The Role of Long‐Range Interactions Between High‐Entropy Single‐Atoms in Catalyzing Sulfur Conversion Reactions

Abstract Sulfur conversion reactions are the foundation of lithium–sulfur batteries but usually possess sluggish kinetics during practical battery operation. Herein, a high‐entropy single‐atom catalyst (HESAC) is synthesized for this process. In contrast to conventional dual‐atom catalysts that form metal–metal bonds, the center metal atoms in HESAC are not bonded but exhibit long‐range interactions at a sub‐nanometer distance (<9 Å). The synergistic effect between the long‐range interactions and entropy changes enables the regulation of d‐ and π‐electron states. This alteration in the electronic structure improves the adsorption and electronic conductivity of intermediate polysulfides, thereby accelerating their conversion kinetics. Consequently, this leads to a significant enhancement in specific capacities by ≈40% at high rates compared to single‐atom catalysts. The resulting lithium–sulfur battery with HESAC demonstrates a remarkable areal capacity of 3.4 mAh cm⁻² at 10 C. These findings provide valuable insights into the design principle of metal atom catalysts for electrochemical reactions.