Interface‐Mediated Architectural Engineering of Silicon for Solid‐State Batteries: Current Status and Future Outlook

Solid‐state lithium batteries promise superior performance and enhanced safety over current lithium‐ion batteries. As lithium metal encounters intrinsic challenges, high‐capacity silicon anodes have gained increasing attention to satisfy the growing demand for higher energy density and safety. However, the commercialization of such systems is impeded by challenges including large volume variation, poor interfacial contact, sluggish charge transport, inferior performance, and excessive pressure reliance. This review discusses fundamental challenges and interface‐mediated architectural engineering strategies. Based on the coupling mode of silicon and solid electrolyte, the developed architectures are classified into three representative categories, with emphasis on their design principles, multiscale construction methodologies, and enhancement mechanisms. In light of the latest advances, this review systematizes the architectural paradigms, and clarifies the synergistic correlations between interfacial compatibility, electron and ion transport, stress relaxation, and side reactions between silicon and solid electrolyte. Scalable manufacturing protocols and sustainable monitoring approaches are then delineated toward practical applications. Finally, the review summarizes the advantages and disadvantages of these classifications and outlines future directions for advancing stable, safe, scalable, and sustainable silicon‐based electrode technologies for viable solid‐state batteries with enhanced energy density, power capability, durability, and manufacturability at low‐pressure operation.