Design Rules for High-Valent Redox in Intercalation Electrodes
| Autor: | Iwnetim Abate, William C. Chueh, Linda F. Nazar, Wanli Yang, William E. Gent |
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| Rok vydání: | 2020 |
| Předmět: |
Solid-state chemistry
Materials science Intercalation (chemistry) Energy landscape 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology Electrochemistry 01 natural sciences Redox 0104 chemical sciences General Energy Transition metal Covalent bond Chemical physics Electrode 0210 nano-technology |
| Zdroj: | Joule. 4:1369-1397 |
| ISSN: | 2542-4351 |
| Popis: | Summary High-valent redox, where over-oxidation of oxygen or transition metals (TMs) drives extensive charge sharing through the formation of short covalent bonds, has historically been avoided in intercalation electrodes because of its association with structural disorder and electrochemical irreversibility. Here, we present a perspective on the origin of these undesirable behaviors and materials design criteria to mitigate them. Drawing parallels between oxygen redox and high-valent TM redox (e.g., CrIII/VI and VIII/V), we reveal that the defect formation energy landscape is the primary factor controlling the electrochemical reversibility of high-valent redox, as it determines which defects form to accommodate the short covalent bonds as well as the nature of those covalent bonding arrangements. By tuning the defect formation energy landscape, researchers can control the nature of the oxidized species while minimizing structural disorder. These concepts reveal a wide range of previously avoided redox mechanisms as promising candidates for high density energy storage. |
| Databáze: | OpenAIRE |
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