| Autor: |
Rinkel BLD; Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, U.K., Hall DS; Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, U.K.; The Faraday Institution, Harwell Campus, Didcot OX11 0RA, U.K., Temprano I; Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, U.K., Grey CP; Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, U.K.; The Faraday Institution, Harwell Campus, Didcot OX11 0RA, U.K. |
| Jazyk: |
angličtina |
| Zdroj: |
Journal of the American Chemical Society [J Am Chem Soc] 2020 Sep 02; Vol. 142 (35), pp. 15058-15074. Date of Electronic Publication: 2020 Aug 18. |
| DOI: |
10.1021/jacs.0c06363 |
| Abstrakt: |
The mitigation of decomposition reactions of lithium-ion battery electrolyte solutions is of critical importance in controlling device lifetime and performance. However, due to the complexity of the system, exacerbated by the diverse set of electrolyte compositions, electrode materials, and operating parameters, a clear understanding of the key chemical mechanisms remains elusive. In this work, operando pressure measurements, solution NMR, and electrochemical methods were combined to study electrolyte oxidation and reduction at multiple cell voltages. Two-compartment LiCoO 2 /Li cells were cycled with a lithium-ion conducting glass-ceramic separator so that the species formed at each electrode could be identified separately and further reactions of these species at the opposite electrode prevented. One principal finding is that chemical oxidation (with an onset voltage of ∼4.7 V vs Li/Li + for LiCoO 2 ), rather than electrochemical reaction, is the dominant decomposition process at the positive electrode surface in this system. This is ascribed to the well-known release of reactive oxygen at higher states-of-charge, indicating that reactions of the electrolyte at the positive electrode are intrinsically linked to surface reactivity of the active material. Soluble electrolyte decomposition products formed at both electrodes are characterized, and a detailed reaction scheme is constructed to rationalize the formation of the observed species. The insights on electrolyte decomposition through reactions with reactive oxygen species identified through this work have a direct impact on understanding and mitigating degradation in high-voltage/higher-energy-density LiCoO 2 -based cells, and more generally for cells containing nickel-containing cathode materials (e.g., LiNi x Mn y Co z O 2 ; NMCs), as they lose oxygen at lower operating voltages. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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