Electrochemical and Structural Analysis in All‐Solid‐State Lithium Batteries by Analytical Electron Microscopy: Progress and Perspectives

: Advanced scanning transmission electron microscopy (STEM) and its associated instruments have made significant contributions to the characterization of all-solid-state (ASS) Li batteries, as these tools provide localized information on the structure, morphology, chemistry, and electronic state of electrodes, electrolytes, and their interfaces at the nano- and atomic scale. Furthermore, the rapid development of in situ techniques has enabled a deep understanding of interfacial dynamic behavior and heterogeneous characteristics during the cycling process. However, due to the beam-sensitive nature of light elements in the interphases, e.g., Li and O, thorough and reliable studies of the interfacial structure and chemistry at an ultrahigh spatial resolution without beam damage is still a formidable challenge. Herein, the following points are discussed: (1) the recent contributions of advanced STEM to the study of ASS Li batteries; (2) current challenges associated with using this method; and (3) potential opportunities for combining cryo-electron microscopy and the STEM phase contrast imaging techniques.