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Highly Li-ion conductive Li
PS
Cl solid-state electrolytes (SSEs) were prepared by solid-state sintering method. The influence of sintering temperature and duration on the phase, ionic conductivity, and activation energy of Li
PS
Cl was systematically investigated. The Li
PS
Cl electrolyte with a high ionic conductivity of 3.15 × 10
S cm
at room temperature (RT) was obtained by sintering at 550 °C for just 10 min, which was more efficient taking into account such a short preparation time in comparison with other reported methods to synthesize Li
PS
Cl SSEs. All-solid-state lithium sulfur batteries (ASSLSBs) based on the Li
PS
Cl SSE were assembled by using the nano-sulfur/multiwall carbon nanotube composite combined with Li
PS
Cl as the cathode and Li-In alloy as the anode. The cell delivered a high discharge capacity of 1850 mAh g
at RT for the first full cycle at 0.176 mA cm
(∼0.1C). The discharge capacity was 1393 mAh g
after 50 cycles. In addition, the Coulombic efficiency remained nearly 100% during galvanostatic cycling. The experimental data showed that Li
PS
Cl was a good candidate for the SSE used in ASSLSBs.