Advancing High‐Performance Si Anodes for Next‐Generation Li‐Ion Batteries: Strategies for Structural Stability, Interfacial Compatibility, and Transport Kinetics

ABSTRACT Silicon (Si) anode materials demonstrate exceptional advantages, including high specific capacity, suitable electrochemical potential, and abundant natural reserves, thereby emerging as a highly promising alternative to conventional graphite electrodes for boosting the high energy density of lithium‐ion batteries (LIBs). However, Si anodes face critical challenges: significant volume expansion during lithiation/delithiation, severe pulverization during cycling, and inherently low electrical conductivity. To mitigate these issues, extensive research has focused on the design of nano‐Si architectures and on bulk and surface modifications to develop high‐performance anode materials to meet the demands of next‐generation LIBs. This review provides a comprehensive analysis of the latest advancements in Si anode materials, focusing on strategies to enhance structural stability, rate capacity, and long‐term cycling performance. We discuss the crucial roles of various nanoarchitecture designs in structural stability, the effect of alloying and doping within the Si matrix on alleviating volume change and improving electrical conductivity, and the influence of surface modification on buffering volume expansion, stabilizing the interface, and enhancing conductivity. The review also highlights the importance of Si anode applications in solid‐state batteries and offers a forward‐looking perspective on future research directions. This work serves as a valuable resource for researchers and engineers, summarizing current progress and identifying key pathways for the successful integration of high‐performance Si materials into commercial LIB technology.