Recent Progress in Silicon‐Based Anodes for High‐Energy Lithium‐Ion Batteries: From the Perspective of “Size Effects”

ABSTRACT Silicon‐based anode materials have garnered considerable attention in lithium‐ion batteries (LIBs) due to their exceptionally high theoretical capacity and energy density. However, intrinsic challenges, such as significant volumetric expansion and the consequent degradation in cycling stability, severely hinder their practical application. As a result, development of silicon anodes that can effectively mitigate volumetric expansions, enhance cycling durability, and improve rate performance has emerged as a critical research focus. However, due to neglect of “size effects”, the modification strategy of silicon‐based electrodes lacks systematic, scientific, and comprehensive guidance. Herein, this review starts from the “size effect” of silicon‐based materials, and reveals in depth the different failure mechanisms of nano‐silicon (Si NPs) and micro‐silicon (μSi). Furthermore, this review provides targeted classification of modification strategies for Si NPs and μSi, and reviews comprehensively, in detail, and in depth the latest research progress on silicon‐based materials. In addition, the review also comprehensively summarizes the cutting‐edge dynamics of matching silicon‐based electrodes with solid electrolytes to construct high‐energy LIBs. It is hoped that this review can provide comprehensive and systematic scientific guidance for modification strategies of silicon‐based electrodes, which is of great significance for promoting the industrialization process of silicon‐based electrodes in high‐energy LIBs.