Abstract
A scanning probe microscopy approach for mapping local irreversible electrochemical processes based on detection of bias-induced frequency shifts of cantilevers in contact with the electrochemically active surface is demonstrated. Using Li-ion conductive glass ceramic as a model, we demonstrate near unity transference numbers for ionic transport and establish detection limits for current-based and strain based detection. The tip-induced electrochemical process is shown to be a first order transformation and nucleation potential is close to the Li-metal reduction potential. Spatial variability of the nucleation bias is explored and linked to the local phase composition. These studies both provide insight into nanoscale ionic phenomena in practical Li-ion electrolyte, and also open pathways for probing irreversible electrochemical, bias-induced, and thermal transformations in nanoscale systems.
