Electrochemistry at conductor/insulator/electrolyte three-phase interlines: A thin layer model

A thin layer model is proposed to assist in the understanding of the electrochemical conversion of insulator to conductor at the conductor/insulator/electrolyte three-phase interline (3PI) when the influence of mass diffusion in the electrolyte phase is negligible. The model predicts, under potentiostatic conditions, a linear variation of the current or the length of the 3PI with time. When polarization is sufficiently large, the logarithm of the current/time ratio or the 3PI-length/time ratio, according to the model, increases linearly with the applied potential. These predictions were tested against and agreed very well with two practical systems: the electroreduction of solid AgCl to Ag in aqueous KCl and of solid SiO2 to Si in molten CaCl2. Kinetic parameters were derived from experimental data using the model. Particularly, the electron transfer coefficient, alpha, was found to be about 0.29 for the reduction of AgCl to Ag in the aqueous KCl solution at room temperature but about 10(-2) for the reduction of SiO2 to Si in molten CaCl2 at 850 degrees C.