations of the battery performance under various current densities and cycle durations show 

that iron utilization plays a determining role in storage capacity and round-trip efficiency. Further studies 

of the battery’s cycle life reveal a unique charge-cycle originated degradation mechanism that can be 

interpreted by a combined vapor-phase transport and electrochemical condensation model. Overall, the 

energy capacity of the new solid oxide iron-air storage battery can be properly balanced with the roundtrip 

efficiency at optimized iron utilization.




October 26-27, 2012 

Thin Film Solar Cells - Fundamental investigations and Device Applications 

B. Reeja Jayan, Chih-Liang Wang, K. L. Harrison, and A. Manthiram 

The University of Texas at Austin, Materials Science and Engineering Program 


Abstract: 


below.) 

Our research explores charge generation and transfer processes at interfaces within thin film solar cells by 

combining data from photovoltaic device performance tests with characterization experiments conducted 

directly on the device. Our work spans polymer-based organic-inorganic hybrid solar cells, which 

combine the processing flexibility of organics (P3HT) with the low-cost and safety benefits offered by 

inorganic materials (TiO 2 ). Bilayer interfacial prototypes with tunable efficiency values ranging from 

around 0.01 to 1.6 % have been demonstrated. The simple bilayer design and stability of these devices are 

beneficial to investigate various device optimization steps, using a host of characterization techniques 

directly on a working device. Examples include X-ray photoelectron spectroscopic (XPS) depth profiling 

analysis of metal-P3HT and P3HT-TiO 2 interfaces and Raman analysis of bonding between metal sulfide 

interlayers like Sb 2 S 3 and P3HT. We also study Kesterite Cu 2 ZnSnS 4 based inorganic solar cells, a 

promising material derived entirely from earth-abundant raw materials. The solution-based approach using 

Cu 2 ZnSnS 4 employed in a low-cost superstrate-type device structure has been demonstrated with 0.4 % 

device efficiency under simulated AM 1.5 G illumination conditions. With the goal of developing a 

fundamental understanding of the way in which thin film solar cells work, we have developed novel 

microwave-assisted low temperature film growth techniques and fabrication approaches to create 

functional solar cells that are low-cost, efficient, and stable.




October 26-27, 2012 

First-Principles Study of Li Defect in Solid Electrolyte (γ-Li 3 PO 4 ) and in 

Electrode/Electrolyte (Li/γ-Li 3 PO 4 ) interface 

Santosh KC 1 , Ka Xiong 1 , Roberto C. Longo 1 , and Kyeongjae Cho 1, 3 * 

1 Department of Materials Science and Engineering, University of Texas at Dallas, Richardson, TX 75080, USA 

3 Department of Physics, University of Texas at Dallas, Richardson, TX, 75080, USA 

*Email: kjcho@utdallas.edu 

Abstract: 

In this work, we present our results of first-principles calculations of defects in solid electrolyte γ-Li 3 PO 4 

and in negative electrode/electrolyte interface (Li/γ-Li 3 PO 4 ). Our results show that Li interstitial defect 

dominates over the vacancy defect. The Li vacancy-interstitial pair defect formation energy of the 

interface model is comparable to the sum of Li vacancy defect at the electrode and Li ion (Li + ) interstitial 

defect in the electrolyte. Our study shows that the high Li + defect formation energy is the determining 

factor for low ionic conductivity of this Li metal/electrolyte interface. Thus, the study of the Li 

metal/electrolyte interface provides information on Li defect formation and migration, which will help us 

to improve the ionic conductivity in future Li-ion battery.




October 26-27, 2012 

Scanning Probe Microscopy Studies in Correlated Electron Systems 

Jeehoon Kim, R. Baumbach, F. Ronning, L. Civale, J. D. Thompson, and Roman Movshovich 

Los Alamos National Laboratory, NM 87545, USA 

Email: jeehoon@lanl.gov Website: 



below.) 

Room-temperature scanning probe microscopy (RT-SPM) is widely used to study electronic and magnetic 

properties at the sub-micron scale in basic and applied science. By analogy with RT-SPM, lowtemperature 

SPM (LT-SPM) is a key tool to investigate phase transitions at low temperature, such as 

ferromagnetism and superconductivity. In this talk, I will present a variety of LT-SPM techniques to 

directly image magnetic and electric properties in ferro- and ferri-magnetic materials, and metal insulator 

transition materials. Recently, we developed a novel technique to measure the absolute value of the 

magnetic penetration in superconductors by magnetic force microscopy (MFM). This technique has been 

applied to unconventional superconductors, such as borocarbides and pnictides, to investigate 

superconducting properties. Also, direct visualization of the interaction between magnetism and 

superconductivity will be present in a ferromagnet-superconductor hybrid.




October 26-27, 2012 

Dual-Electrolyte Li-Air Batteries 

Longjun Li and Arumugam Manthiram 

Materials Science and Engineering Program and Texas Material Institute 

The University of Texas at Austin, Austin, TX 78712, United States 

Email: rmanth@mail.utexas.edu; Website: http://www.me.utexas.edu/~manthiram/index.htm 

Lthium-air cells based on aprotic electrolytes suffer from clocking of the porous air electrode by insoluble 

products like Li 2 O 2 or Li 2 O and attack of the aprotic electrolyte by moisture or carbon dioxide from the 

ambient air. To solve these problems, a novel dual-electrolyte Li-air battery with high capacity and 

voltage has been developed. The lithium anode is protected from contaminates in the air by a Li-ion solid 

electrolyte and the discharge products are soluble in the catholyte. But the Li-ion solid electrolyte is not 

stable in strong acidic or alkaline solutions. A phosphate buffer solution with a moderate pH has been 

developed as a possible catholyte to keep the Li-ion solid electrolyte stable and reduce internal resistance 

and overpotential. All the three protons of the phosphoric acid can be effectively utilized to achieve a high 

capacity of 740 mAh g -1 at an average cell voltage of 3.3 V with good rechargeability and stability. Nanocrystalline 

IrO 2 has been utilized as the oxygen evolution catalyst to lower the charge overpotential. The 

large internal resistance has been decreased by elevating the operating temperature or increasing the ionic 

conductivity of the Li-ion solid electrolyte. After optimization, the maximum power density reaches 40 

mW cm -2 and the battery conversion efficiency reaches 80 % ( 2 mA cm -2 ) at 40 °C.




October 26-27, 2012 

Local structure and orbital ordering in YTiO 3 

Bing Li and Despina Louca 

Department of Physics, University of Virginia, Charlottesville, VA 22904 

Email: dl4f@virginia.edu 

Website: http://www.phys.virginia.edu/People/personal.aspUID=dl4f 



below.) 

The local atomic structure of YTiO 3 has been investigated by using neutron diffraction and the pair 

density function analysis from 10 to 350 K. Upon warming from base temperature, deviations are 

observed of the local from the average crystal symmetry and these are attributed to distortions involving 

the Y and O atoms. In the case of Y, the in-plane x-y displacements result in an antiferrodistortive motion 

exerting influence on Y-O1 (apical sites of octahedral) bonds seen in the temperature dependence. At the 

same time, the O ion site in the basal plane of the octahedron is split to two (O2 and O3), giving rise to 

two unequivalent Ti-O bonds. The splitting of the oxygen site is in contrast to the equivalent sites in the 

corresponding average structure and calls for a lower symmetry than the Pnma currently used to describe 

the crystal structure. The oxygen displacements are of the order of 0.05 to 0.07 Å and lead to bending of 

the octahedra. The distortion of the in-plane O ions leads to quite different O-Ti-O bond angles. This may 

in turn have consequences on the linear combination of the atomic orbitals, where the proportion of the d zy 

to d xy components may be affected. However, it is expected that the antiferro-orbital ordering be 

preserved.




October 26-27, 2012 

Electrochemical and electronic properties of tetrahedral silicates Li2MSiO4 as cathode 

materials for Li-ion batteries 

R. C. Longo, K. Xiong, Santosh KC and K. Cho 

Department of Materials Science & Engineering, The University of Texas at Dallas, 800 W. Campbell 

Road, Richardson, TX, 75080, USA 

Emails: roberto.longo@utdallas.edu and kjcho@utdallas.edu 



below.) 

Using density functional theory (DFT), we investigate the structural, electronic and electrochemical 

properties of different tetrahedral silicate polymorphs recently synthesized and experimentally 

characterized. This family of compounds can insert and/or extract two Li atoms in two consecutive 

electron redox processes, giving rise to a much higher capacity (330 mAh/g) than that of the current 

cathodes (e.g., 160 mAh/g for LiCoO 2 ). Our DFT study includes the lithiated and both semi- and fully 

delithiated phases, in order to analyze how the charge/discharge process affects their structural stability. 

We also describe the electronic structure of these compounds accurately, trying to point out the main 

favorable mechanisms for both ionic and electronic conductivities. Finally, we show that, with suitable 

doping, it is possible to tailor the voltage and band gap of these silicates, improving their performance and 

making them promosing candidates as new cathode materials of rechargeable Li-ion batteries. 

Acknowledgments 

The authors also acknowledge the Texas Advanced Computing Center (TACC) for providing HPC 

resources.




October 26-27, 2012 

Finding Unusually Strong Spin‐Orbit Coupling in Post‐Perovskite CaIrO 3 via X‐ray 

Magnetic Circular Dichroism 

Luke G. Marshall 1 , Jinguang Cheng 1,2 , Jianshi Zhou 1 , John B. Goodenough 1 , Daniel Haskel 3 , 

and Michel Van Veenendaal 3,4 

1 Texas Materials Institute, The University of Texas at Austin, 

204 E. Dean Keeton St. C2201, 

Austin, TX 78712-1591 

2 The Institute of Physics, Chinese Academy of Sciences 

3 Advanced Photon Source, Argonne National Laboratory 

4 Department of Physics, Northern Illinois University 

Email: luke.g.marshall@utexas.edu Website: http://lukegmarshall.wordpress.com 

Abstract: 

Strong spin-orbit coupling (SOC) and strong correlations have been considered essential in understanding 

the unusual physical properties of the 4d and 5d transition-metal oxides, such as the SOC driven Mott 

insulating state in Sr 2 IrO 4 . Recently, an unusual atomic-like orbital moment and strong SOC have been 

confirmed experimentally in 9R-BaIrO 3 through analysis of the branching ratio at the Ir L 2,3 absorption 

edges as obtained from x-ray absorption spectroscopy and x-ray magnetic circular dichroism (XMCD) 

measurements. We have applied the same techniques to probe unusual ferromagnetism and SOC in the 

post-perovskite (pPv) CaIrO 3 , which is an insulator and exhibits weak ferromagnetism below T c ~ 110K. 

The branching ratio at the Ir L 2,3 absorption edges, which is close to unity in pPv CaIrO 3 , appears to 

indicate an even stronger spin-orbit interaction in the pPv CaIrO 3 than in 9R-BaIrO 3 . However, it has been 

challenging to model the Ir 5d orbital moment, as probed by the XMCD measurements, due to the 

understood local octahedral-site distortions.

The John B. Goodenough Symposium in Materials Science & Engineering– 



October 26-27, 2012 

Understanding Interfacial Reactivity of Silicon Nanostructures 

Sankaran Murugesan ± , Kjell Schroder*, Justin T. Harris + , Lauren Webb* ,± , Brian A. Korgel* ,+ and Keith J. Stevenson* , ± 

± Department of Chemistry & Biochemistry, + Department of Chemical Engineering, *Materials Science and 

Engineering Program, The University of Texas at Austin 



below.) 

In recent years Si has drawn considerable interest as an anode material for Lithium ion batteries 

(LIB) due to its high gravimetric and volumetric energy density. Si can react with Li and form an alloy of 

Li 15 Si 4 , corresponding to a very high charge storage capacity of 3579 mAh/g that is approximately 10 

times higher in gravimetric capacity than graphite. However, Si-based anodes face several challenges. 

First, crystalline Si anodes undergo a 400% volume expansion during the lithiation process. Typically 

large irreversible capacity losses are observed during lithiation/delithiation since volume expansion and 

contraction cause pulverization of the Si and loss of electrical contact with the current collector. Secondly, 

the electrochemical alloying potential of Si is above the solvent reduction level, which leads to the 

formation of a solid electrolyte interface (SEI). These fundamental processes are investigated through high 

resolution spectroscopic techniques. What effects volumetric expansion/contraction processes in Si and 

how can they be controlled What factors govern charge transfer kinetics and how can charge transfer 

resistance be controlled What influence do morphology and surface chemistry have on reversibility and 

charge storage capacity What role does SEI play in the charge transfer process between the electrolyte 

and electrode




October 26-27, 2012 

MXene - A New Family of Two Dimensional Materials for Use in Lithium Ion Batteries 

and Lithium Ion Capacitors 

Michael Naguib 1 , Jérémy Come 2 , Yohan Dallagnese, 1 Olha Mashtalir 1 , Volker Presser 1 , Pierre-Louis Taberna 2 , 

Patrice Simon 2 , Michel W. Barsoum 1 , and Yury Gogotsi 1 * 

Affiliation & Address 

1 

Department of Materials Science and Engineering & A.J. Drexel Nanotechnology Institute, Drexel 

University, Philadelphia, PA 19104, USA 

2 

Université Paul Sabatier, CIRIMAT UMR CNRS 5085, 31062 Toulouse Cedex 4, France and Réseau 

sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, France 

* gogotsi@drexel.edu 



below.) 

Recently, we reported on the fabrication of a new family of two-dimensional (2-D) sheets of early 

transition metal carbides produced by the exfoliation of the MAX phases [1, 2]. The latter are a large 

family of machinable, layered ternary carbides and nitrides, where “M” is an early transition metal, “A” is 

a group 13 to 16 element and “X” is C and/or N [3]. We labeled this new materials “MXene” to indicate 

the selective etching of the A layers from the MAX phases and the similarity of the 2-D layers to graphene. 

More recently, we showed that Ti 2 C can be used as an anode material in lithium ion batteries [4]. The 

performance was found similar to titania based anodes; the lithiation and delithiation potentials were 

found to be around 1.6 and 2.0V respectively. Already the very first study [4] showed stable capacity of 

225 mAh.g -1 was obtained for the Ti 2 C-based MXene anode at C/25. Ti 2 C can be cycled at high rates, for 

example at 10C a stable capacity of 70 mAh.g -1 was obtained. Anodes of delaminated MXenes showed a 

much higher Li uptake at high cycling rates. The ability to charge/discharge Li at such high rates suggests 

that Ti 2 C could be used in hybrid cells that combine the advantages of batteries and supercapacitors [5]. 

References: 

[1] M. Naguib, M. Kurtoglu, V. Presser, J. Lu, J. Niu, M. Heon, L. Hultman, Y. Gogotsi, M.W. Barsoum, 

Advanced Materials, 23 (2011) 4248–4253. 

[2] M. Naguib, O. Mashtalir, J. Carle, V. Presser, J. Lu, L. Hultman, Y. Gogotsi, M.W. Barsoum, ACS 

Nano, 6 (2) 1322–1331 (2012). 

[3] M.W. Barsoum, Progress in Solid State Chemistry, 28 (2000) 201-281. 

[4] M. Naguib, J. Come, B. Dyatkin, V. Presser, P.-L. Taberna, P. Simon, M.W. Barsoum, Y. Gogotsi, 

Electrochemistry Communications, 16 (2012) 61-64. 

[5] J Come M Naguib P Rozier M W Barsoum Y Gogotsi P -L Taberna M Morcrette P Simon




October 26-27, 2012 

Enhanced charge-transfer kinetics by anion surface modification of LiFePO 4 

Kyu-Sung Park 1 , Penghao Xiao 2 , Anthony Dylla 2 , Graeme Henkelman 2 , Keith J. Stevenson 2 , John B. Goodenough 1 

1 Texas Materials Institute, University of Texas at Austin, Austin, Texas 78712, United States 

2 Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, United States 

Email: kspark37@gmail.com 

Abstract 

Despite the great achievement in understanding the materials properties and powder engineering of 

LiFePO 4 , the chemical bonding at the surface has been almost ignored. Herein, we demonstrate that the 

undercoordinated Fe 2+ /Fe 3+ redox couple at the surface gives a high barrier for charge transfer, but it can 

be stabilized by nitrogen or sulfur adsorption. The surface modification improves greatly the charge 

transfer kinetics and the charge/discharge performance of a LiFePO 4 cathode. DFT calculation estimates 

the origin of the improvement in terms of an electronic and ionic contribution based on a surface model 

probed by TOF-SIMS; the calculation agrees well with an experimental rate-constant analysis.




October 26-27, 2012 

In-situ synchrotron high-energy x-ray characterization of advanced materials for 

rechargeable batteries 

Yang Ren and Zonghai Chen 

Argonne National Laboratory, 9700 S. Cass Avenue, Argonne, IL 60439, USA 

Email: yren@anl.gov Website: 



below.) 

The increasing demand in safer and higher performance rechargeable batteries for broad applications has 

led to global efforts to develop advanced electrode materials, electrolyte components and additives, and 

other cell components. There is a critical need in understanding key material issues in batteries under 

realistic conditions and in real time. We will present here a recent application of synchrotron high-energy 

x-ray diffraction (HEXRD) for in-situ structural characterization of advanced battery materials. Our 

experimental work includes in-situ HEXRD studies of cathode materials during solid-state synthesis, timeresolved 

measurements during hybrid pulse characteristic test (HPPC) of a full battery, in-situ study of Si- 

Li interaction and nondestructive material characterization of commercial 18650 cells during cycling, and 

in-situ monitoring reaction pathways of electrodes with electrolytes during thermal runaway. Our results 

provide important property-structure-performance information for in-depth understanding of advanced 

energy materials and the safety and performance of batteries. (Use of the Advanced Photon Source was 

supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under 

Contract No. DE-AC02-06CH11357.)




October 26-27, 2012 

Polymer assisted deposition of transition-metal-oxide thin films 

Francisco Rivadulla 

Center for Research in Biological Chemistry and Molecular Materials (CIQUS), University of Santiago de 

Email: f.rivadulla@usc.es 

Compostela, 15782-Santiago de Compostela, Spain 

Website: http://www.usc.es/ciqus/en/research/research-teams/rivadulla-lazzari 



below.) 

The spectacular advances in physical deposition techniques during the last decades made possible the 

fabrication of thin-films of the required quality for either fundamental studies or highly demanding 

applications. Chemical methods, although more cost effective, are normally not competitive with physical 

techniques of deposition when the final quality required (smoothness, interface roughness, long-range 

homogeneity, etc) is important. 

I will present results of the epitaxial growth of ultra-thin films of different oxides (LnMnO 3 , LaCoO 3 , 

SrRuO 3 , etc.) on SrTiO 3 and LaAlO 3 by spin-coating of a polymer/metal aqueous solution. The films show 

morphological and structural parameters similar to the best reported by physical methods, over large areas. 

Moreover, the use of aqueous-based solutions of environmentally friendly polymers represents an 

important improvement over other methods of chemical deposition. 

This simple chemical method produces the high-quality films required for either fundamental studies or 

applications, similar to physical deposition techniques.




October 26-27, 2012 

LiFePO 4 Electrodes with conductive polymers and no elemental carbon particles. 

Steen B. Schougaard 

Université du Québec à Montréal 2005 Jeanne Mance, Montréal, QC H2X 2J6, Canada 

Email: schougaard.steen@uqam.ca Website: http://www.lab-schougaard.uqam.ca 



below.) 

Since its original discovery by Prof. Goodenough [1], LiFePO 4 has become a material of choice for 

lithium-ion batteries, when toxicity, cycling stability and safety are considered. However, to function in 

practical batteries, it requires a conductive coating. 

We have in past years developed an alternative technology to the industrial standard of pyrolytic carbon 

coating. Our processes [2] uses the intrinsic oxidative power of Li 1-x FePO 4 to polymerize a 2-3 nm thick 

conductive coating on the particle surface. This process, unlike the pyrolysis, takes place at low 

temperature (




October 26-27, 2012 

Greening Digital Systems Requires Better Quantum Models 

Bob Schubring 

Wonder Funding 1680 Vine Street, Suite 325, Los Angeles, CA 90028 

office: 323.733.1000 | mobile: 734.320.3435 

Email: rschubring@gmail.com 

Website: http://www.wonderfunding.com 



below.) 

Polarization gradients in compositionally-graded perovskite ferroelectric thin films are known to generate 

electrical current by an unexplained mechanism that is not corrosion. Barium strontium titanate thin films 

have been engineered by compositional grading to compensate for geometric effects, and function as 

commercially nonvolatile random-access memories in microcontrollers. Further advancement requires 

elucidation of the mechanism by which the unexplained currents happen. The benefits are potentially 

enormous. Conventional RAM requires refresh at every clock cycle of the computer. Ferroelectric RAM 

holds data indefinitely without refresh, for periods up to 7 years, and does not degrade mechanically as 

does flash memory. If feature sizes are reduced and switching speeds increased to match conventional 

RAM, the energy and cooling savings will be vast, because most RAM-cached data is not read every clock 

cycle. Markets do not price in the cost advantages of these energy savings, because too little is known 

about the anomalous current mechanism and how it may limit switching speeds in alternative memory 

materials. To overcome this obstacle will require an advanced quantum-mechanical model that accounts 

for the anomalous current. The current may be the effect of polarization-driven quantum tunneling but this 

is unproven. Thermoelectric tunneling effects were not measurable by thermometry in graded potassium 

tantalate niobate thin films, but new calculations show that the likely temperature differences were within 

experimental error of the thermometry study. Thus, a secondary benefit of improved quantum-mechanical 

models, is that waste heat may be harvested by resulting ferroelectric RAM devices.




October 26-27, 2012 

A-site ordered perovskite-structure oxides with intriguing properties 

Yuichi Shimakawa 

Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan 

Email: shimak@scl.kyoto-u.ac.jp Website: http://www.scl.kyoto-u.ac.jp/ ~ shimakgr 



below.) 

A very unusual ordered arrangement of the A-site ions in the simple ABO 3 perovskite produces 

AA’ 3 B 4 O 12 A-site ordered perovskites. The A site accommodates alkaline metals, alkaline-earth metals, 

and lanthanides like those in the simple perovskites. At the originally 12-fold coordinated A’ site, 

transition-metal ions such as Cu 2+ and Mn 3+ form square coordinated units that align perpendicular to each 

other. The presence of the transition-metal ions at both A’ and B sites produces A’-A’ and and/or A’-B 

interactions in addition to B-B interaction usually seen in the simple perovskite materials. Competitive 

and/or cooperative interplay of these interactions gives rise to diverse and intriguing physical properties. 

Two new A-site ordered perovskite-structure oxides, CaCu 3 Fe 4 O 12 and LaCu 3 Fe 4 O 12 , are 

highlighted. They were synthesized under high-pressure and high-temperature conditions. The 

compounds contain unusually high valence states of iron: Fe 4+ in CaCu 3 Fe 4 O 12 and Fe 3.75+ in 

LaCu 3 Fe 4 O 12 . Instabilities of the high oxidation states at low temperatures are resolved in CaCu 3 Fe 4 O 12 

by charge disproportionation from Fe 4+ to Fe 3+ and Fe 5+ , and in LaCu 3 Fe 4 O 12 by charge transfer between 

A-site Cu and B-site Fe ions. The charge disproportionation and the charge transfer are accompanied by 

significant changes in structural, transport, and magnetic properties.




October 26-27, 2012 

Covalency influence on crystal chemistry of some inorganic compounds with 

octahedral-site cations 

Y. Shirako 1 

1 Department of Chemistry, Gakushuin University, 1-5-1, Mejiro, Toshima-ku, Tokyo, 171-8588, Japan 



below.) 

The purpose of this presentation is to explain the local structures which is a network of octahedral 

ionic clusters in inorganic compounds using a modification of the methods to predict a shape of severalatomic 

molecules [1], and then to restrict the adopted inorganic crystal structure of each composition. This 

way is a qualitative rule and yet easily available. In particular, the improved method may be effective to 

classify pressure-induced structural phase transition sequences of various compounds. 

In the covalency-dominant small molecules such as CO 2 and NH 3 , shape of the molecule depends on 

number of electrons in valence shell orbitals of molecule (Walsh’s rule) [1]. Essence of the rule is 

delocalization of the lone-pair electrons. The author extends the Walsh’s rule to be able to apply to 

inorganic crystal structures with frameworks of the octahedra. The modified rule can be called “extended 

Walsh’s rule”. In the extended rule, number of electrons in outer shell orbitals can be used as a qualitative 

parameter to relate stability of the inorganic crystal structures with those compositions. For example, all 

M-X-M angles in post-perovskite compounds AMX 3 are more bent to 90 º than those in the perovskite 

which is less dense than the post-perovskite. The extended Walsh’s rule suggests that, if all 4-electrons on 

p orbitals of closed-shell X can be delocalized to t 2g orbitals on M’s, linear M-X-M fragments are stable, 

or else bent M-X-M fragments are stable since the electrons can be delocalized through e g orbitals on M’s. 

Therefore, the M-X-M fragments in which the M ions have at least one of d orbitals with inability of 

formation of -bond (filled orbitals), unlike Ti 4+ , Nb 4+ and Re 4+ , are expected to be bent by covalent 

effect. Actually, post-perovskite compounds containing the -bond ability cations such as Ti 4+ and Zr 4+ in 

octahedral-sites are almost not reported. 

The previous articles have been reported on the similar topic [2, 3, 4]. Goodenough and Kafalas (1973) 

[2] described discussion about contribution of covalency, electrostatic energy, and ionic size for crystal




October 26-27, 2012 

Interaction-Enhanced Coherence Between Two-Dimensional Dirac Layers 

Inti Sodemann, Dmytro Pesin and Allan MacDonald 

University of Texas at Austin 

Email: sodemann@physics.utexas.edu 

We estimate the interaction induced coherence gap between parallel layers of two-dimensional Dirac 

electron liquids by accounting explicitly for the retardation of the effective inter-layer interaction and selfconsistently 

incorporating the influence of the gap on screening. We apply our results to graphene doublelayers 

and topological insulator thin films.




October 26-27, 2012 

Electrode and Cell Configuration Design of Rechargeable Lithium–Sulfur Batteries 

Yu-Sheng Su, Chenxi Zu, Sheng-Heng Chung, Yongzhu Fu and Arumugam Manthiram* 

Electrochemical Energy Laboratory, Materials Science and Engineering Program, The University of Texas at 

Austin, Austin, TX 78712, USA 

Email: manth@austin.utexas.edu Website: http://www.me.utexas.edu/~manthiram/index.htm 



below.) 

The limitations in the cathode capacity compared to the capacity of anode have been an impediment to 

make advances in the lithium-ion battery area. The lithium–sulfur (Li–S) system is appealing in this 

regard as sulfur exhibits an order of magnitude higher capacity (1,675 mAh g -1 ) than the currently used 

cathodes. However, low active material utilization and poor cycle life hinder the practicality of Li–S 

batteries due to the insulating nature of sulfur/lithium sulfide redox products and dissolution behavior of 

polysulfide species. We present here several state-of-the-art designs based on electrode/cell configuration 

aspects to tackle the drawbacks in the cathode region. Various carbon–sulfur and polymer–sulfur 

composite materials have been developed to retain intermediate polysulfides during charge/discharge, 

leading to good cycle stability. Additionally, a simple adjustment to the traditional Li–S battery system 

configuration has been designed to achieve high capacity with a long and stable cycle life. Carbon 

interlayers with different framework structures act as a liaison between the cathode and the separator, 

resulting in a significant improvement not only in the efficiency of active material utilization but also in 

capacity retention, without involving complex synthesis. Surface modification applied to the carbon 

interlayer can further enhance the cycle performance. Sulfur cathodes with 3D architectures also offer 

excellent capacity retention by a single-step processing. These approaches decrease the internal charge 

transfer resistance and localize the soluble polysulfide species, facilitating a feasible means of fabricating 

commercially viable lithium–sulfur batteries.

Abstract 




October 26-27, 2012 

High Capacity Lithium-Metal-Oxide Electrodes: Challenges and Opportunities 

Michael M. Thackeray 1 , J. R. Croy 1 , D. Kim 1 , M. Balasubramanian 2 and S.-H. Kang 3 

1 Electrochemical Energy Storage Department 

Chemical Sciences and Engineering Division 

2 X-ray Science Division, Advanced Photon Source, Argonne National Laboratory 

Argonne, IL 60439, USA 

3 Samsung SDI, Yongin, Gyeonggi-do, Korea 

Email: thackeray@anl.gov 

It is well known that lithium-manganese-oxide electrodes are significantly more stable than their cobalt 

and nickel analogues, particularly at high states of charge, and that some manganese-based structures can 

provide a very high rechargeable capacity (~250 mAh/g) between 4.6 and 2.5 V, albeit it a relatively slow 

current rate. The urgent need to design and develop safe, high energy and power lithium-ion batteries that 

are not prone to thermal runaway and fire has therefore placed considerable attention on manganese oxide 

systems, particularly for electrically-powered vehicles. On the other hand, lithium-manganese-oxides tend 

to suffer from chemical and physical instabilities induced, for example, by oxygen loss at high potentials, 

dissolution phenomena, crystallographic changes and voltage decay during charge and discharge; these 

phenomena can severely impact the capacity, rate and cycle life of the cells. A significant worldwide 

effort is therefore being made to address these chemical, electrochemical and structural limitations. 

The results of recent research conducted at Argonne National Laboratory in designing and stabilizing high 

capacity lithium- and manganese-rich electrode structures for Li-ion cells will be presented. The 

versatility of using a layered Li 2 MnO 3 precursor as a template to synthesize ‘layered-layered’ 

(xLi 2 MnO 3 [1-x] LiMO 2 ), ‘layered-spinel’ and ‘layered-rocksalt’ composite electrode structures will be 

highlighted. Electrochemical data and structural insights of these highly complex materials as determined 

by powder X-ray diffraction and absorption techniques at Argonne’s Advanced Photon Source will be 

presented.




October 26-27, 2012 

H + ↔Li + Ion-Exchange Chemistry of Ceramic Garnet-Type Electrolytes 

Lina Truong and Venkataraman Thangadurai* 

University of Calgary, 2500 University Drive NW, Calgary, Alberta, T2N 1N4 

Email: vthangad@ucalgary.ca Website: www.chem.ucalgary.ca/research/groups/vthangad/index.html 



below.) 

Chemical stability and ion-exchange of the garnet-type fast Li ion conducting Li 5+x Ba x La 3-x Nb 2 O 12 (x = 0, 

0.5, 1) were studied in various media such as water and organic acids. The H + /Li + reaction was found to be 

most successful for x = 0, which showed ~89% H + /Li + exchange reaction, while x = 0.5 showed ~46% 

and x = 1 showed ~20% in water at room temperature. In Li 5 La 3 Nb 2 O 12 , more of the Li ions occupy the 

tetrahedral sites, the ion-exchange reaction occurs readily and to a greater extent. The relative population 

of Li ions that reside in the octahedral sites increases with increasing Li content in Li 5+x Ba x La 3-x Nb 2 O 12 

and the proton-exchange proceeds to a lesser extent in water. The reaction was also shown to be 

reversible, where ionic conductivity of the reverse Li exchanged product from the H-garnet, for x = 0, was 

found to show comparable values to its original solid state synthesized Li 5 La 3 Nb 2 O 12 . Similar trends were 

found when the H + /Li + ion-exchange reaction was done at room temperature using weak organic acids, 

including CH 3 COOH and C 6 H 5 COOH as proton sources. The exchange was almost (100%) completed 

using the x = 0 member in CH 3 COOH.

Abstract: 




October 26-27, 2012 

In situ Electron Microscopy of Electrical Energy Storage Materials 

R.R. Unocic, X. Sun, L. Baggetto, G.M. Veith, K.A. Unocic, S. Dai, N.J. Dudney, K.L.More 

1 Oak Ridge National Laboratory, Oak Ridge, TN 37831 

Email: unocicrr@ornl.gov 

Electrode/electrolyte interfaces play an active role in controlling the electrochemical energy conversion process in 

lithium ion batteries. Of critical importance to the performance and life-cycle is the formation of the solid 

electrolyte interphase (SEI), which is a passive interfacial, nm-scale film that forms at the electrode/electrolyte 

(solid/liquid) interface as a result of electrolyte decomposition reactions during electrochemical cycling. Due to the 

dynamic nature of the SEI, it has proven difficult to design experiments that will reveal details regarding SEI 

formation mechanisms as well as how its structure and chemistry evolves during electrochemical cycling. In-situ 

transmission electron microscopy provides a viable means for directly correlating structure-property relationships in 

materials where dynamically evolving processes can be studied in real-time and at high spatial and temporal 

resolution. Here we investigate the formation of the SEI on graphite anodes during electrochemical cycling 

experiments with organic liquid electrolytes. The unique feature of this method is the capability to wholly contain 

volatile and corrosive liquid electrolytes when placed into the high vacuum environment of the TEM. By sealing the 

electrodes and electrolytes between silicon nitride membranes, direct imaging of the electrode material, interfaces, 

and surfaces under electrochemical charge/discharge cycling is permissible. The development and implementation 

of this unique tool will enable fundamental research related to electrical energy storage systems. 

Research supported by (1) the Office of Vehicle Technologies, Office of Energy Efficiency and Renewable Energy 

(2) the Fluid Interface Reactions, Structures and Transport (FIRST) Center, an Energy Frontier Research Center 

funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences and (3) ORNL's 

Shared Research Equipment (ShaRE) User Facility, which is sponsored by the Office of Basic Energy Sciences, 

U.S. Department of Energy.




October 26-27, 2012 

Novel Cathode and Anode Materials for Solid Oxide Fuel Cells 

Matthew West, 1 Daeil Yoon, 2 and Arumugam Manthiram 1,2 

1 Department of Chemical Engineering and 2 Materials Science and Engineering Program 

The University of Texas at Austin, Austin, TX 




below.) 

Solid oxides fuel cells (SOFCs) offer great promise for future energy production due to their high 

efficiencies and fuel flexibility. Despite their benefits, the commercialization of SOFCs is hampered by 

severe materials challenges, and there is significant interest in reducing their operating temperatures from 

the conventional > 800 o C to an intermediate range of 500 o C – 800 o C and in utilizing hydrocarbon fuels 

like natural gas directly instead of hydrogen fuel. We present here the development of new materials and 

novel synthesis approaches to address some of these issues. A new series of cathode materials RBaM 4 O 7 

(R = rare earth) identified in our group exhibits good catalytic activity with an ideal matching of the 

thermal expansion coefficient to that of conventional electrolytes like YSZ. However, the RBaM 4 O 7 series 

suffers from long-term stability issues, and attempts to improve stability often come at the expense of 

reduced catalytic activity for the oxygen reduction reaction. Through appropriate cationic substitutions 

with small amount of dopants in the crystal lattice, we have been able to resolve the stability issues 

without significantly sacrificing the electrochemical performance. As for the anode, the oxidation of 

hydrocarbon fuels on conventional Ni-YSZ catalyst is accompanied by carbon deposition on Ni, resulting 

in a reduction in catalytic activity and overall life expectancy of the cell. To alleviate these problems and 

enhance the performance of SOFC anodes, both heterogeneous anode catalysts and new synthesis 

techniques for traditional materials are being investigated.




October 26-27, 2012 

Surprising superexchange interactions in osmate double perovskites 

Patrick M. Woodward 

Department of Chemistry 

Ohio State University 

Email: woodward.55@osu.edu 



below.) 

The synthesis, structures and magnetic behavior of A 2 MOsO 6 osmate double perovskites are presented in this 

poster. The compounds A 2 CrOsO 6 , A 2 FeOsO 6 , A 2 CoOsO 6 and A 2 MgOsO 6 (A = Sr, Ca) have been prepared and 

characterized. All of the compounds are ordered double perovskites, many of which undergo ocathedral tilting 

distortions. All of the compounds studied contain localized electrons and their magnetism is dictated by 

superexchange interactions. However, the strength and sign of the superexchange interactions, particularly between 

3d transition metal ions and osmium, defy conventional expectations in many cases. For example in Sr 2 CoOsO 6 , 

the Co(II) and Os(VI) ions order independently despite the fact that the two sublattices are completely 

interpenetrating. This suggests that the four bond Os–O–Co–O–Os and Co–O–Os–O–Co superexchange 

interactions are stronger than the much shorter Os–O–Co superexchange interactions. This surprising conclusion is 

supported by DFT calculations. In Sr 2 FeOsO 6 , which contains the d 5 high spin Fe(III) ion and the d 3 Os(V) ion, the 

Goodenough-Kanamori rules predict ferromagnetic coupling, but antiferromagnetism is observed. The behavior of 

this family of compounds highlights the need for deeper understanding of superexchange interactions between 

transition metals with very different d-orbital energies and sizes.




October 26-27, 2012




October 26-27, 2012 

Atomic and electronic structures of superionic solid electrolyte Li 10 GeP 2 S 12 

K. Xiong a , R. C. Longo a , and Kyeongjae Cho a,b,* 

a Materials Science & Engineering Dept, The University of Texas at Dallas, Richardson, TX 75080, USA 

b Physics Dept, The University of Texas at Dallas, Richardson, TX 75080, USA 

Email: ka.xiong@utdallas.edu Website: 



below.) 

Inorganic solid electrolytes have attracted much attention for being used in lithium batteries to replace 

conventional liquid electrolytes to achieve better safety and reliability. This has led to intensive research 

during the last three decades and many electrolyte candidates have been proposed such as lithium 

phosphate oxynitride and Li 2 S-P 2 S 5 -based glasses such as lithium thiophosphate. LiPON has been used as 

commercial solid electrolyte in thin-film batteries. However, its ionic conductivity is rather low (10 -6 S 

cm -1 ). To improve the performance of the battery cell, the electrolyte material should have high ionic 

conductivity. It has been found recently that a superionic conductor, Li 10 GeP 2 S 12 , possesses an extremely 

high ion conductivity of 10 mS cm -1 . To date, few theoretical studies have been carried out on 

understanding the fundamental properties of this material. For this purpose, we use first principles 

calculations to investigate the impact of Li defects on the atomic and electronic structures of Li 10 GeP 2 S 12 . 

To understand the mechanisms of ion transport, we investigate the Li ion migration in Li 10 GeP 2 S 12 by 

calculating the activation energy barriers of various possible diffusion pathways. In addition, we propose 

possible solutions (e.g. doping) to optimize the Li ion migration in these materials. This study will help us 

to gain fundamental understanding on the Li ion diffusion process and possible mechanisms to maximize 

it.




October 26-27, 2012 

Flowerlike Co 3 O 4 particles Loaded with Copper Nanoparticle as a Bifunctional 

Catalyst for Lithium-Air Batteries 

Wei Yang, Jason Salim, Chunwen Sun, LiquanChen, and Youngsik Kim 

Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 

100190, China 

Email: csun@iphy.ac.cn 

Website: 



below.) 

The high cost of energy storage and conversion devices such as PEM fuel cells and metal/air batteries 

restrains their practical use. For lithium-air battery, another issue that has to be addressed in the current 

technology is the limitations of oxygen reduction reaction (ORR) during discharging process and oxygen 

evolution reaction (OER) during charging process. The sluggish kinetics of ORR and OER in lithium-air 

batteries is ascribed to the low efficiency of catalysts. A low-cost and stable electrocatalysts is the solution 

to tackle this problem. In this study, we found that porous flowerlike Co 3 O 4 particles prepared by 

hydrothermal method and loaded with copper nanoparticles on their surface have shown to be a high 

performance and stable bifunctional electrocatalyst for the ORR and OER reactions. The cobalt oxidebased 

catalysts show better performance during the discharging and charging process at a current density 

of 0.05 mA cm -2 compared with that of the Vulcan XC-72 and close to that of the 50% Pt/carbon-black 

catalyst. This electrocatalyst could be used in a metal/air battery or a PEM fuel cell as an efficient and 

stable bifunctional catalyst. 

5.0 

5 

4.5 

4 

Cell Voltage (V) 

4.0 

V 

3.5 

3.0 

Cell Voltage (V) 

3 

2 

1 

50% Pt/C 

Vulcan XC-72 

2.5 

Co 3 O 4 

Co 3 O 4 - Cu 

2.0 

0 2 4 6 8 10 

Time (h) 

0 

0 200 400 600 800 1000 1200 1400 

Capacity (mAHg -1 Co 3 O 4 -Cu ) 

Figure 1 Comparison of the charge and discharge curves of the prepared lithium-air batteries with various catalysts. 

Figure 2 Voltage versus discharge/charge capacity for the lithium-air batteries with the Co 3 O 4 -Cu catalyst at a current density of 0.05 mA cm -2 with the active 

catalyst (Co 3 O 4 -Cu) mass loading of 0.5 mg/cm 2 .




October 26-27, 2012 

Multiscale Simulation Study of Si Anode Material for Li-ion Battery Applications 

Hengji Zhang 1 , Janghyuk Moon 2 , Maenghyo Cho 2 , Kyeongjae Cho 1, 2 

1 Department of Physics and Department of Materials Science and Engineering, University of Texas at Dallas, 

Richardson, Texas, 75080, US 

2 Division of WCU Multiscale Mechanical Design, School of Mechanical and Aerospace Engineering, 

Seoul National University, Seoul 151-742, Republic of Korea 

Email: hengji@utdallas.edu Website: http://www.utdallas.edu/~hxz083000/ 



below.) 

Si based anode materials have attracted much interests for Li-ion battery applications because of its known 

advantages such as high energy density, high operating voltage, and low cost and toxicity. Despite of these 

attractive features, Si based anode materials often shows structure failure caused by rapid volume 

expansion during the battery charging process. To understand the mechanism of this structure failure, we 

use first principle method to study the kinetics of Li diffusion in Si anode materials, and the mechanical 

strength of Li-Si alloy phases. Based on these first principle results, we try to develop Li-Si Reactive 

Force Field (Reaxff) potential parameters to run classical MD simulations, which can be useful to 

investigate the evolution of structures and compositions for the lithiation of Si anode materials. In this 

work, we compare the results predicted both from first principle method and classical MD simulations.


In Honor of His 90 th Birthday – 


October 26-27, 2012 

Structure – Electrochemical and Magnetic Property Relationships 

in Transition Metal Oxides for Energy Applications 

Xiao-Dong Zhou 

Department of Chemical Engineering, University of South Carolina 

Email: xiao-dong.zhou@sc.edu Website: www.che.sc.edu/faculty/zhou 

The aim of this paper is to present a theoretical and practical view of electronic, electrochemical and 

magnetic properties of functional oxides, with a focus on correlating structure and properties with the 

chemical composition, defect chemistry and microstructures. I will use oxides for solid oxide fuel cells, 

thermoelectric converters, and lithium-ion batteries as examples to illustrate the closely coupled structureproperty 

relationships in perovskite-type oxides, misfitted layered Ca 3 CO 4 O 9+ , Fe 3 O 4- nanoparticles, 

MnO 2 nanowires, and SnO x nanoribbons. 

Disproportionation reaction will be discussed in (La,Sr)MnO 3 , while distinct oxidation states (e.g. III, IV, 

and V) of Fe in (La,Sr)FeO 3 are observed and presented in this poster. Electronic conductivity will be 

correlated with defect and magnetic properties in these compounds. Defect chemistry and transport 

properties will be discussed in Ca 3 Co 4 O 9+δ , which adopts a misfit layered structure: the CdI 2 type for the 

“CoO 2 ” layer and the rock salt type for the “Ca 2 CoO 3 ” layer. Copper nanoribbon supported Fe 3 O 4 and 

SnO x as the negative electrodes for lithium-ion batteries will be discussed to correlate structureelectrochemical 

property relationship. Superior recyclability can be achieved by improving the interfacial 

structures. 

The specific attention of this poster will be on the physical understanding of the origin of activity-stability 

dichotomy and the engineering solutions to decouple this conjugation.

Invited Talks: Transition Metal Oxides - University Blog Service - The ...

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