The all-solid-state lithium batteries (ASSLBs) have drawn increasing interests and demands as the next-generation rechargeable batteries for electric vehicles and energy storage devices since they have much more potentials (e.g., higher safety, reliability, power density, and design flexibility) than conventional lithium batteries. However, all we know any further advances in ASSLBs are not possible without solving the current raising issues of ASSLBs, such as low lithium ion conductivity, structural instability, and high resistance of electrode/electrolyte interface. Especially, the unveiling the mechanism of lithium ion conduction in solid electrolytes, and the development of a superior solid-state lithium ion conductor are required.

Here we present the recent advances and understandings in Li-P-S based solid electrolytes for the next-generation ASSLBs using a novel atomistic alloying and annealing process. Employing the low-temperature milling and quantitative bulk/surface analyses, we demonstrate the tuning ionic structures in sulfide glass-ceramics for superior solid-state electrolytes, and unveil the roles of atomistic alloying in the mechanochemical pulverization and high-temperature annealing in the amorphous-crystal transition to seek the highly active, stable, and versatile Li-P-S based solid electrolytes. Controlling ionic structures and understanding such atomistic alloying and annealing effects of lithium super-conducting sulfides provides insights for designing advanced solid electrolyte materials. We also believe these research activities lead to the promising technological advances and provide new guidelines in developing the sulfide based solid electrolyte for ASSLBs.