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Mechanism of Ultrafast (Dis)charging of Li Ion Batteries by Heterogeneous Doping of LiFePO4

Published online by Cambridge University Press:  01 February 2011

Stefan Adams ,
R. Prasada Rao  and
Haiping Choo
Stefan Adams
Affiliation:
mseasn@nus.edu.sg, National University of Singapore, Materials Science and Engineering, Singapore, Singapore
R. Prasada Rao
Affiliation:
mserpr@nus.edu.sg, National University of Singapore, Materials Science and Engineering, Singapore, Singapore
Haiping Choo
Affiliation:
haipingchoo@nus.edu.sg, National University of Singapore, Materials Science and Engineering, Singapore, Singapore
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Abstract

Molecular dynamics (MD) simulations with a dedicated force-field and our bond valence (BV) pathway analysis have been employed to reproduce and explain the experimentally observed ultrafast Li+ transport in surface modified LixFePO4-δ as a consequence of heterogeneous doping, i.e. the Li+ redistribution in the vicinity of the interface between LixFePO4 and a pyrophosphate glass surface layer. Over the usual working temperature range of LIBs Li+ ion conductivity in the surface modified LixFePO4 phase is enhanced by 2-3 orders of magnitude, while the enhancement practically vanishes for T > 700K. Simulations for the bulk phase reproduce the experimental conductivities and the activation energy of 0.57eV (for x ≈ 1). A layer-by-layer analysis of structurally relaxed multilayer systems indicates a continuous variation of Li+ mobility with the distance from the interface and the maximum mobility close to the interface, but Li+ diffusion rate remains enhanced (compared to bulk values) even at the center of the simulated cathode material crystallites. Our BV migration pathway analysis in the dynamic local structure models shows that the ion mobility is related to the extension of unoccupied accessible pathway regions. The change in the extent of Li redistribution across the interface with the overall Li content constitutes a fast pseudo-capacitive (dis)charging contribution.

Keywords

Lisimulationionic conductor
Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 1263: Symposium Y – Computational Approaches to Materials for Energy , 2010 , 1263-Y02-09
Copyright
Copyright © Materials Research Society 2010

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