V. Focused Fundamental Research - EERE - U.S. Department of ...

Ceder – MIT, Grey – Stony Brook U.
V.B.1 First Principles Calculations and NMR Spectroscopy (MIT, Stony Brook U.)
lithium-ion diffusion. We have identified compounds
based on the crystal structure of the sidorenkite (a rare
mineral of formula Na 3 Mn(CO 3 )(PO 4 ) to be of interest as
cathode materials. Two-electron activity and high specific
energies (> 800 Wh/kg) can be expected from this class of
materials. We have also performed a further computational
stability exploration, evaluating the stability of the generic
A 3 M(YO 3 )(XO 4 ) compositions (with A=Na, Li, M=a
redox active element and Y=C, B) in the sidorenkite
crystal structure. Figure V - 7 shows the result of this stability
analysis. Each line represents a mixture of polyanions
(e.g., SO 4 -CO 3 ), and each column a specific metal cation.
Experimental work on some of these materials has been
initiated. Some of the materials predicted have now been
successfully synthesized and their electrochemical
properties are being tested as a potential cathode material
for a Na-ion or Li-ion battery. Structural characterization,
including time-resolved powder diffraction and 23 Na NMR
spectrosopy, has been carried out to evaluate limitations to
performance.
Figure V - 7: Stability of the generic A3M(YO3)(XO4) compositions (with
A=Na,Li, M= and Y=C,B) in the sidorenkite crystal structure. The color is a
measure of thermodynamic stability. Light (dark) colors indicate instability
(stability)
Conclusions and Future Directions
In conclusion, relationships between morphology and
electrochemical performance have been explored both
theoretically and experimentally, highlighting the role that
defects, ionic transport and the amount of active surface
areas (for Li insertion/removal) play in controlling rate.
New NMR in and ex situ methodologies to investigate
local and microstructure have been developed. The
approaches have been used to investigate silicon and Li
dendrite formation.
FY 2011 Publications/Presentations
1. Presentation to the 2010 DOE Annual Peer Review
Meeting.
2. “Pair Distribution Function Analysis and Solid State
NMR Studies of Silicon Electrodes for Lithium Ion
Batteries: Understanding the (De)lithiation
Mechanisms,” B. Key, M. Morcrette, J-M. Tarascon
and C.P. Grey, J. Am. Chem. Soc., 133, 503-512
(2011).
3. “LiCoO 2 Concaved Cuboctahedrons from Symmetry-
Controlled Topological Reactions,” H.L. Chen, L.J.
Wu, L.H. Zhang, Y.M. Zhu and C.P. Grey, J. Am.
Chem. Soc., 133, 262–270 (2011).
4. “Effect of Ball-Milling and Lithium Insertion on the
Lithium Mobility and Structure of Li 3 Fe 2 (PO 4 ) 3, ” J.
Cabana, J. Shirakawa, M. Nakayama, M. Wakihara
and C.P. Grey, J. Mater. Chem., 21, 10012-10020
(2011).
5. “C-13 Solid State NMR Suggests Unusual Breakdown
Products in SEI Formation on Lithium Ion
Electrodes,” N. Leifer, M.C. Smart, G.K.S. Prakash,
L. Gonzalez, L. Sanchez, K.A. Smith, P. Bhalla, C.P.
Grey and S.G. Greenbaum, J. Electrochem. Soc., 158,
A471-A480, (2011).
6. “Citric Acid- and Ammonium-Mediated
Morphological Transformations of Olivine LiFePO 4
Particles,” Z. Lu, H. Chen, R. Robert, B.Y.X. Zhu, J.
Deng, L. Wu, C.Y. Chung and C.P. Grey, Chem.
Mat., 23, 2848-2859, (2011).
7. “Resolving the different silicon clusters in Li 12 Si 7 by
29 Si and 6,7 Li Solid State Nuclear Magnetic Resonance
Spectroscopy”, T. K.-J. Köster, E. Salager, A. J.
Morris, B. Key, V. Seznec, M. Morcrette, C. J.
Pickard, C. P. Grey, Angewandte, in press (2011).
Presentation to the 2010 DOE Annual Peer Review
Meeting.
8. “Iron and Manganese Pyrophosphates as Cathodes for
Lithium-Ion Batteries,” H. Zhou, S. Upreti, N.A.
Chernova, G. Hautier, G. Ceder, M.S. Whittingham,
Chem. Mater., 23 (2), 293-300 (2011).
9. “Recharging Lithium Battery Research With First-
Principles Methods,” G. Ceder, G. Hautier, A. Jain,
S.P. Ong, MRS Bulletin, 36, pp. 185-191 (2011).
10. “Comparison of Small Polaron Migration and Phase
Separation in Olivine LiMnPO4 and LiFePO4 Using
Hybrid Density Functional Theory,” S.P. Ong, V.
Chevrier, G. Ceder, Physical Review B, 83, 075112
(2011).
11. “Challenges for Na-ion Negative Electrodes,” V.L.
Chevrier, G. Ceder, Journal of the Electrochemical
Society, 158 (9), A1011-A1014 (2011).
12. “Voltage, Stability and Diffusion Barrier Differences
Between Sodium-Ion and Lithium-Ion Intercalation
Materials,” S.P. Ong, V.L. Chevrier, G. Hautier, A.
FY 2011 Annual Progress Report 473 Energy Storage R&D