Material characterization that informs research and development of batteries is generally based on well-established ex situ and in situ experimental methods that do not consider the band structure. This is because experimental extraction of structural information for liquid-electrolyte batteries is extremely challenging. However, this hole in the available experimental data negatively affects the development of new battery systems. Herein, we determined the entire band structure of a model thin-film solid-state battery with respect to an absolute potential using operando hard X-ray photoelectron spectroscopy by treating the battery as a semiconductor device. We confirmed drastic changes in the band structure during charging, such as interfacial band bending, and determined the electrolyte potential window and overpotential location at high voltage. This enabled us to identify possible interfacial side reactions, for example, the formation of the decomposition layer and the space charge layer. Notably, this information can only be obtained by evaluating the battery band structure during operation. The obtained insights deepen our understanding of battery reactions and provide a novel protocol for battery design.

The performances of next generation all-solid-state batteries might be improved by using multi-valent cation doped Li₆PS₅Cl solid electrolytes.

Li₁₀GeP₂S₁₂ solid electrolytes for all-solid-state batteries were synthesised rapidly through liquid-phase method in 7.5 h.