K 3 SbS 4 as a Potassium Superionic Conductor with Low Activation Energy for K–S Batteries

Abstract Solid‐state K‐ion conducting electrolytes are key elements to address the current problems in K secondary batteries. Here, we report a sulfide‐based K‐ion conductor K 3 SbS 4 with a low‐activation energy of 0.27 eV. W‐doped K 3− x Sb 1− x W x S 4 ( x =0.04, 0.06, 0.08, 0.10 and 0.12) compounds were also explored for increasing vacancy concentrations and improving ionic conductivity. Among them, K 2.92 Sb 0.92 W 0.08 S 4 exhibits the highest conductivity of 1.4×10 −4 S cm −1 at 40 °C, which is among the best reported potassium‐ion conductors at ambient temperature. In addition, K 2.92 Sb 0.92 W 0.08 S 4 is electrochemically stable with long‐chained potassium polysulfide of K 2 S x . A room‐temperature solid potassium–sulfur (K−S) battery system has therefore been successfully demonstrated, which is the first K−S battery prototype using non‐commercial inorganic‐based electrolyte to block the polysulfide shuttle.