Pre‐Fluorination Interface Engineering of Silicon‐Based Anode for Durable Lithium‐Ion Batteries

Abstract Silicon (Si) anodes are considered promising candidates for next‐generation lithium‐ion batteries (LIBs) due to their high theoretical capacity (≈10 times that of graphite). However, the substantial volume expansion during cycling (>300%) results in the degradation of the solid electrolyte interphase (SEI) and pulverization of Si anodes. Herein, an AlF 3 coating layer is introduced onto commercial Si‐C composites (Si‐C@AF‐x) as an artificial SEI layer, which effectively modulates the interfacial environment with higher kinetics and stability. The Si‐C@AF‐1 anode achieves excellent cycling stability (capacity of 916.0 mA h g −1 after 100 cycles at 0.5 C and retention of 91.6%) and rate capability (549.7 mA h g −1 at 3.0 C). Even under extreme temperatures, the AlF 3 coating layer can still support the fast and stable operation of the Si‐C@AF‐1 electrode, and the Si‐C@AF‐1||NCM811 full cell delivers 85.2% capacity retention after 100 cycles at 0.5 C. This work proves the effectiveness of designing a robust artificial SEI for enhancing the interfacial kinetics and stability, which also fits well with the commercial‐scale production of electrode materials, thereby highlighting its strong commercialization potential for high‐durability LIBs.