Detection of Charge‐Neutral Near‐Equilibrium Processes at Na‐Metal Electrodes by Electrochemical Microcalorimetry

Investigations on electrochemical kinetics usually rely on the measurement of current or potential as a function of time. Charge-neutral process steps or side reactions are naturally disguised in the electrical signals and have only indirect
impact. However, all processes will contribute to heat evolution. In this work, heat absorption/liberation is measured as a function of time for pulsed Na deposition/dissolution on a Na-electrode in a 1 m NaPF$_6$ /diglyme solution, in addition to the standard electrochemical signals. While potential and current transients both exhibited sharp rectangular shapes, indicating instantaneous electrochemical Na deposition or dissolution on the time scale of the pulse (10 ms), heat absorption or liberation continued up to about 0.5 s after the pulse. Since heat evolution is to large extent reversible, this corresponded to entropy changes in the absence of external electric current flow, pointing to a reversible, charge-neutral chemical process accompanying Na deposition or dissolution. From the observed entropy changes, it is suggested that upon Na deposition solvated Na$^+$ ions are instantaneously transferred into the outer layers of the solid electrolyte interphase, followed by slow desolvation.