High‐Entropy Complementary d‐Band Decoupling of Redox Kinetics for Bidirectional Catalysis in Lithium–Sulfur Batteries
Di Wang, Zihan Dong, Shiyi Liu, Hailong Yan, Fangqing Liu, Yi Huang, Zhipeng Sun, Le Huang, Zaiping GuoABSTRACT
The reversible conversion of sulfur and Li 2 S in lithium–sulfur (Li–S) batteries is limited by the bidirectional redox kinetics. A single‐component catalyst is difficult to simultaneously meet the differentiated adsorption and catalytic requirements in the multi‐step conversion of polysulfides. We propose a high‐entropy complementary d‐band center model, extending the classical d‐band center theory to multi‐metal systems. The complementary d‐band centers of multiple metals align the HOMO and LUMO of sulfur species, coordinating the electron transfer balance and accelerating the redox kinetics. The multi‐metal sites collaboratively construct a “highly efficient capture → cascade conversion → rapid desorption” closed‐loop pathway, with the d‐p hybridization network regulating the adsorption energy and effectively suppressing the shuttle effect. Based on this design, the high‐entropy selenide catalyst with a customized electronic structure and strong synergy effect has achieved excellent cycle stability and rate performance in Li‐S batteries.