Thermodynamic Origin of Reaction Non-Uniformity in Battery Porous Electrodes and Its Mitigation
Abstract
The development of non-uniform reaction current distribution within porous electrodes is a ubiquitous phenomenon during battery charging/discharging and frequently controls the rate performance of battery cells. Reaction inhomogeneity in porous electrodes is usually attributed to the kinetic limitation of mass transport within the electrolyte and/or solid electrode phase. In this work, however, we reveal that it is also strongly influenced by the intrinsic thermodynamic behavior of electrode materials, specifically the dependence of the equilibrium potential on the state of charge: the electrode reaction becomes increasingly non-uniform when the slope of the equilibrium potential curve is reduced. We employ numerical simulations and equivalent circuit model to elucidate such a correlation and show that the degree of reaction inhomogeneity and the resultant discharge capacity can be predicted by a dimensionless reaction uniformity number. For electrode materials that have equilibrium potentials insensitive to the state of charge and exhibit significant reaction non-uniformity, we demonstrate several approaches to spatially homogenizing the reaction current inside porous electrodes, including matching the electronic and ionic resistances, introducing graded electronic conductivity and reducing the surface reaction kinetics.
- Publication Date:
- Research Org.:
- United States Advanced Batter Consortium, LLC, Southfield, MI (United States); Rice Univ., Houston, TX (United States); Univ. of California, Oakland, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office
- OSTI Identifier:
- 1658645
- Alternate Identifier(s):
- OSTI ID: 1799199
- Grant/Contract Number:
- EE0006250; SC0019111; AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Name: Journal of the Electrochemical Society Journal Volume: 167 Journal Issue: 12; Journal ID: ISSN 0013-4651
- Publisher:
- The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 42 ENGINEERING; 25 ENERGY STORAGE; Electrochemistry; Materials Science
Citation Formats
Wang, Fan, and Tang, Ming. Thermodynamic Origin of Reaction Non-Uniformity in Battery Porous Electrodes and Its Mitigation. United States: N. p., 2020.
Web. doi:10.1149/1945-7111/abb383.
Wang, Fan, & Tang, Ming. Thermodynamic Origin of Reaction Non-Uniformity in Battery Porous Electrodes and Its Mitigation. United States. https://doi.org/10.1149/1945-7111/abb383
Wang, Fan, and Tang, Ming. Mon .
"Thermodynamic Origin of Reaction Non-Uniformity in Battery Porous Electrodes and Its Mitigation". United States. https://doi.org/10.1149/1945-7111/abb383.
@article{osti_1658645,
title = {Thermodynamic Origin of Reaction Non-Uniformity in Battery Porous Electrodes and Its Mitigation},
author = {Wang, Fan and Tang, Ming},
abstractNote = {The development of non-uniform reaction current distribution within porous electrodes is a ubiquitous phenomenon during battery charging/discharging and frequently controls the rate performance of battery cells. Reaction inhomogeneity in porous electrodes is usually attributed to the kinetic limitation of mass transport within the electrolyte and/or solid electrode phase. In this work, however, we reveal that it is also strongly influenced by the intrinsic thermodynamic behavior of electrode materials, specifically the dependence of the equilibrium potential on the state of charge: the electrode reaction becomes increasingly non-uniform when the slope of the equilibrium potential curve is reduced. We employ numerical simulations and equivalent circuit model to elucidate such a correlation and show that the degree of reaction inhomogeneity and the resultant discharge capacity can be predicted by a dimensionless reaction uniformity number. For electrode materials that have equilibrium potentials insensitive to the state of charge and exhibit significant reaction non-uniformity, we demonstrate several approaches to spatially homogenizing the reaction current inside porous electrodes, including matching the electronic and ionic resistances, introducing graded electronic conductivity and reducing the surface reaction kinetics.},
doi = {10.1149/1945-7111/abb383},
journal = {Journal of the Electrochemical Society},
number = 12,
volume = 167,
place = {United States},
year = {2020},
month = {9}
}
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