A study of Ag-for-Na ion substitution kinetics was carried out by using an electrochemical method. The Ag metal anode, a reference and counter-electrode were deposited as thin films onto a 0.6SiO2-0.2B2O3-0.2Na2O glassy electrolyte. Anode dissolution was studied by using a chronoamperometric method. It was found that generally used interdiffusion models, which assumed constant diffusion coefficients for Ag+ and Na+ cations, were unable to explain the experimentally observed voltage versus time relationships. The deviation from the theoretical predictions could be minimized by assuming the occurrence of a mixed cation effect in the glass, and by taking account of the concentration dependence of the Ag+ and Na+ diffusion coefficients.

C.Thévenin-Annequin, M.Levy, T.Pagnier: Solid State Ionics, 1995, 80[3-4], 175-9