Emerging Roles of Silicon‐Based Materials in Advanced Composite Solid‐State Electrolytes for Lithium Batteries: From Silicates to Silanes

Solid-state lithium batteries are of great interest due to their high energy density and safety. However, solid-state electrolytes, their core component, still face challenges such as limited ionic conductivity, poor interfacial stability, and inadequate mechanical strength. Organic-inorganic composite solid-state electrolytes (OICSEs) offer a viable solution by integrating the flexibility of polymers with the high ionic conductivity of inorganic materials. Silicon (Si)-based materials, including silicate, silica, and silanes, stand out due to their excellent thermal stability, high efficiency in dissolving lithium salts, and excellent compatibility with polymer matrices. The incorporation of Si-based materials can substantially enhance the ionic conductivity, interfacial compatibility, and mechanical properties of OICSEs. This review provides a comprehensive overview of recent advances in Si-based materials for OICSEs, with emphasis on their mechanisms in enhancing ionic conductivity, interfacial stability, and structural optimization. Si-based materials significantly improve the overall performance of OICSEs by suppressing polymer crystallinity, constructing efficient ion transport channels, and enhancing interfacial stability. Furthermore, the review outlines future application prospects of Si-based materials in the design of OICSEs, identifies current technological bottlenecks, and proposes corresponding solutions. This review aims to offer scientific insight and design principles for the development of next-generation high-performance OICSEs in solid-state lithium batteries.