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A Thermodynamic Model for the Insertion Electrochemistry of Battery Cathodes
- The transition to Ni‐based battery cathodes enhances the energy density and reduces the cost of batteries. However, this comes at the expense of losing energy efficiency which could be a consequence of charge–discharge hysteresis. Here, a thermodynamic model is developed to understand the extent and origin of charge–discharge hysteresis in battery cathodes based on their cyclic voltammograms (CVs). This was possible by defining a Gibbs energy function that weights random ion insertion/expulsion, i. e., a solid solution pathway, against selective ion insertion/expulsion, i. e., a phase separation route. The model was verified experimentally by the CVs of CoOOH and Ni(OH)2 as solid‐solution and phase‐separating cathodes, respectively. Finally, a microscopic view reveals that phase separation and hysteresis are a consequence of large ionic radii difference of the reduced and oxidized central metal atoms.
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| Author: | Keyvan Malaie, Fritz Scholz, Uwe Schröder |
|---|---|
| URN: | urn:nbn:de:gbv:9-opus-83054 |
| DOI: | https://doi.org/10.1002/celc.202201118 |
| ISSN: | 2196-0216 |
| Parent Title (English): | ChemElectroChem |
| Publisher: | Wiley |
| Place of publication: | Hoboken, NJ |
| Document Type: | Article |
| Language: | English |
| Date of Publication (online): | 2023/01/23 |
| Date of first Publication: | 2023/04/03 |
| Release Date: | 2024/02/02 |
| Tag: | Cobalt; Hysteresis; Ion insertion; Nickel; Phase transition |
| Volume: | 10 |
| Issue: | 7 |
| Article Number: | e202201118 |
| Page Number: | 8 |
| Faculties: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Biochemie |
| Collections: | Artikel aus DFG-gefördertem Publikationsfonds |
| Licence (German): |  Creative Commons - Namensnennung |