To overcome the persistent challenges of sluggish lithium polysulfide (LiPS) conversion kinetics and the shuttle effect in Li–S batteries, this work introduces a novel, cost-effective thermal treatment strategy for synthesizing high-entropy metal phosphide catalysts using cation-bonded phosphate resins. For the first time, we successfully fabricated single-phase high-entropy Fe0.20Co0.62Ni0.14Cu0.23Mn0.38P nanoparticles anchored on a porous carbon network (HEP/C). The HEP/C demonstrates enhanced electronic conductivity and superior LiPS adsorption capability, substantially accelerating their redox kinetics. These catalytic improvements arise from (1) synergistic electronic modulation by the five constituent metals, which elevates d-band electron energy levels, and (2) lattice distortion induced by atomic radius mismatches, collectively generating a dense array of highly active catalytic sites. The HEP/C@S cathode delivers an ultrahigh initial specific capacity of 1402.18 mAh g−1 at 0.2C, outstanding cycling stability with merely 0.05% capacity decay per cycleover 1000 cycles at 5C, and a remarkable initial energy density of 455 Wh kg−1 in practical pouch cells. This work not only presents an efficient synthesis strategy for high-entropy materials but also provides fundamental insights into the design principles of advanced LiPS conversion catalysts for high-performance Li–S batteries.
