Rational Design of High‐Entropy Phosphorus‐Based Alloy Anodes for Fast‐Charging Lithium‐Ion Batteries

Abstract The introduction of diverse metal elements to form high‐entropy phosphorus‐based alloys retains low‐cost and high theoretical capacity while improving stability and conductivity of elemental phosphorus. However, the metal selection and composition design are lacking of rational principles. Here, 13 metal elements based on atomic electronegativity, redox compatibility, and M─P bond length distributionvare systematically evaluated. The analysis reveals that isovalent charge systems exhibit high substitution compatibility, and “soft” cations can effectively regulate lattice stress, thereby expanding the substitution ratio. By integrating these findings with key metrics such as lithiation potential, theoretical capacity, raw material cost, and conductivity, Si, Ge, Sn, Sb, Cu, and Zn are identified as the optimal elements. Through precise stoichiometric control, a single‐phase Cu 2 Ge 2 Si 2 SnSb 6 Zn 6 P 24 is successfully achieved. In situ XRD characterization further confirms its reversible structural evolution during lithiation/delithiation. Remarkably, it exhibits exceptional electrochemical performance, including a 92% initial Coulombic efficiency, over 1000 mAh g −1 capacity retention after 300 cycles, and retains 570 mAh g −1 after 150 cycles at 13 mA cm −2 , outperforming conventional P‐based anodes and commercial Si/C, demonstrating superior rate capability. Additionally, its superior tap density and conductivity provide further evidence of advantages over existing anode materials.