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

Abstract

AbstractA cost‐effective, scalable ball milling process is employed to synthesize the InGeSiP3 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 InGeSiP3 exhibits significantly higher electronic conductivity, larger Li‐ion diffusivity, and greater tolerance to volume change than its parent phases InGe (or Si)P2 or In (or Ge, or Si)P. These improvements stem from its elevated configurational entropy. Multiple characterizations validate that InGeSiP3 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 InGeSiP3‐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)InGeSiP5, CuZnInGeSiP5, GaCuZnInGeSiP6, InGeSiP2S (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.