Role of solvent-anion charge transfer in oxidative degradation of battery electrolytes
© 2019, The Author(s). Electrochemical stability windows of electrolytes largely determine the limitations of operating regimes of lithium-ion batteries, but the degradation mechanisms are difficult to characterize and poorly understood. Using computational quantum chemistry to investigate the oxida...
| Main Authors: | , , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Springer Science and Business Media LLC
2021
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| Online Access: | https://hdl.handle.net/1721.1/136398 |
| _version_ | 1811071149235240960 |
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| author | Fadel, Eric R Faglioni, Francesco Samsonidze, Georgy Molinari, Nicola Merinov, Boris V Goddard III, William A Grossman, Jeffrey C Mailoa, Jonathan P Kozinsky, Boris |
| author_facet | Fadel, Eric R Faglioni, Francesco Samsonidze, Georgy Molinari, Nicola Merinov, Boris V Goddard III, William A Grossman, Jeffrey C Mailoa, Jonathan P Kozinsky, Boris |
| author_sort | Fadel, Eric R |
| collection | MIT |
| description | © 2019, The Author(s). Electrochemical stability windows of electrolytes largely determine the limitations of operating regimes of lithium-ion batteries, but the degradation mechanisms are difficult to characterize and poorly understood. Using computational quantum chemistry to investigate the oxidative decomposition that govern voltage stability of multi-component organic electrolytes, we find that electrolyte decomposition is a process involving the solvent and the salt anion and requires explicit treatment of their coupling. We find that the ionization potential of the solvent-anion system is often lower than that of the isolated solvent or the anion. This mutual weakening effect is explained by the formation of the anion-solvent charge-transfer complex, which we study for 16 anion-solvent combinations. This understanding of the oxidation mechanism allows the formulation of a simple predictive model that explains experimentally observed trends in the onset voltages of degradation of electrolytes near the cathode. This model opens opportunities for rapid rational design of stable electrolytes for high-energy batteries. |
| first_indexed | 2024-09-23T08:46:47Z |
| format | Article |
| id | mit-1721.1/136398 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T08:46:47Z |
| publishDate | 2021 |
| publisher | Springer Science and Business Media LLC |
| record_format | dspace |
| spelling | mit-1721.1/1363982022-03-30T14:32:48Z Role of solvent-anion charge transfer in oxidative degradation of battery electrolytes Fadel, Eric R Faglioni, Francesco Samsonidze, Georgy Molinari, Nicola Merinov, Boris V Goddard III, William A Grossman, Jeffrey C Mailoa, Jonathan P Kozinsky, Boris © 2019, The Author(s). Electrochemical stability windows of electrolytes largely determine the limitations of operating regimes of lithium-ion batteries, but the degradation mechanisms are difficult to characterize and poorly understood. Using computational quantum chemistry to investigate the oxidative decomposition that govern voltage stability of multi-component organic electrolytes, we find that electrolyte decomposition is a process involving the solvent and the salt anion and requires explicit treatment of their coupling. We find that the ionization potential of the solvent-anion system is often lower than that of the isolated solvent or the anion. This mutual weakening effect is explained by the formation of the anion-solvent charge-transfer complex, which we study for 16 anion-solvent combinations. This understanding of the oxidation mechanism allows the formulation of a simple predictive model that explains experimentally observed trends in the onset voltages of degradation of electrolytes near the cathode. This model opens opportunities for rapid rational design of stable electrolytes for high-energy batteries. 2021-10-27T20:35:11Z 2021-10-27T20:35:11Z 2019 2019-09-19T14:43:38Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/136398 en 10.1038/s41467-019-11317-3 Nature Communications Creative Commons Attribution 4.0 International license https://creativecommons.org/licenses/by/4.0/ application/pdf Springer Science and Business Media LLC Nature |
| spellingShingle | Fadel, Eric R Faglioni, Francesco Samsonidze, Georgy Molinari, Nicola Merinov, Boris V Goddard III, William A Grossman, Jeffrey C Mailoa, Jonathan P Kozinsky, Boris Role of solvent-anion charge transfer in oxidative degradation of battery electrolytes |
| title | Role of solvent-anion charge transfer in oxidative degradation of battery electrolytes |
| title_full | Role of solvent-anion charge transfer in oxidative degradation of battery electrolytes |
| title_fullStr | Role of solvent-anion charge transfer in oxidative degradation of battery electrolytes |
| title_full_unstemmed | Role of solvent-anion charge transfer in oxidative degradation of battery electrolytes |
| title_short | Role of solvent-anion charge transfer in oxidative degradation of battery electrolytes |
| title_sort | role of solvent anion charge transfer in oxidative degradation of battery electrolytes |
| url | https://hdl.handle.net/1721.1/136398 |
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