A High‐Entropy Metal Phosphide With Engineered d‑Orbital Interactions for High‐Efficiency Lithium Polysulfide Electrocatalysis

ABSTRACT Lithium–sulfur (Li–S) batteries are emerging next‐generation energy storage systems, yet their development is hindered by the shuttle effect and sluggish conversion kinetics of lithium polysulfides (LiPSs). In this study, a thermal treatment strategy is proposed for synthesizing high‐entropy metal phosphide (Co 0.60 Ni 0.23 Cu 0.30 Mn 0.24 Mo 0.63 P, HEMP). The as‐prepared HEMP material shows a low energy barrier for Li + diffusion, favorable electronic conductivity, and strong adsorption to LiPS intermediates. Owing to these unique properties, the HEMP/C@S coin cell exhibits an outstanding initial specific capacity of 1339.2 mAh g −1 at 0.2C, and the HEMP/C@S pouch cell achieves a superior energy density of 441.3 Wh kg −1 . In situ experimental and modelling techniques reveal that the superior catalytic performance originates from: (1) The synergistic interplay among the five metal constituents, with d‐orbital interactions broadening the electronic state distribution and elevating the d‐band center, thus enhancing the conductivity of HEMP and its adsorption capability toward LiPSs; (2) The lattice distortion induced by atomic size differences, which exposes abundant active sites and lowers Li + diffusion energy barrier. The approach based on entropy‐driven engineered d‐orbital interactions provides valuable insights into the development of LiPSs catalysts for high‐performance Li–S batteries.