Synergistic Modulation and Compositional Orchestration of Triphasic Hybrid Phosphides with Multi‐Atom Active Sites Toward High‐Performance Lithium‐Ion Batteries

Abstract High‐capacity phosphide‐based anodes present promise for lithium‐ion batteries (LIBs), but have limited intrinsic activity, and undergo sluggish Li ⁺ diffusion rate during cycling, resulting in a poor rate capability and short cycle life. Herein, a heteroatom co‐doped triphasic phosphide (CoNiFeP/CNP) is designed with frogspawn‐like heterostructure, engineered with multi‐phase synergistic principles to enhance ion transport and electrochemical activity. Comprehensive investigations and theoretical calculations demonstrate the critical roles of introduced Co and Fe atoms in tuning the electronic configuration of CoNiFeP/CNP and optimizing binding strength of Ni site. Furthermore, the synergistic Co/Ni/Fe triad constructs a hierarchical defect network that increases electronic conductivity and fine‐tunes Li ⁺ adsorption ability. When used as anode for LIBs, the CoNiFeP/CNP nanocomposite exhibits a superior reversible capacity of 819.2 mAh g ⁻¹ at 0.2 A g ⁻¹ after 100 cycles, outstanding rate capability, and ultralong cycle life (383.8 mAh g ⁻¹ at 2 A g ⁻¹ after 1000 cycles). This work offers a new perspective to regulate multi‐ion storage architectures of phosphide and breaks new path to design electrode with enhanced reversible capacity and excellent rate capability.