Use of electrochemical impedance spectroscopy for determining the diffusion layer thickness at the surface of ion-exchange membranes

Three ion-exchange membranes (an AMX homogeneous anion-exchange membrane, a MK-40 heterogeneous cation-exchange membrane, and a Nafion-117 homogeneous cation-exchange membrane) have been studied by electrochemical impedance spectroscopy. Processing of the experimental impedance spectra according to the model developed previously has made it possible to find the Nernst diffusion boundary layer (DBL) thickness δ as a function of current density. The behavior of the AMX membrane has been shown to be close to the “ideal” one described by the model: the impedance spectrum of the membrane is close to the theoretical spectrum and the value of δ is only slightly smaller than the quantity δ _Lev calculated by the Leveque equation derived in terms of classical convective diffusion theory. The behavior of the MK-40 and Nafion membranes markedly differs from the “ideal” behavior: the reactive component of the impedance in the region of medium frequencies corresponding to the maximum point in the low-frequency range of a Warburg type finite-length impedance spectrum is significantly lower than its theoretically predicted value. The value of δ is less than δ _Lev even for underlimiting currents, and the deviation increases with the increasing current density. This specific behavior of the membranes correlate well with the voltammetry data. The behavior of the studied membranes is associated with the surface properties: the heterogeneity (case of MK-40) and, especially, high hydrophobicity of the (Nafion-117) surface facilitate the development of electroconvection. Homogeneity and high hydrophilicity of the surface of the AMX membrane determine its behavior, which is close to the ideal.