| Abstract: | Owing to their safety, high energy density, and long cycling life, all‐solid‐state lithium batteries (ASSLBs) have been identified as promising systems to power portable electronic devices and electric vehicles. Developing high‐performance solid‐state electrolytes is vital for the successful commercialization of ASSLBs. In particular, polymer‐based composite solid electrolytes (PCSEs), derived from the incorporation of inorganic fillers into polymer solid electrolytes, have emerged as one of the most promising electrolyte candidates for ASSLBs because they can synergistically integrate many merits from their components. The development of PCSEs is summarized. Their major components, including typical polymer matrices and diverse inorganic fillers, are reviewed in detail. The effects of fillers on their ionic conductivity, mechanical strength, thermal/interfacial stability and possible Li+‐conductive mechanisms are discussed. Recent progress in a number of rationally constructed PCSEs by compositional and structural modulation based on different design concepts is introduced. Successful applications of PCSEs in various lithium‐battery systems including lithium–sulfur and lithium–gas batteries are evaluated. Finally, the challenges and future perspectives for developing high‐performance PCSEs are proposed. |
