In Situ Characterization of Interface Evolution in Argyrodite‐Based All‐Solid‐State Li Batteries

Abstract Interfacial stability is one of the critical challenges in all‐solid‐state Li metal batteries. Multiple processes such as solid electrolyte (SE) decomposition and lithium dendrite growth take place at the solid interfaces during cycling, leading to the overall cell failure. To deconvolute these complex processes, in situ characterization is of paramount importance to elucidate the interfacial evolution on the SE upon Li plating/stripping. Herein, an all‐solid‐state asymmetric in situ cell is developed that allows the direct visualization of the highly localized Li plating/stripping processes under the optical microscope. Moreover, this cell configuration enables reliable post‐mortem chemical and morphological analysis of the intact SE/Li interface. Using combined scanning electron microscopy and energy‐dispersive X‐ray spectroscopy, the study reveals that the evolution of the Li argyrodite interface is strongly influenced by the current density, particularly in terms of chemical distribution and Li plating morphology. More specifically, the solid interface is LiCl‐rich with the formation of Li cubes at low current densities, while high currents result in more uniform elemental distribution and filament morphology. These findings elucidate the dynamic evolution mechanism at solid interfaces and offer valuable guidance for developing stable solid interfaces in all‐solid‐state Li metal batteries.