title: Mapping irreversible electrochemical processes on the nanoscale: ionic phenomena in li ion conductive glass ceramics.
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.
authors.affiliation: The Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37922, United States.
authors.forename: Thomas M
authors.initials: TM
authors.lastname: Arruda
authors.forename: Amit
authors.initials: A
authors.lastname: Kumar
authors.forename: Sergei V
authors.initials: SV
authors.lastname: Kalinin
authors.forename: Stephen
authors.initials: S
authors.lastname: Jesse