Simultaneous Scanning Ion Conductance and Electrochemical Microscopy in Lithium‐Ion Battery Research

Abstract Deeper understanding of processes involved in operation of lithium‐ion batteries (LIBs) is necessary to further optimize them for future applications. Extensive research was conducted on the formation of a solid electrolyte interphase (SEI) on negative battery electrodes, still leaving several questions unanswered. Scanning probe microscopies (SPMs) enable in situ and operando investigations and have the potential to explain some phenomena. Scanning electrochemical microscopy (SECM) and scanning ion conductance microscopy (SICM) could be employed in LIB studies. A novel SICM method based on the redox couple ferrocene/ferrocenium is introduced for applications in carbonate solvents widely used in LIBs. Proof of concept measurements were conducted with a micro milled copper circuit board as model substrate. Furthermore, the proposed SICM approach was hyphenated with feedback mode SECM resulting in the simultaneous mapping of morphology and electrochemical activity. A flexible dual‐probe arrangement was developed enabling usage of both SPM techniques at the same time, and furthermore, an easy replacement of both individual probes if needed. The setup was applied in the characterisation of commercial graphite electrodes for LIBs before and after conducting a pre‐charging protocol. Changes in electrochemical activity and topography of the graphite electrode were resolved in simultaneously generated SECM/SICM recordings.