Synergistic Engineering of Heterointerface and Architecture in New‐Type ZnS/Sn Heterostructures In Situ Encapsulated in Nitrogen‐Doped Carbon Toward High‐Efficient Lithium‐Ion Storage

Abstract Engineering heterogeneous composite electrodes consisting of multiple active components for meeting various electrochemical and structural demands have proven indispensable for significantly boosting the performance of lithium‐ion batteries (LIBs). Here, a novel design of ZnS/Sn heterostructures with rich phase boundaries concurrently encapsulated into hierarchical interconnected porous nitrogen‐doped carbon frameworks (ZnS/Sn@NPC) working as superior anode for LIBs, is showcased. These ZnS/Sn@NPC heterostructures with abundant heterointerfaces, a unique interconnected porous architecture, as well as a highly conductive N‐doped C matrix can provide plentiful Li + ‐storage active sites, facilitate charge transfer, and reinforce the structural stability. Accordingly, the as‐fabricated ZnS/Sn@NPC anode for LIBs has achieved a high reversible capacity (769 mAh g −1 , 150 cycles at 0.1 A g −1 ), high‐rate capability and long cycling stability (600 cycles, 645.3 mAh g −1 at 1 A g −1 , 92.3% capacity retention). By integrating in situ/ex situ microscopic and spectroscopic characterizations with theoretical simulations, a multiscale and in‐depth fundamental understanding of underlying reaction mechanisms and origins of enhanced performance of ZnS/Sn@NPC is explicitly elucidated. Furthermore, a full cell assembled with prelithiated ZnS/Sn@NPC anode and LiFePO 4 cathode displays superior rate and cycling performance. This work highlights the significance of chemical heterointerface engineering in rationally designing high‐performance electrodes for LIBs.