The electrochemical reaction mainly occurs at the electrode/electrolyte interface in the electrochemical system. For a fundamental insight into the interfacial reaction mechanism, in situ/operando analysis of the interfacial evolution at the microscale is essential. Scanning probe microscopy (SPM), noted for its high spatial resolution, real-time imaging, and multifunctional detection, is considered as one of the most important in situ analytical tools for the electrochemical interfaces from the atomic/molecular scale to the nanoscale. This review first introduces the brief principles of typical SPM, such as scanning tunneling microscopy, atomic force microscopy, and scanning electrochemical microscopy. The applications of in situ SPM in surface and interface analysis for electrochemical energy systems, including electrocatalysts and energy storage batteries, are then presented. In addition, in situ detection of the electric double layer and space charge layer is further discussed. Challenges and future developments in the field are proposed in the outlook.
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