Geometric Remodeling of Silicon Crystal Structure Through Atomic‐Level Fluorine Incorporation for High‐Performance Lithium‐Ion Batteries

ABSTRACT Sustainable electrification continues to drive growing interest in high‐performance lithium‐ion batteries (LIBs), which are essential energy storage systems for this transition. However, conventional graphite‐based LIBs cannot meet the stringent requirements of next‐generation applications, necessitating advanced alternatives. Herein, we report the design of fluorine‐incorporated silicon (FIS) nanostructures through a novel solid–vapor–solid synthesis method that integrates metallothermic reduction with combined top‐down and bottom‐up processes. Crucially, fluorine (F) atoms are inherently positioned both at interstitial sites within the silicon (Si) lattice and on the particle surface. Interstitial F modifies the direct‐allowed band structure of Si and expands lithium penetration pathways, thereby enhancing charge transport through improved electronic conductivity and ion migration. Meanwhile, surface‐bound F induces superhydrophobicity, enabling hydrofluoric acid‐free processing during both synthesis and electrode fabrication. Comprehensively, unveiled features of FIS offer a cost‐effective manufacturing, improved structural and electrochemical stability, and superior performance, leading to cycle‐stable, fast‐charging Si anodes for advanced LIBs.