The shuttle effect and sluggish redox kinetics of polysulfides pose significant challenges to the long-cycle stability of alkali metal-sulfur batteries, necessitating the development of highly efficient catalysts. High-entropy alloys (HEAs) have emerged as promising electrocatalysts for energy storage due to their unique electronic properties and high configurational entropy. Tailoring the electronic configuration of HEAs to achieve a well-positioned d-band center is a vital strategy for enhancing catalytic performance in alkali metal-sulfur batteries systems. In this study, the electronic configurations of HEAs were systematically tuned by varying the fifth metal element. Among them, NiCoFeCuMo (HEA-Mo) exhibited an optimized electronic configuration and a favorable d-band center, fully demonstrating the “cocktail effect” and thereby enhancing interactions with polysulfides. To evaluate its practical performance, HEA-Mo was integrated into polypropylene (PP) separators (HEA-Mo@PP) for Li-S and room-temperature Na-S batteries, both exhibiting excellent cyclic stability attributed to enhanced polysulfides adsorption and catalytic conversion. This work provides critical insight into the rational design of non-noble HEAs via electronic configuration modulation, offering a generalizable strategy for advancing next-generation energy storage systems.
