Efficient Lithium Transport and Reversible Lithium Plating in Silicon Anodes: Synergistic Design of Porous Structure and LiF‐Rich SEI for Fast Charging

Abstract Silicon (Si) anodes hold great promise for enhancing the energy density of lithium‐ion batteries (LIBs). However, issues such as slow intrinsic kinetics and unstable interfaces caused by significant volume changes hinder the practical deployment of Si anodes. Fast charging is desired by Si‐related issues that worsen Li plating and dead Li, making it essential to overcome these for safe, reversible charging. Herein, a novel approach is proposed by combining structural design and solid electrolyte interface (SEI) modulation to enable efficient and safe fast charging of LIBs. 3D porous micro‐particles consisting of Si nanosheets coated with a pitch‐based carbon layer are successfully prepared. This design provides enhanced ion transport pathways while maintaining the material's intrinsic rate performance and tap density. Furthermore, the designed localized high‐concentration electrolyte (LHCE) exhibits a lower Li + desolvation energy barrier and leads to the formation of a LiF‐rich SEI, mitigating the Li plating “tip effect” during fast charging, maintaining interface stability, and demonstrating high Coulombic efficiency. Overall, this study highlights the synergistic importance of structure design and SEI regulation in enhancing LIB anodes for fast charging, aiding in developing superior, safe energy storage.