We reveal the reversible redox mechanism of LiPSCl in composite cathodes for practical all-solid-state lithium-sulfur batteries. The limited electrochemical reactivity of the non-conducting sulfur-based active material induces the formation of LiPSCl decomposition products, which allows the recrystallization of LiPSCl through a reversible redox process, contributing to the composite cathode capacity.
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