An Ultrafast Charge‐Driven Topological Intercalation Prelithiation Strategy for Carbon‐Silicon Composite Anodes

Abstract Prelithiation emerges as an effective technique to enhance the initial Coulombic efficiency (ICE) and cycling stability of silicon oxide based carbon composite (C/SiO x ) anodes, yet traditional approaches remain plagued by sluggish kinetics, cumbersome procedures, safety hazards, and inadequate precision. Here, a facile topological intercalation prelithiation method capable of forming a robust and homogeneous solid electrolyte interface (SEI) network on porous C/SiO x nanofiber anodes in merely 30 s is reported. Through constructing three charge‐driven topology models derived from flexible SiO x /porous carbon nanofiber (SiO x /PCNF) films, the mechanism of this fast Li + ‐intercalation process is unraveled. Abundant surface defects on SiO x /PCNF enhance lithium salt adsorption and dissociation, while the active solvated Li + ‐ions can quickly intercalate into SiO x /PCNF along an orientation pathway, realizing a high ICE of 99.44%. This topological prelithiation forges a 3D inorganic‐rich SEI architecture that dualizes functionality: It curtails electrolyte degradation while alleviating volume fluctuation and mechanical stress, while enabling precision Li + ‐ion replenishment. This topochemical paradigm not only achieves ICE reinforcement and cycling resilience (1000 stable cycles), but also slashes prelithiation duration by orders of magnitude.