题目：

Cooperative Catalysis of Polysulfides in Lithium–Sulfur Batteries through Adsorption Competition by Tuning Cationic Geometric Configuration of Dual-active Sites in Spinel Oxides

作者：

Hongtai Li^1#, Pei Shi^2,3#, Lei Wang¹,Tianran Yan¹, Tong Guo⁴, Xiao Xia¹,Chi Chen^2,3, Jing Mao⁵,Dan Sun^2,3,and Liang Zhang^1,6*

单位：

¹Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University Suzhou 215123, China

²CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences, Fuzhou 350002, China

³Xiamen Institute of Rare Earth Materials, Haixi Institute Chinese Academy of Sciences, Xiamen 361021, China

⁴Key Laboratory for Soft Chemistry and Functional Materials of Ministry of Education, Nanjing University of Science and Technology Nanjing 210094, China

⁵School of Materials Science and Engineering, Zhengzhou University Zhengzhou 450001, China

⁶Jiangsu Key Laboratory of Advanced Negative Carbon Technologies, Soochow University Suzhou 215123, China

摘要：

Fundamentally understanding the structure-property relationship is critical to design advanced electrocatalysts for lithium–sulfur (Li–S) batteries, which remains a formidable challenge. Herein, by manipulating the regulable cations in spinel oxides, their geometrical-site-dependent catalytic activity for sulfur redox is investigated. Experimental and theoretical analyses validate that the modulation essence of cooperative catalysis of lithium polysulfides (LiPSs) is dominated by LiPSs adsorption competition between Co³⁺ tetrahedral (Td) and Mn³⁺ octahedral (Oh) sites on Mn³⁺_Oh-O-Co³⁺_Td backbones. Specifically, high-spin Co³⁺ with stronger Co-S covalency anchors LiPSs persistently, while electron delocalized Mn³⁺_Oh with adsorptive orbital (d_z²) functions better in catalyzing specialized LiPSs conversion. This work inaugurates a universal strategy for sculpting geometrical configuration to achieve charge, spin, and orbital topological regulation in electrocatalysts for Li–S batteries.

影响因子：

16.823

分区情况：

一区

链接：

https://doi.org/10.1002/anie.202216286