Coupled Design of Silicon Anodes and Solid-State Electrolytes for High-Performance All-Solid-State Batteries

Silicon-based solid-state batteries (Si-SSBs) offer enhanced safety and higher energy density over conventional liquid-electrolyte systems, yet their practical realization is critically hindered by severe volume expansion of silicon anodes and poor interfacial compatibility with solid-state electrolytes. This review provides a comprehensive evaluation of recent advances from a coupled design perspective, integrating silicon anode engineering, electrolyte compatibility optimization, and interfacial stabilization. We systematically examine emerging strategies for silicon anodes alongside compatibility approaches tailored to each electrolyte type, with a particular focus on the coupled chemo-mechanical degradation at the silicon/electrolyte interface. A systematic compatibility mapping linking different Si architectures with specific electrolyte families reveals the most promising material combinations and their underlying design principles. Beyond materials design, we address critical manufacturing challenges including stack pressure management, scalable processing, and prelithiation techniques essential for industrial translation. Finally, we propose a forward-looking roadmap integrating multiscale characterization, AI-assisted design, and scalable fabrication, providing both theoretical guidance and practical strategies for developing high-performance, commercially viable Si-SSBs.