Curvature‐Activated Graphite Scaffolds Guide Charge Migration and Stress Distribution in Silicon Anodes

ABSTRACT Despite its pronounced impact on charge transport and local stress‐field regulation, interfacial curvature remains an underexplored design parameter for silicon anodes. Here, we report a silicon anode encapsulated by a molecularly curved, sp 3 ‐rich graphite framework constructed via high‐energy ball milling. This curvature‐defect architecture transforms the typically inert graphite host into an active mediator for interfacial charge redistribution and stress relaxation. The curvature induces built‐in work‐function gradients and local electric fields that direct Li + /electron transport and suppress early stress hotspots; concurrently, curvature‐enhanced sp 3 ‐C sites catalyze in situ Si─C bond formation and drive interfacial charge redistribution, leading to partial Si de‐electronation and reversible core contraction. These coupled mechanisms homogenize 3D stress propagation, suppress crack initiation during lithiation. This curvature‐field‐stress coupling effectively overcomes the long‐standing challenge of multistage stress accumulation and unstable interfacial charge dynamics at the silicon‐graphite anode interface, thereby contributing to enhanced rate capability and long‐term cycling stability. Electrochemical characterizations reveal that the composite exhibits ultralow capacity decay (∼0.025% per cycle over 1200 cycles at 1 A g −1 ) and retains ∼492 mA h g −1 at 5 A g −1 . This curvature‐defect paradigm provides a scalable, mechanistically grounded pathway to activate inert graphite hosts and design stress‐tolerant, long‐lived silicon‐carbon anodes.