Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S–S
| Autor: | Zheng-Wen Fu, Paul Northrup, Ming-Hui Cao, Xiaosong Liu, Pan Liu, Tian Wang, Xiao-Qing Yang, Seong-Min Bak, Guoxi Ren, Jie-Nan Zhang, Ji-Li Yue, Mingwei Chen, Zulipiya Shadike |
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| Rok vydání: | 2019 |
| Předmět: |
Science
General Physics and Astronomy chemistry.chemical_element 02 engineering and technology Electron hole Crystal structure 010402 general chemistry Photochemistry 01 natural sciences Redox Article General Biochemistry Genetics and Molecular Biology law.invention Ion Batteries law Mössbauer spectroscopy lcsh:Science Energy Multidisciplinary Precipitation (chemistry) General Chemistry 021001 nanoscience & nanotechnology Sulfur Cathode 0104 chemical sciences chemistry lcsh:Q 0210 nano-technology |
| Zdroj: | Nature Communications, Vol 10, Iss 1, Pp 1-12 (2019) Nature Communications |
| ISSN: | 2041-1723 |
| DOI: | 10.1038/s41467-019-12310-6 |
| Popis: | The use of anion redox reactions is gaining interest for increasing rechargeable capacities in alkaline ion batteries. Although anion redox coupling of S2− and (S2)2− through dimerization of S–S in sulfides have been studied and reported, an anion redox process through electron hole formation has not been investigated to the best of our knowledge. Here, we report an O3-NaCr2/3Ti1/3S2 cathode that delivers a high reversible capacity of ~186 mAh g−1 (0.95 Na) based on the cation and anion redox process. Various charge compensation mechanisms of the sulfur anionic redox process in layered NaCr2/3Ti1/3S2, which occur through the formation of disulfide-like species, the precipitation of elemental sulfur, S–S dimerization, and especially through the formation of electron holes, are investigated. Direct structural evidence for formation of electron holes and (S2)n− species with shortened S–S distances is obtained. These results provide valuable information for the development of materials based on the anionic redox reaction. Anionic redox reactions are gaining interest as a means to optimize capacities of alkaline ion batteries. Here, the authors investigate various charge compensation mechanisms and report S–S dimerization and the formation of electron holes on sulfur in a model sulfide cathode. |
| Databáze: | OpenAIRE |
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