Micro‐Scale Dual Interface Layer With N‐Coordination Encapsulated on Coralloid Si Anode for Lithium‐Ion Batteries

Micro‐scale silicon (μSi) anodes are promising candidates for enhancing energy density of lithium‐ion batteries, yet their commercialization is hindered by severe volumetric expansion and interfacial instability. Herein, we present a coralloid μSi encapsulated in a micro‐scale N‐coordinated dual‐carbon interface (μSi@CNC) structure via simple AlSi melt modification and spray carbonization to alleviate these problems. The unique multifunctional carbon architecture efficiently tackles the challenges of interfacial instability and poor conductivity for the coralloid μSi matrix. Synergistic with N coordination, the fabricated μSi@CNC anode delivers robust structural integrity and rapid charge transfer kinetics. Finite element analysis demonstrates the optimized ionic insertion/extraction kinetics and suppressed irreversible SEI formation achieved by engineering the interfacial network. Therefore, the μSi@CNC anode achieves a high initial Coulombic efficiency of 85.7% and retains 792.1 mAh g −1 after 500 cycles. Both LiCoO 2 ||μSi@CNC full cell and μSi@CNC/graphite hybrid anode demonstrate high capacity with excellent cycling stability. This work establishes a novel and scalable route for fabricating high‐performance μSi anode in advanced lithium‐ion batteries.