Peroxo Species Formed in the Bulk of Silicate Cathodes
| Autor: | Zhifeng Zhang, Lirong Zheng, Helmut Ehrenberg, Xianhui Zhang, Liyuan Huai, Zhenlian Chen, Wenqiang Du, Bjoern Schwarz, Ailing Tian, Jun Li, Ying Zhang, Xiao Cheng Zeng, Jinlei Wu, Zhiyong Zhang, Deyu Wang |
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| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Technology
Dimer Kinetics Lithium‐Ion Batteries | Hot Paper lithium-ion batteries chemistry.chemical_element 010402 general chemistry Photochemistry Electrochemistry 01 natural sciences Oxygen Redox Catalysis chemistry.chemical_compound Electron transfer Research Articles peroxo formation oxygen redox 010405 organic chemistry Chemistry ab initio calculations General Chemistry General Medicine Silicate 0104 chemical sciences Covalent bond ddc:540 X-ray spectroscopy ddc:600 Research Article |
| Zdroj: | Angewandte Chemie / International edition 60(18), 10056-10063 (2021). doi:10.1002/anie.202100730 Angewandte Chemie / International edition, 60 (18), 10056–10063 Angewandte Chemie (International Ed. in English) |
| ISSN: | 1433-7851 1521-3773 |
| Popis: | Angewandte Chemie / International edition 60(18), 10056 - 10063 (2021). doi:10.1002/anie.202100730 Oxygen redox in Li-rich oxides may boost the energy density of lithium-ion batteries by incorporating oxygen chemistry in solid cathodes. However, oxygen redox in the bulk usually entangles with voltage hysteresis and oxygen release, resulting in a prolonged controversy in literature on oxygen transformation. Here, we report spectroscopic evidence of peroxo species formed and confined in silicate cathodes amid oxygen redox at high voltage, accompanied by Co$^{2+}$/Co$^{3+}$ redox dominant at low voltage. First-principles calculations reveal that localized electrons on dangling oxygen drive the O-O dimerization. The covalence between the binding cation and the O-O dimer determines the degree of electron transfer in oxygen transformation. Dimerization induces irreversible structural distortion and slow kinetics. But peroxo formation can minimize the voltage drop and volume expansion in cumulative cationic and anionic redox. These findings offer insights into oxygen redox in the bulk for the rational design of high-energy-density cathodes. Published by Wiley-VCH, Weinheim |
| Databáze: | OpenAIRE |
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