Bi‐Metallic Coupling‐Induced Electronic‐State Modulation of Metal Phosphides for Kinetics‐Enhanced and Dendrite‐Free Li–S Batteries

Abstract Lithium–sulfur (Li–S) batteries are considered as next‐generation promising batteries, yet suffer from severe capacity decay and low‐rate capability. Transition metal compounds can solve these problems due to their unique electronic band structure, good chemical adsorption ability, and exceptional catalytic capability. Unraveling the essence of electronic states of metal compounds can fundamentally guide their structure design and promote Li–S battery performance. Herein, bi‐metallic coupling‐induced electronic‐state modulation of metal phosphides is reported for kinetics‐enhanced and dendrite‐free Li–S batteries. Bimetallic phosphides nanoparticles‐anchored N, P‐co‐doped porous carbons (NiCoP–NPPC) are facilely constructed via a laser‐induced micro‐explosion strategy. Theoretical calculations reveal that the electronic‐state can be modulated via NiCo coupling, leading to lower polysulfides/Li + diffusion and conversion barriers. As a result, the assembled Li–S full cells based on NiCoP–NPPC exhibit greatly improved capacity (1150 mAh g ‐1 at 0.5 C) and cycle stability (84.3% capacity retention after 1000 cycles). Furthermore, they can be operated even under lean electrolyte (5.2 µL mg ‐1 ) with a high sulfur loading (6.9 mg cm ‐2 ), achieving a high areal capacity of 6.8 mAh cm ‐2 at 0.5 C. This study demonstrates that bi‐metallic coupling‐induced electronic‐state modulation is an effective approach for developing high‐performance Li–S batteries.