Challenges and opportunities towards silicon-based all-solid-state batteries

Silicon-based all-solid-state batteries (Si-based ASSBs) are recognized as the most promising alternatives to lithium-based (Li-based) ASSBs due to their low-cost, high-energy density, and reliable safety. In this review, we describe in detail the electro-chemo-mechanical behavior of Si anode during cycling, including the lithiation mechanism, volume expansion, dynamic solid-electrolyte-interphase (SEI) reconstruction of Si anode, the evolution and effect of stress in Si-based ASSBs as well. We also comprehensively summarize the development of all-solid-state electrolytes (ASSEs, e.g., LiPON, sulfide, garnet, and polymer) and structural designs of Si anodes (e.g., nano-structure and composite structure) in Si-based ASSBs. Moreover, we elaborate in detail the challenges and strategies towards high-voltage cathodes of Si-based ASSBs for further construction and application of full batteries. Hence, the significant research advancements of Si-based ASSBs from fundamentals to applications are presented in detail. Finally, we propose some rational suggestions and prospects for in-depth research on failure mechanisms and the further development of ASSEs and Si-based anodes in Si-based ASSBs. We hope that this review will provide valuable insights into failure mechanisms and advanced optimization strategies for the development of next-generation Si-based ASSBs, and bridge the gap between fundamental research and practical applications, particularly for the readers who are new to this field and have an interest in it.