ZnS Nanoseeds Sealed in N, P, S Co‐Doped Carbon Hollow Rhombic Dodecahedra as a Superlithiophilic Host for Dendrite‐Free Lithium Metal Anodes

Abstract Lithium (Li) metal is considered a hopeful anode for next‐generation Li‐ion batteries thanks to its ultra‐high theoretical specific capacity, extra‐low theoretical density, and low negative potential. However, the uncontrolled growth of Li dendrites and volume fluctuation during plating/stripping processes severely hamper its commercial application. Herein, ZnS seeds sealed in N, P, S co‐doped carbon hollow rhombic dodecahedra (ZnS@NPS‐C HRD) is fabricated as a superlithiophilic host for Li metal anodes (LMAs) to solve the above problems. In addition, the Li nucleation and deposition mechanism on ZnS@NPS‐C HRD is investigated by in situ optical microscopy, ex‐situ X‐ray diffraction, scanning electron microscopy, and theoretical calculations. Owing to the synergistic strategy of ZnS seeds‐inducing nucleation and Li‐limited growth, the as‐prepared composite exhibits stability for 300 cycles in asymmetric cells and a long lifespan over 1100 h in symmetric cells. Moreover, the ZnS@NPS‐C HRD@Li|LiFePO 4 full cell demonstrates a reversible capacity of 100.91 mAh g −1 after 400 cycles at 1 C.