All-solid-state lithium−sulfur batteries (ASSLSBs) employing sulfide-based solid electrolytes have gained widespread attention for their high energy density and intrinsic safety. Li 10 SnP 2 S 12 is identified as one of the most rivaling candidates in sulfide electrolytes. Herein, a highly Li-ion-conductive Li 10 SnP 2 S 12 solidstate electrolyte (SSE) is synthesized via a combination of high-energy ball-milling and heat treatment processes, which is more facile and efficient compared with other previously reported methods. The obtained Li 10 SnP 2 S 12 SSE exhibits high ionic conductivity (3.2 × 10 −3 S cm −1 ) at room temperature (RT). The effects of the annealing temperature on the Li-ion conductivity and activation energy of Li 10 SnP 2 S 12 are also thoroughly studied. Moreover, the ASSLSBs based on the Li 10 SnP 2 S 12 electrolyte are constructed, and they deliver a high initial capacity of 1601.7 mAh g −1 at 40 mA g −1 . A favorable capacity retention upon cycling and a good rate performance are also achieved at RT. Concomitantly, the Coulombic efficiency approaches 100% during the prolonged cycling. This work tremendously accelerates the practical applications of the Li 10 SnP 2 S 12 SSE among the emerging high-energy ASSLSBs.
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