Thermodynamic Origin of Reaction Non-Uniformity in Battery Porous Electrodes and Its Mitigation

Wang, Fan; Tang, Ming

doi:10.1149/1945-7111/abb383

Thermodynamic Origin of Reaction Non-Uniformity in Battery Porous Electrodes and Its Mitigation

Journal Article · Mon Sep 07 00:00:00 EDT 2020 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1945-7111/abb383· OSTI ID:1658645

Wang, Fan;

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.

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Research Organization:: Rice Univ., Houston, TX (United States); United States Advanced Batter Consortium, LLC, Southfield, MI (United States); Univ. of California, Oakland, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; EE0006250; SC0019111

OSTI ID:: 1658645

Alternate ID(s):: OSTI ID: 1799199

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 12 Vol. 167; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (38)

Ultrathin Direct Atomic Layer Deposition on Composite Electrodes for Highly Durable and Safe Li-Ion Batteries Jung, Yoon Seok; Cavanagh, Andrew S.; Riley, Leah A. Advanced Materials, Vol. 22, Issue 19 https://doi.org/10.1002/adma.200903951	journal	April 2010
Design of Battery Electrodes with Dual-Scale Porosity to Minimize Tortuosity and Maximize Performance Bae, Chang-Jun; Erdonmez, Can K.; Halloran, John W. Advanced Materials, Vol. 25, Issue 9 https://doi.org/10.1002/adma.201204055	journal	December 2012
Understanding Inhomogeneous Reactions in Li-Ion Batteries: Operando Synchrotron X-Ray Diffraction on Two-Layer Electrodes Sasaki, Tsuyoshi; Villevieille, Claire; Takeuchi, Yoji Advanced Science, Vol. 2, Issue 7 https://doi.org/10.1002/advs.201500083	journal	May 2015
Fabrication of Low-Tortuosity Ultrahigh-Area-Capacity Battery Electrodes through Magnetic Alignment of Emulsion-Based Slurries Li, Linsen; Erb, Randall M.; Wang, Jiajun Advanced Energy Materials, Vol. 9, Issue 2 https://doi.org/10.1002/aenm.201802472	journal	November 2018
Reducing the Charge Carrier Transport Barrier in Functionally Layer-Graded Electrodes Zhang, Yanyan; Malyi, Oleksandr I.; Tang, Yuxin Angewandte Chemie International Edition, Vol. 56, Issue 47 https://doi.org/10.1002/anie.201707883	journal	October 2017
Stromverteilung in porösen elektroden Euler, J.; Nonnenmacher, W. Electrochimica Acta, Vol. 2, Issue 4 https://doi.org/10.1016/0013-4686(60)80025-4	journal	May 1960
Comparative study on transport properties for LiFAP and LiPF6 in alkyl-carbonates as electrolytes through conductivity, viscosity and NMR self-diffusion measurements Porion, Patrice; Dougassa, Yvon Rodrigue; Tessier, Cécile Electrochimica Acta, Vol. 114 https://doi.org/10.1016/j.electacta.2013.10.015	journal	December 2013
A Modified Multiphysics model for Lithium-Ion batteries with a LixNi1/3Mn1/3Co1/3O2 electrode Smekens, J.; Paulsen, J.; Yang, W. Electrochimica Acta, Vol. 174 https://doi.org/10.1016/j.electacta.2015.06.015	journal	August 2015
The effect of local current density on electrode design for lithium-ion batteries Wang, Ming; Li, Jianjun; He, Xiangming Journal of Power Sources, Vol. 207 https://doi.org/10.1016/j.jpowsour.2011.12.063	journal	June 2012
Significant impact on cathode performance of lithium-ion batteries by precisely controlled metal oxide nanocoatings via atomic layer deposition Li, Xifei; Liu, Jian; Meng, Xiangbo Journal of Power Sources, Vol. 247 https://doi.org/10.1016/j.jpowsour.2013.08.042	journal	February 2014
Enhanced lithiation and fracture behavior of silicon mesoscale pillars via atomic layer coatings and geometry design Ye, J. C.; An, Y. H.; Heo, T. W. Journal of Power Sources, Vol. 248 https://doi.org/10.1016/j.jpowsour.2013.09.097	journal	February 2014
Tailored porous electrode resistance for controlling electrolyte depletion and improving charging response in electrochemical systems Palko, James W.; Hemmatifar, Ali; Santiago, Juan G. Journal of Power Sources, Vol. 397 https://doi.org/10.1016/j.jpowsour.2018.06.102	journal	September 2018
A Quantitative Analytical Model for Predicting and Optimizing the Rate Performance of Battery Cells Wang, Fan; Tang, Ming Cell Reports Physical Science, Vol. 1, Issue 9 https://doi.org/10.1016/j.xcrp.2020.100192	journal	September 2020
Quantifying the Effect of Electronic Conductivity on the Rate Performance of Nanocomposite Battery Electrodes Tian, Ruiyuan; Alcala, Nolito; O’Neill, Stephen J. K. ACS Applied Energy Materials, Vol. 3, Issue 3 https://doi.org/10.1021/acsaem.0c00034	journal	January 2020
Galvanostatic Intermittent Titration Technique for Phase-Transformation Electrodes Zhu, Yujie; Wang, Chunsheng The Journal of Physical Chemistry C, Vol. 114, Issue 6 https://doi.org/10.1021/jp9113333	journal	January 2010
Visualization of Charge Distribution in a Lithium Battery Electrode Liu, Jun; Kunz, Martin; Chen, Kai The Journal of Physical Chemistry Letters, Vol. 1, Issue 14 https://doi.org/10.1021/jz100634n	journal	June 2010
Charge transfer kinetics at the solid–solid interface in porous electrodes Bai, Peng; Bazant, Martin Z. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4585	journal	April 2014
Magnetically aligned graphite electrodes for high-rate performance Li-ion batteries Billaud, Juliette; Bouville, Florian; Magrini, Tommaso Nature Energy, Vol. 1, Issue 8 https://doi.org/10.1038/nenergy.2016.97	journal	July 2016
High-performance battery electrodes via magnetic templating Sander, J. S.; Erb, R. M.; Li, L. Nature Energy, Vol. 1, Issue 8 https://doi.org/10.1038/nenergy.2016.99	journal	July 2016
Percolation threshold of graphene nanosheets as conductive additives in Li4Ti5O12 anodes of Li-ion batteries Zhang, Biao; Yu, Yang; Liu, Yusi Nanoscale, Vol. 5, Issue 5 https://doi.org/10.1039/c2nr33099g	journal	January 2013
Discharge Model for the Lithium Iron-Phosphate Electrode Srinivasan, Venkat; Newman, John Journal of The Electrochemical Society, Vol. 151, Issue 10 https://doi.org/10.1149/1.1785012	journal	January 2004
Design and Optimization of a Natural Graphite/Iron Phosphate Lithium-Ion Cell Srinivasan, Venkat; Newman, John Journal of The Electrochemical Society, Vol. 151, Issue 10 https://doi.org/10.1149/1.1785013	journal	January 2004
Simulation and Optimization of the Dual Lithium Ion Insertion Cell Fuller, Thomas F. Journal of The Electrochemical Society, Vol. 141, Issue 1 https://doi.org/10.1149/1.2054684	journal	January 1994
Modeling of Galvanostatic Charge and Discharge of the Lithium/Polymer/Insertion Cell Doyle, Marc Journal of The Electrochemical Society, Vol. 140, Issue 6 https://doi.org/10.1149/1.2221597	journal	January 1993
Theoretical Analysis of Current Distribution in Porous Electrodes Newman, John S.; Tobias, Charles W. Journal of The Electrochemical Society, Vol. 109, Issue 12 https://doi.org/10.1149/1.2425269	journal	January 1962
Approximate Solution Methods for Solid-State Diffusion in Phase-Change Electrodes Jagannathan, Kamakshi Journal of The Electrochemical Society, Vol. 156, Issue 12 https://doi.org/10.1149/1.3237142	journal	January 2009
The Relationship between Shunt Currents and Edge Corrosion in Flow Batteries Darling, Robert M.; Shiau, Huai-Suen; Weber, Adam Z. Journal of The Electrochemical Society, Vol. 164, Issue 11 https://doi.org/10.1149/2.0081711jes	journal	January 2017
Characterization of Electronic and Ionic Transport in Li _1- _x Ni _0.33 Mn _0.33 Co _0.33 O ₂ (NMC ₃₃₃ ) and Li _1- _x Ni _0.50 Mn _0.20 Co _0.30 O ₂ (NMC ₅₂₃ ) as a Function of Li Content Amin, Ruhul; Chiang, Yet-Ming Journal of The Electrochemical Society, Vol. 163, Issue 8 https://doi.org/10.1149/2.0131608jes	journal	January 2016
Multiphase Porous Electrode Theory Smith, Raymond B.; Bazant, Martin Z. Journal of The Electrochemical Society, Vol. 164, Issue 11 https://doi.org/10.1149/2.0171711jes	journal	January 2017
An Inverse Method for Estimating the Electrochemical Parameters of Lithium-Ion Batteries: II: Implementation Rajabloo, Barzin; Jokar, Ali; Désilets, Martin Journal of The Electrochemical Society, Vol. 164, Issue 2 https://doi.org/10.1149/2.0221702jes	journal	December 2016
On Graded Electrode Porosity as a Design Tool for Improving the Energy Density of Batteries Dai, Yiling; Srinivasan, Venkat Journal of The Electrochemical Society, Vol. 163, Issue 3 https://doi.org/10.1149/2.0301603jes	journal	December 2015
Optimizing Areal Capacities through Understanding the Limitations of Lithium-Ion Electrodes Gallagher, Kevin G.; Trask, Stephen E.; Bauer, Christoph Journal of The Electrochemical Society, Vol. 163, Issue 2 https://doi.org/10.1149/2.0321602jes	journal	November 2015
Multi-Particle Model for a Commercial Blended Lithium-Ion Electrode Mao, Z.; Farkhondeh, M.; Pritzker, M. Journal of The Electrochemical Society, Vol. 163, Issue 3 https://doi.org/10.1149/2.0321603jes	journal	December 2015
Nonequilibrium Thermodynamics of Porous Electrodes Ferguson, Todd R.; Bazant, Martin Z. Journal of The Electrochemical Society, Vol. 159, Issue 12 https://doi.org/10.1149/2.048212jes	journal	January 2012
Graphene-Sandwiched LiNi _0.5 Mn _1.5 O ₄ Cathode Composites for Enhanced High Voltage Performance in Li Ion Batteries Prabakar, S. J. Richard; Hwang, Yun-Hwa; Lee, Bichna Journal of The Electrochemical Society, Vol. 160, Issue 6 https://doi.org/10.1149/2.085306jes	journal	January 2013
Experimental and Simulation Investigations of Porosity Graded Cathodes in Mitigating Battery Degradation of High Voltage Lithium-Ion Batteries Liu, Lin; Guan, Pengjian; Liu, Changhong Journal of The Electrochemical Society, Vol. 164, Issue 13 https://doi.org/10.1149/2.1021713jes	journal	January 2017
Is There a Benefit in Employing Graded Electrodes for Lithium-Ion Batteries? Qi, Yanbo; Jang, Taejin; Ramadesigan, Venkatasailanathan Journal of The Electrochemical Society, Vol. 164, Issue 13 https://doi.org/10.1149/2.1051713jes	journal	January 2017
Impact of Pore Tortuosity on Electrode Kinetics in Lithium Battery Electrodes: Study in Directionally Freeze-Cast LiNi _0.8 Co _0.15 Al _0.05 O ₂ (NCA) Delattre, Benjamin; Amin, Ruhul; Sander, Jonathan Journal of The Electrochemical Society, Vol. 165, Issue 2 https://doi.org/10.1149/2.1321802jes	journal	January 2018

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