Theoretical voltammetric response of electrodes coated by solid polymer electrolyte membranes

• Discretized model for an interface of covered electrodes.
• Two limiting behaviors are capture: double-layer and conductive interfaces.
• Additional phenomena are included easily: acid/base equilibrium, ion mobility.
• The model provides explanations to observed phenomena that is vaguely explained in the literature.
• Implications on electrodes in fuel cells are given and it opens avenues to understand and design such systems.

A model for the differential capacitance of metal electrodes coated by solid polymer electrolyte membranes, with acid/base groups attached to the membrane backbone, and in contact with an electrolyte solution is developed. With proper model parameters, the model is able to predict a limit response, given by Mott–Schottky or Gouy–Chapman–Stern theories depending on the dissociation degree and the density of ionizable acid/base groups. The model is also valid for other ionic membranes with proton donor/acceptor molecules as membrane counterions. Results are discussed in light of the electron transfer rate at membrane-coated electrodes for electrochemical reactions that strongly depend on the double layer structure. In this sense, the model provides a tool towards the understanding of the electro-catalytic activity on modified electrodes. It is shown that local maxima and minima in the differential capacitance as a function of the electrode potential may occur as consequence of the dissociation of acid/base molecular species, in absence of specific adsorption of immobile polymer anions on the electrode surface. Although the model extends the conceptual framework for the interpretation of cyclic voltammograms for these systems and the general theory about electrified interfaces, structural features of real systems are more complex and so, presented results only are qualitatively compared with experiments.

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