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Title: Comprehensive Study of the Polarization Behavior of LiFePO4 Electrodes Based on a Many-Particle Model

Journal Article · · Journal of the Electrochemical Society

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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1483404
Journal Information:
Journal of the Electrochemical Society, Vol. 165, Issue 10; ISSN 0013-4651
Publisher:
The Electrochemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 20 works
Citation information provided by
Web of Science

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Cited By (4)

Memory-effect-induced electrochemical oscillation of an Al-doped Li 4 Ti 5 O 12 composite in Li-ion batteries journal January 2019
Thermodynamically Consistent and Computationally Efficient 0D Lithium Intercalation Model of a Phase Separating Cathode Particle journal January 2019
Complex Impedance of Li-Ion-Battery Phase-Transformation Electrodes at History-Dependent States of Charge journal January 2019
Modelling electrode heterogeneity in lithium-ion batteries: unimodal and bimodal particle-size distributions preprint January 2020