Editors' Choice—Electrolyte Film Thickness Effects on the Cathodic Current Availability in a Galvanic Couple

Abstract

A combined modeling and experimental study was performed to understand the dependence of the cathodic current delivery capacity on the electrolyte film thickness and cathode size in a galvanic couple. The appropriate cathodic kinetics for the modeling were generated by use of a rotating disk electrode to simulate the electrolyte film thickness. These results provided boundary conditions for a finite element model which calculated the potential distribution along a metallic surface and the associated cathodic current supplied for electrolyte layers of varying thickness. The total cathodic current was then calculated through integration of the current density across the surface. Electrolyte layer domains were delineated by three limits which described, in order of decreasing film thickness, i) transition in exposure condition from full immersion to thick film, ii) the hydrodynamic boundary layer due to natural convection which defined the upper limit of the thin film regime, and iii) the relative dominance of ohmic resistance over mass transport in determining the total current output. This study also showed that for sufficiently thin films, this total current was independent of the size of the cathode and the nature of kinetics at the electrochemical interface, being solely driven by the ohmic resistance in solution.