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Title: Comprehensive Study of the Polarization Behavior of LiFePO 4 Electrodes Based on a Many-Particle Model

Abstract

The unique polarization behavior of LiFePO 4 electrodes was investigated using mathematical simulations with a many-particle model, which have a non-monotonic potential profile for each LiFePO 4 particle, and analyzed by the active population concept. The present simulations reveal two known polarization behaviors, namely the memory effect and path dependence. Notably, a hitherto unknown polarization behavior, the so-called relaxation-induced polarization (RIP), was also identified. The memory effect requires, at a minimum, a sequential four-step operation. By comparison, RIP is triggered only by a one-step operation, namely a long rest. In effect, the polarization associated with the memory effect and RIP was caused by a reduction of the active particles in the two-phase region via relaxation during a rest. The path-dependence mechanism was attributed to kinetically inhomogeneous reactions for each particle. We further found that narrowing the particle size distribution was an effective means to reduce polarization viz. the memory effect and path dependence of LiFePO 4 electrodes. However, RIP could not be suppressed by narrowing the particle size distribution. Furthermore, a comprehensive understanding of these polarization behaviors with our model provides a more accurate way to estimate the state of charge in Li-ion batteries with LiFePO 4 electrodes.

Authors:
ORCiD logo [1];  [2];  [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Toyota Central R&D Labs., Aichi (Japan)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1483404
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 165; Journal Issue: 10; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Electrochemistry; LiFePO4; Lithium-ion battery; Many-particle model; Positive electrode; Li-ion battery; Mathematical simulation

Citation Formats

Kondo, Hiroki, Sasaki, Tsuyoshi, Barai, Pallab, and Srinivasan, Venkat. Comprehensive Study of the Polarization Behavior of LiFePO4 Electrodes Based on a Many-Particle Model. United States: N. p., 2018. Web. doi:10.1149/2.0181810jes.
Kondo, Hiroki, Sasaki, Tsuyoshi, Barai, Pallab, & Srinivasan, Venkat. Comprehensive Study of the Polarization Behavior of LiFePO4 Electrodes Based on a Many-Particle Model. United States. doi:10.1149/2.0181810jes.
Kondo, Hiroki, Sasaki, Tsuyoshi, Barai, Pallab, and Srinivasan, Venkat. Fri . "Comprehensive Study of the Polarization Behavior of LiFePO4 Electrodes Based on a Many-Particle Model". United States. doi:10.1149/2.0181810jes. https://www.osti.gov/servlets/purl/1483404.
@article{osti_1483404,
title = {Comprehensive Study of the Polarization Behavior of LiFePO4 Electrodes Based on a Many-Particle Model},
author = {Kondo, Hiroki and Sasaki, Tsuyoshi and Barai, Pallab and Srinivasan, Venkat},
abstractNote = {The unique polarization behavior of LiFePO4 electrodes was investigated using mathematical simulations with a many-particle model, which have a non-monotonic potential profile for each LiFePO4 particle, and analyzed by the active population concept. The present simulations reveal two known polarization behaviors, namely the memory effect and path dependence. Notably, a hitherto unknown polarization behavior, the so-called relaxation-induced polarization (RIP), was also identified. The memory effect requires, at a minimum, a sequential four-step operation. By comparison, RIP is triggered only by a one-step operation, namely a long rest. In effect, the polarization associated with the memory effect and RIP was caused by a reduction of the active particles in the two-phase region via relaxation during a rest. The path-dependence mechanism was attributed to kinetically inhomogeneous reactions for each particle. We further found that narrowing the particle size distribution was an effective means to reduce polarization viz. the memory effect and path dependence of LiFePO4 electrodes. However, RIP could not be suppressed by narrowing the particle size distribution. Furthermore, a comprehensive understanding of these polarization behaviors with our model provides a more accurate way to estimate the state of charge in Li-ion batteries with LiFePO4 electrodes.},
doi = {10.1149/2.0181810jes},
journal = {Journal of the Electrochemical Society},
number = 10,
volume = 165,
place = {United States},
year = {Fri Jul 06 00:00:00 EDT 2018},
month = {Fri Jul 06 00:00:00 EDT 2018}
}

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Works referenced in this record:

Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries
journal, April 1997

  • Padhi, A. K.
  • Journal of The Electrochemical Society, Vol. 144, Issue 4, p. 1188-1194
  • DOI: 10.1149/1.1837571