Fast ion conduction in solid-state matrices constitutes the foundation for a wide spectrum of electrochemical systems that use solid electrolytes (SEs), examples of which include solid-state batteries (SSBs), solid oxide fuel cells (SOFCs), and diversified gas sensors. Mixing different solid conductors to form composite solid electrolytes (CSEs) introduces unique opportunities for SEs to possess exceptional overall performance far superior to their individual parental solids, thanks to the abundant chemistry and physics at the new interfaces thus created. In this review, we provide a comprehensive and in-depth examination of the development and understanding of CSEs for SSBs, with special focus on their physiochemical properties and mechanisms of ion transport therein. The origin of the enhanced ionic conductivity in CSEs relative to their single-phase parents is discussed in the context of defect chemistry and interfacial reactions. The models/theories for ion movement in diversified composites are critically reviewed to interrogate a general strategy to the design of novel CSEs, while properties such as mechanical strength and electrochemical stability are discussed in view of their perspective applications in lithium metal batteries and beyond. As an integral component of understanding how ions interact with their composite environments, characterization techniques to probe the ion transport kinetics across different temporal and spatial time scales are also summarized.

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