Theoretical and Numerical Study of Formation of Near-Electrode Layers in Ionic Conductor Liquids at High Voltages.

A novel approach is developed to predict the thickness of the equivalent one-dimensional Stern layer near conducting electrodes subjected to high voltage and carrying electric current. The nonspecific (nonelectric) ion adsorption responsible for the formation of the Stern compact layer at the electrode surface is attributed to the Langmuir-Brunauer-Emmett-Teller mechanism. The compact Stern layer is implied to be intrinsically two-dimensional and forming on the oxide or impurity islands on the electrode surface, which prevents electron transfer to or from the adsorbed ions. On the other hand, electrons are transferred through the open parts of the metallic electrode surface by electron transfer faradaic reactions characterized by the Frumkin-Butler-Volmer kinetics. Then, the one-dimensional Stern layer appears to be an approximation of the abovementioned two-dimensional model. In the framework of this model, the equivalent one-dimensional Stern layer thickness is predicted, rather than used as an adjustable parameter, as frequently done in the literature.