Promoting Li Transfer and Storage in Si Anode Through Dynamically Precise Modulation of Constructed Carbon Coating

Abstract Silicon is considered as a promising anode material for lithium‐ion batteries due to its high capacity. However, its huge volume expansion during lithium de‐embedding and low Li + /electron diffusion pose a great challenge for practical applications, while carbon coatings are important strategies to enhance the cycling performance of Si anode. Herein, three kinds of carbon coatings are designed with different microstructures and evaluated the relationship between microstructure and electrochemical behaviors. Combining Li + diffusion kinetics and interfacial composition analyses, this study finds that a hard‐carbon‐like coating with uniformly distributed expanded graphite layer and pores (EG/P) provides rapid Li + /electron diffusion channels. In addition, such a hard‐carbon‐like structure effectively buffers silicon swelling, as observed by in situ electron microscopy with deep learning (DL), the lithiation of Si also operates within the framework of carbon coating, which is also validated at the entire electrode scale. As a result, electrode exhibits higher electrochemical stability and enhanced rate capability compared with conventional carbon coatings. The strategy can also be extended to other alloy‐type negative (Ge, Sn) electrode materials. This study provides insight into the rational design of carbon coating structures as high‐performance anode materials for batteries.