Tailoring the d-Band Center via Multi-Metal-Phosphorus d-p Orbital Hybridization in a High-Entropy Metal Phosphide to Enable Accelerated Sulfur Redox Kinetics.

Guo, Manchuan; Jiang, Jianhong; Liang, Fengxing; Zhu, Yanqiu; Zhu, Jinliang · Adv Mater · 2026

basic_science · Level V

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Abstract

Sluggish lithium polysulfide (LiPS) reduction kinetics and the shuttle effect lead to low active mass utilization and poor cycling stability, thereby seriously hampering the commercial application of Li-S batteries. Herein, a theoretically guided high-entropy phosphide (Fe<sub>0.74</sub>Co<sub>0.64</sub>Ni<sub>0.61</sub>Cu<sub>0.32</sub>Mo<sub>0.24</sub>P, FCNCMP-HEMP) nanoparticle is designed to enhance LiPS conversion. The electronic interaction among the S 3p orbitals of S<sub>x</sub> <sup>2-</sup> in LiPSs, the metal d orbitals, and the P 3p orbitals in FCNCMP-HEMP enables favorable catalytic activity for LiPS conversion. Impressively, FCNCMP-HEMP/C exhibits a higher electron transfer number and lower activation energy in solid-liquid-solid LiPS reduction reactions, indicating enhanced LiPS conversion kinetics. Specifically, Li-S cells with FCNCMP-HEMP/C@S cathodes deliver a high discharge capacity of 744 mAh g<sup>-</sup> <sup>1</sup> and an ultralow capacity decay of 0.014% per cycle over 2000 cycles at 5 C. Moreover, the assembled pouch cell with the FCNCMP-HEMP/C@S cathode shows a high energy density of 456 Wh kg<sup>-</sup> <sup>1</sup>. This work opens a new pathway for designing high-entropy metal phosphides for high-performance Li-S batteries.