Lithium Superionic Conduction in BH(4)‐Substituted Thiophosphate Solid Electrolytes

Compared with conventional liquid electrolytes, solid electrolytes can better improve the safety properties and achieve high‐energy‐density Li‐ion batteries. Sulfide‐based solid electrolytes have attracted significant attention owing to their high ionic conductivities, which are comparable to those of their liquid counterparts. Among them, Li thiophosphates, including Li‐argyrodites, are widely studied. In this study, Li thiophosphate solid electrolytes containing BH(4) (−) anions are prepared via a simple and fast milling method even without heat treatment. The synthesized materials exhibit a high ionic conductivity of up to 11 mS cm(−1) at 25 °C, which is much higher than reported values. To elucidate the mechanism behind, the thiophosphate local structure, whose effect on the ionic conductivity remains unclear to date, is investigated. Raman and solid‐state NMR spectroscopies are performed to identify the thiophosphate local structure in the sulfide samples. Based on the analysis results, the ratios of the different thiophosphate units in the prepared electrolyte samples are determined. It is found that the thiophosphate local structure can be varied by changing the amount of LiBH(4) and the milling conditions, which significantly impact the ionic conductivity. The all‐solid‐state cell with the prepared solid electrolyte exhibits superior cycle and rate performances.