Electrochemical Kinetics of SEI Growth on Carbon Black: Part II. Modeling
© 2019 The Electrochemical Society. Mathematical models of capacity fade can reduce the time and cost of lithium-ion battery development and deployment, and growth of the solid-electrolyte interphase (SEI) is a major source of capacity fade. Experiments in Part I reveal nonlinear voltage dependence...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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The Electrochemical Society
2021
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| Online Access: | https://hdl.handle.net/1721.1/135121 |
| _version_ | 1811097577843589120 |
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| author | Das, Supratim Attia, Peter M Chueh, William C Bazant, Martin Z |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Das, Supratim Attia, Peter M Chueh, William C Bazant, Martin Z |
| author_sort | Das, Supratim |
| collection | MIT |
| description | © 2019 The Electrochemical Society. Mathematical models of capacity fade can reduce the time and cost of lithium-ion battery development and deployment, and growth of the solid-electrolyte interphase (SEI) is a major source of capacity fade. Experiments in Part I reveal nonlinear voltage dependence and strong charge-discharge asymmetry in SEI growth on carbon black negative electrodes, which is not captured by previous models. Here, we present a theoretical model for the electrochemical kinetics of SEI growth coupled to lithium intercalation, which accurately predicts experimental results with few adjustable parameters. The key hypothesis is that the initial SEI is a mixed ionelectron conductor, and its electronic conductivity varies approximately with the square of the local lithium concentration, consistent with hopping conduction of electrons along percolating networks. By including a lithium-ion concentration dependence for the electronic conductivity in the SEI, the bulk SEI thus modulates the overpotential and exchange current of the electrolyte reduction reaction. As a result, SEI growth is promoted during lithiation but suppressed during delithiation. This new insight establishes the fundamental electrochemistry of SEI growth kinetics. Our model improves upon existing models by introducing the effects of electrochemical SEI growth and its dependence on potential, current magnitude, and current direction in predicting capacity fade. |
| first_indexed | 2024-09-23T17:01:49Z |
| format | Article |
| id | mit-1721.1/135121 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T17:01:49Z |
| publishDate | 2021 |
| publisher | The Electrochemical Society |
| record_format | dspace |
| spelling | mit-1721.1/1351212023-11-07T19:52:06Z Electrochemical Kinetics of SEI Growth on Carbon Black: Part II. Modeling Das, Supratim Attia, Peter M Chueh, William C Bazant, Martin Z Massachusetts Institute of Technology. Department of Chemical Engineering © 2019 The Electrochemical Society. Mathematical models of capacity fade can reduce the time and cost of lithium-ion battery development and deployment, and growth of the solid-electrolyte interphase (SEI) is a major source of capacity fade. Experiments in Part I reveal nonlinear voltage dependence and strong charge-discharge asymmetry in SEI growth on carbon black negative electrodes, which is not captured by previous models. Here, we present a theoretical model for the electrochemical kinetics of SEI growth coupled to lithium intercalation, which accurately predicts experimental results with few adjustable parameters. The key hypothesis is that the initial SEI is a mixed ionelectron conductor, and its electronic conductivity varies approximately with the square of the local lithium concentration, consistent with hopping conduction of electrons along percolating networks. By including a lithium-ion concentration dependence for the electronic conductivity in the SEI, the bulk SEI thus modulates the overpotential and exchange current of the electrolyte reduction reaction. As a result, SEI growth is promoted during lithiation but suppressed during delithiation. This new insight establishes the fundamental electrochemistry of SEI growth kinetics. Our model improves upon existing models by introducing the effects of electrochemical SEI growth and its dependence on potential, current magnitude, and current direction in predicting capacity fade. 2021-10-27T20:10:49Z 2021-10-27T20:10:49Z 2019 2019-08-14T12:46:31Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/135121 en 10.1149/2.0241904JES Journal of The Electrochemical Society Creative Commons Attribution 4.0 International license https://creativecommons.org/licenses/by/4.0/ application/pdf The Electrochemical Society Electrochemical Society (ECS) |
| spellingShingle | Das, Supratim Attia, Peter M Chueh, William C Bazant, Martin Z Electrochemical Kinetics of SEI Growth on Carbon Black: Part II. Modeling |
| title | Electrochemical Kinetics of SEI Growth on Carbon Black: Part II. Modeling |
| title_full | Electrochemical Kinetics of SEI Growth on Carbon Black: Part II. Modeling |
| title_fullStr | Electrochemical Kinetics of SEI Growth on Carbon Black: Part II. Modeling |
| title_full_unstemmed | Electrochemical Kinetics of SEI Growth on Carbon Black: Part II. Modeling |
| title_short | Electrochemical Kinetics of SEI Growth on Carbon Black: Part II. Modeling |
| title_sort | electrochemical kinetics of sei growth on carbon black part ii modeling |
| url | https://hdl.handle.net/1721.1/135121 |
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