Advances in High‐Entropy Catalysts for Lithium–Sulfur Batteries: Design Principles, Recent Progress, and Prospects

Abstract Lithium–sulfur (Li–S) batteries are regarded as one of the most promising next‐generation energy storage technologies due to their exceptionally high theoretical energy density, cost‐effectiveness, and environmental sustainability. Nevertheless, their practical deployment is significantly constrained by several challenges, including the intrinsic low conductivity of sulfur, the shuttle effect of lithium polysulfides (LiPS), sluggish redox kinetics, and instability of the Li anode. To overcome these limitations, the integration of catalytic materials has emerged as an effective strategy to accelerate sulfur redox reactions, promote LiPS conversion, and enhance cycling stability. Recently, high‐entropy catalysts (HEC), comprising five or more metallic elements in near‐equimolar ratios, have garnered increasing attention owing to their entropy‐stabilized structures, abundant active sites, and tunable electronic properties. This review presents a comprehensive overview of the design principles, synthesis methods, and electrochemical applications of various HEC families, including high‐entropy alloys, oxides, sulfides, nitrides, phosphides, MXenes, and Prussian blue analogues, in Li–S battery systems. The synergistic effects arising from multicomponent interactions, structural advantages, and underlying catalytic mechanisms are systematically discussed. Finally, key challenges such as scalable synthesis, in‐depth mechanistic elucidation, and rational compositional design are addressed, along with future directions aimed at advancing high‐performance HEC‐based Li–S battery systems.