Are Sulfide‐Based Solid‐State Electrolytes the Best Pair for Si Anodes in Li‐Ion Batteries?

Abstract The integration of Si‐based anodes within sulfide‐based solid electrolyte (SSE) Li‐ion batteries (LIB) has emerged as a promising avenue of research and development, attracting increasing interest in recent years. This work comprehensively examines the latest research directions and major strides in this field. It covers the key advances in the design and engineering of nano‐ and micro‐structured Si anode architectures, and strategies of surface modification. Additionally, it explores the impacts of external pressure, the role of binders and conductive additives, and the implications of varying Si particle size. Beyond providing a detailed account of the evolution of Si anodes within SSE LIBs, this work also identifies critical research challenges that urgently need addressing. These include the electrochemical‐mechanical evolution behavior and failure mechanism of Si anodes in SSE LIBs, strategies for structural and interface modifications, methods for preparing Si electrodes, advancements in high‐performance SSEs, and the development of scalable technologies for SSE thin films. Moreover, it discusses high‐energy cathodes tailored for Si‐based SSE LIBs. The identified research priorities are set to offer crucial guidance and insights, supporting the ongoing investigations and innovations in this dynamic area of research.