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Mesopores inside electrode particles can change the Li-ion transport mechanism and diffusion-induced stress

Published online by Cambridge University Press:  31 January 2011

Stephen J. Harris ,
Rutooj D. Deshpande ,
Yue Qi ,
Indrajit Dutta  and
Yang-Tse Cheng
Stephen J. Harris*
Affiliation:
General Motors R&D Center—Electrochemistry and Battery Systems, Warren, Michigan 48090
Rutooj D. Deshpande
Affiliation:
University of Kentucky, Department of Chemical and Materials Engineering, Lexington, Kentucky 40506-0046
Yue Qi
Affiliation:
General Motors R&D Center—Materials and Processes Laboratory Warren, Michigan 48090
Indrajit Dutta
Affiliation:
Trison Business Solutions, Inc.
Yang-Tse Cheng*
Affiliation:
University of Kentucky, Department of Chemical and Materials Engineering, Lexington, Kentucky 40506-0046
*
a)Address all correspondence to this author.e-mail:Stephen.j.harris@gm.com
b)This author was an editor of this journal during the review and decision stage. For the JMR policy on review and publication of manuscripts authored by editors, please refer to http://www.mrs.org/jmr_policy
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Abstract

Following earlier work of Huggins and Nix [Ionics6, 57 (2000)], several recent theoretical studies have used the shrinking core model to predict intraparticle Li concentration profiles and associated stress fields. A goal of such efforts is to understand and predict particle fracture, which is sometimes observed in degraded electrodes. In this paper we present experimental data on LiCoO2 and graphite active particles, consistent with previously published data, showing the presence of numerous internal pores or cracks in both positive and negative active electrode particles. New calculations presented here show that the presence of free surfaces, from even small internal cracks or pores, both quantitatively and qualitatively alters the internal stress distributions such that particles are prone to internal cracking rather than to the surface cracking that had been predicted previously. Thus, the fracture strength of particles depends largely on the internal microstructure of particles, about which little is known, rather than on the intrinsic mechanical properties of the particle materials. The validity of the shrinking core model for explaining either stress maps or transport is questioned for particles with internal structure, which includes most, if not all, secondary electrode particles.

Keywords

LiMicrostructureStress/strain relationship
Type
Articles
Information
Journal of Materials Research , Volume 25 , Issue 8: Materials for Electrical Energy Storage , August 2010 , pp. 1433 - 1440
Copyright
Copyright © Materials Research Society 2010

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