Nanoscale Visualization of Lithium Plating/Stripping Tuned by On‐site Formed Solid Electrolyte Interphase in All‐Solid‐State Lithium‐Metal Batteries

Abstract The interfacial processes, mainly the lithium (Li) plating/stripping and the evolution of the solid electrolyte interphase (SEI), are directly related to the performance of all‐solid‐state Li‐metal batteries (ASSLBs). However, the complex processes at solid‐solid interfaces are embedded under the solid‐state electrolyte, making it challenging to analyze the dynamic processes in real time. Here, using in situ electrochemical atomic force microscopy and optical microscopy, we directly visualized the Li plating/stripping/replating behavior, and measured the morphological and mechanical properties of the on‐site formed SEI at nanoscale. Li spheres plating/stripping/replating at the argyrodite solid electrolyte (Li 6 PS 5 Cl)/Li electrode interface is coupled with the formation/wrinkling/inflating of the SEI on its surface. Combined with in situ X‐ray photoelectron spectroscopy, details of the stepwise formation and physicochemical properties of SEI on the Li spheres are obtained. It is shown that higher operation rates can decrease the uniformity of the Li + ‐conducting networks in the SEI and worsen Li plating/stripping reversibility. By regulating the applied current rates, uniform nucleation and reversible plating/stripping processes can be achieved, leading to the extension of the cycling life. The in situ analysis of the on‐site formed SEI at solid‐solid interfaces provides the correlation between the interfacial evolution and the electrochemical performance in ASSLBs.