DOI: 10.1002/adfm.200600938. Strain Accommodation during Phase Transformations in Olivine‐Based Cathodes as a Materials Selection Criterion for High‐Power Rechargeable Batteries

Strain Accommodation during Phase Transformations in Olivine‐Based Cathodes as a Materials Selection Criterion for High‐Power Rechargeable Batteries

10.1002/adfm.200600938

Crossref journal-article

Wiley

Advanced Functional Materials (311)

Abstract

AbstractHigh energy lithium‐ion batteries have improved performance in a wide variety of mobile electronic devices. A new goal in portable power is the achievement of safe and durable high‐power batteries for applications such as power tools and electric vehicles. Towards this end, olivine‐based positive electrodes are amongst the most important and technologically enabling materials. While certain lithium metal phosphate olivines have been shown to be promising, not all olivines demonstrate beneficial properties. The mechanisms allowing high power in these compounds have been extensively debated. Here we show that certain high rate capability olivines are distinguished by having extended lithium nonstoichiometry (up to ca. 20 %), with which is correlated a reduced lattice misfit as the material undergoes an electrochemically driven, reversible, first‐order phase transformation. The rate capability in several other intercalation oxides can also be correlated with lattice strain, and suggests that nanomechanics plays an important and previously unrecognized role in determining battery performance.

Bibliography

Meethong, N., Huang, H. âY. S., Speakman, S. A., Carter, W. C., & Chiang, Y. âM. (2007). Strain Accommodation during Phase Transformations in OlivineâBased Cathodes as a Materials Selection Criterion for HighâPower Rechargeable Batteries. Advanced Functional Materials, 17(7), 1115â1123. Portico.

Authors 5

N. Meethong (first)
H.‐Y. S. Huang (additional)
S. A. Speakman (additional)
W. C. Carter (additional)
Y.‐M. Chiang (additional)

References 35 Referenced 394

10.1149/1.1837571
10.1149/1.1390960
10.1038/nmat732
10.1038/nmat1009b
Ravet et al. [6] contended that the high rate capability was due to inadvertent carbon coating despite TEM evidence to the contrary [2]. Striebel et al. [7] attributed the rate capability to particle size alone arguing that their “core/shell” transport model could adequately model the behavior without changing the assumed chemical diffusion coefficient of lithium. Subramanya Herle et al. [10] argued that the high electronic conductivities reported by Chung et al. were due to nanoscale networks of phosphide‐carbide phases but their observations were of sintered pellets and no electrochemical measurements were reported. Delacourt et al. [8 9] have argued firstly that aliovalent doping of LiFePO4is not possible and secondly that the process used by Chung et al. results in conductive coatings of carbon or metal phosphides on the particles again despite high‐resolution microscopy results refuting both [3]. Neither Delacourt et al. [8] nor Subramanya Herle et al. [10] provided electrochemical tests of their doped materials.
10.1038/nmat1009a
10.1149/1.1862477
C. Delacourt C. Wurm L. Laffont F. Sauvage J.‐B. Leriche R. Bouchet M. Morcrette J.‐M. Tarascon C. Masquelier inProc. MRS Fall Meeting(Eds: P. Knauth C. Masquelier E. Traversa E. D. Wachsman) The Materials Research Society Warrendale PA2004 321.
10.1038/nmat1335
10.1038/nmat1063
10.1149/1.1773731
10.1149/1.1884787
10.1149/1.2191432
10.1149/1.1785012
A. Chu Development of HEV batteries with lithium iron phosphate cathodes presented at the Advanced Automotive Battery Conf. Baltimore MD June 2006. See also:www.A123Systems.com.
10.1149/1.1945373
10.1149/1.2164548
10.1038/nmat1634
10.1111/j.1151-2916.1981.tb09875.x
10.1111/j.1151-2916.1993.tb03964.x
10.1111/j.1151-2916.1993.tb03965.x
N. Meethong H.‐Y. S. Huang W. C. Carter Y.‐M. Chiang Electrochem. Solid‐State Lett. in press.
10.1103/PhysRevB.73.174112
10.1149/1.2192695
E. A. Fitzgerald Dislocations in Strained‐Layer Epitaxy: Theory Experiments and Applications North‐Holland New York1991. (10.1016/0920-2307(91)90006-9)
10.1002/adfm.200500633
10.1149/1.2161523
10.1016/j.electacta.2005.05.053
10.1016/S0079-6786(97)81003-5
10.1149/1.1391631
10.1149/1.1581262
10.1021/cm000569z
N. Meethong D.‐W. Kim Y.‐M. Chiang unpublished.
10.1149/1.1385377
10.1016/S0378-7753(99)00203-7

Dates

Type	When
Created	18 years, 5 months ago (March 21, 2007, 12:33 p.m.)
Deposited	1 year, 11 months ago (Sept. 12, 2023, 2:21 a.m.)
Indexed	2 weeks, 2 days ago (Aug. 7, 2025, 4:55 a.m.)
Issued	18 years, 5 months ago (March 21, 2007)
Published	18 years, 5 months ago (March 21, 2007)
Published Online	18 years, 5 months ago (March 21, 2007)
Published Print	18 years, 3 months ago (May 7, 2007)

Funders 1

Royal Thai Government Scholarship Program

BibTeX

@article{Meethong_2007, title={Strain Accommodation during Phase Transformations in Olivine‐Based Cathodes as a Materials Selection Criterion for High‐Power Rechargeable Batteries}, volume={17}, ISSN={1616-3028}, url={http://dx.doi.org/10.1002/adfm.200600938}, DOI={10.1002/adfm.200600938}, number={7}, journal={Advanced Functional Materials}, publisher={Wiley}, author={Meethong, N. and Huang, H.‐Y. S. and Speakman, S. A. and Carter, W. C. and Chiang, Y.‐M.}, year={2007}, month=mar, pages={1115–1123} }

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