Percolative Channels for Superionic Conduction in an Amorphous Conductor

All-solid-state batteries greatly rely on high-performance solid electrolytes. However, the bottlenecks in solid electrolytes are their low ionic conductivity and stability. Here we report a new series of amorphous xAgI·(1-x)Ag₃PS₄ (x = 0∼0.8 with interval of 0.1) conductors, among which the sample with x = 0.8 exhibits the highest ionic conductivity (about 1.1 × 10^-2 S cm^-1) and ultrahigh chemical stability. We discovered the existence of mixed disordered Ag₃PS₄ and AgI clusters in the amorphous conductors using solid-state nuclear magnetic resonance spectroscopy. The high ionic conductivity was ascribed to the formation of the interconnecting AgI clusters, i.e., the percolative channels for superionic conduction. The composition dependence of the ionic conductivity for this series of amorphous conductors was clarified by a continuum percolation model. These findings provide fundamental guidance for designing and fabricating high-performance amorphous solid electrolytes for all-solid-state batteries.