High‐Entropy Engineering of Cubic SiP with Metallic Conductivity for Fast and Durable Li‐Ion Batteries

Abstract A cost‐effective, scalable ball milling process is employed to synthesize the InGeSiP 3 compound with a cubic ZnS structure, aiming to address the sluggish reaction kinetics of Si‐based anodes for Lithium‐ion batteries. Experimental measurements and first‐principles calculations confirm that the synthesized InGeSiP 3 exhibits significantly higher electronic conductivity, larger Li‐ion diffusivity, and greater tolerance to volume change than its parent phases InGe (or Si)P 2 or In (or Ge, or Si)P. These improvements stem from its elevated configurational entropy. Multiple characterizations validate that InGeSiP 3 undergoes a reversible Li‐storage mechanism that involves intercalation, followed by conversion and alloy reactions, resulting in a reversible capacity of 1733 mA h g −1 with an initial Coulombic efficiency of 90%. Moreover, the InGeSiP 3 ‐based electrodes exhibit exceptional cycling stability, retaining an 1121 mA h g −1 capacity with a retention rate of ≈87% after 1500 cycles at 2000 mA g −1 and remarkable high‐rate capability, achieving 882 mA h g −1 at 10 000 mA g −1 . Inspired by the distinctive characteristic of high entropy, the synthesis is extended to high entropy GaCu (or Zn)InGeSiP 5 , CuZnInGeSiP 5 , GaCuZnInGeSiP 6 , InGeSiP 2 S (or Se), and InGeSiPSSe. This endeavor overcomes the immiscibility of different metals and non‐metals, paving the way for the electrochemical energy storage application of high‐entropy silicon‐phosphides.