Electrochemical insertion/de-intercalation reactions were typically associated with significant change in molar volume of the host compound. This strong coupling between ionic currents and strains underpins image formation mechanisms in electrochemical strain microscopy, and allowed exploring the tip-induced electrochemical processes locally. Here the signal formation mechanism in electrochemical strain microscopy was analyzed, and an analytical description of operation in the frequency and time domains was developed. The electrochemical strain microscopy spectroscopic modes were compared to classical electrochemical methods, including potentiostatic and galvanostatic intermittent titration, and electrochemical impedance spectroscopy. This analysis illustrated the feasibility of spatially resolved studies of Li-ion dynamics on the sub-10nm level using electromechanical detection.

Local Probing of Ionic Diffusion by Electrochemical Strain Microscopy: Spatial Resolution and Signal Formation Mechanisms. A.N.Morozovska, E.A.Eliseev, N.Balke, S.V.Kalinin: Journal of Applied Physics, 2010, 108[5], 053712