As exciting candidates for next-generation energy storage, all-solid-state lithium batteries (ASSLBs) are highly dependent on advanced solid-state electrolytes (SSEs). Here, using cost-effective LaCl and CeCl lattice (UCl -type structure) as the host and further combined with a multiple-cation mixed strategy, we report a series of UCl -type SSEs with high room-temperature ionic conductivities over 10 S cm and good compatibility with high-voltage oxide cathodes. The intrinsic large-size hexagonal one-dimensional channels and highly disordered amorphous phase induced by multi-metal cation species are believed to trigger fast multiple ionic conductions of Li , Na , K , Cu , and Ag . The UCl -type SSEs enable a stable prototype ASSLB capable of over 3000 cycles and high reversibility at -30 °C. Further exploration of the brand-new multiple-cation mixed chlorides is likely to lead to the development of advanced halide SSEs suitable for ASSLBs with high energy density.
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