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Vol. 16 (2024)

Enhanced Redox Electrocatalysis in High-Entropy Perovskite Fluorides by Tailoring d–p Hybridization

https://doi.org/10.1007/s40820-023-01275-3
Xudong Li
Department of Applied Chemistry, Harbin Institute of Technology at Weihai, Weihai 264209, People’s Republic of China
Zhuomin Qiang
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, People’s Republic of China
Guokang Han
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, People’s Republic of China
Shuyun Guan
Department of Applied Chemistry, Harbin Institute of Technology at Weihai, Weihai 264209, People’s Republic of China
Yang Zhao
Department of Applied Chemistry, Harbin Institute of Technology at Weihai, Weihai 264209, People’s Republic of China
Shuaifeng Lou
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, People’s Republic of China
Yongming Zhu
Department of Applied Chemistry, Harbin Institute of Technology at Weihai, Weihai 264209, People’s Republic of China

Corresponding Author: Yongming Zhu

hitonline@163.com

Nano-Micro Letters, Vol. 16 (2024), Article Number: 55

Abstract

High-entropy catalysts featuring exceptional properties are, in no doubt, playing an increasingly significant role in aprotic lithium-oxygen batteries. Despite extensive effort devoted to tracing the origin of their unparalleled performance, the relationships between multiple active sites and reaction intermediates are still obscure. Here, enlightened by theoretical screening, we tailor a high-entropy perovskite fluoride (KCoMnNiMgZnF3-HEC) with various active sites to overcome the limitations of conventional catalysts in redox process. The entropy effect modulates the d-band center and d orbital occupancy of active centers, which optimizes the d–p hybridization between catalytic sites and key intermediates, enabling a moderate adsorption of LiO2 and thus reinforcing the reaction kinetics. As a result, the Li–O2 battery with KCoMnNiMgZnF3-HEC catalyst delivers a minimal discharge/charge polarization and long-term cycle stability, preceding majority of traditional catalysts reported. These encouraging results provide inspiring insights into the electron manipulation and d orbital structure optimization for advanced electrocatalyst.


Highlights:
1 The tailored KCoMnNiMgZnF3-HEC cathode delivers extremely high discharge capacity (22,104 mAh g−1), outstanding long-term cyclability (over 500 h), preceding majority of traditional catalysts reported.
2 Entropy effect of multiple sites in KCoMnNiMgZnF3-HEC engenders appropriate regulation of 3d orbital structure, leading to a moderate hybridization with the p orbital of key intermediate.
3 The homogeneous nucleation of Li2O2 is achieved on multiple cation site, contributing to effective mass transfer at the three-phase interface, and thus, the reversibility of O2/Li2O2 conversion.

Keywords

Lithium–oxygen batteries KCoMnNiMgZnF3-HEC perovskite fluoride Entropy effect Catalytic kinetics d–p orbital hybridization
Li, Xudong, Zhuomin Qiang, Guokang Han, Shuyun Guan, Yang Zhao, Shuaifeng Lou, and Yongming Zhu. 2023. “Enhanced Redox Electrocatalysis in High-Entropy Perovskite Fluorides by Tailoring d–p Hybridization”. Nano-Micro Letters 16 (December):55. https://doi.org/10.1007/s40820-023-01275-3.
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