Tracking Passivation and Cation Flux at Incipient Solid‐Electrolyte Interphases on Multi‐Layer Graphene using High Resolution Scanning Electrochemical Microscopy

Abstract The solid electrolyte interphase (SEI) is a dynamic, electronically insulating film that forms on the negative electrode of Li + batteries (LIBs) and enables ion movement to/from the interface while preventing electrolyte breakdown. However, there is limited comparative understanding of LIB SEIs with respect to those formed on Na + and K + electrolytes for emerging battery concepts. We used scanning electrochemical microscopy (SECM) for the in situ interfacial analysis of incipient SEIs in Li + , K + and Na + electrolytes formed on multi‐layer graphene. Feedback images using 300 nm SECM probes and ion‐sensitive measurements indicated a superior passivation and highest cation flux for a Li + ‐SEI in contrast to Na + and K + ‐SEIs. Ex situ X‐ray photoelectron spectroscopy indicated significant fluoride formation for only Li + and Na + ‐SEIs, enabling correlation to in situ SECM measurements. While SEI chemistry remains complex, these electroanalytical methods reveal links between chemical variables and the interfacial properties of materials for energy storage.