High‐Entropy Complementary d‐Band Decoupling of Redox Kinetics for Bidirectional Catalysis in Lithium–Sulfur Batteries

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.