title: Electrochemical characteristics of ideal polarizable interfaces with limited number of charge carriers.
abstract: Recent progress in material chemistry and surface engineering has led to emergence of new electrode materials with unique physical and electrochemical properties. Here, we introduce a physical model describing charging of ideal polarizable electrode-electrolyte interface where the electrode is characterized by a limited capacity to store charge. The analytical model treats the electrode and electrolyte phases as independent nonlinear capacitors that are eventually coupled through the condition of equality of the total stored electrical charge opposite in sign. Gouy-Chapman and condensed layer theories applied to a general 1:n valent electrolyte are used to predict dependencies of differential capacitance of the electrolyte phase and surface concentration of the electrical charge on the applied potential. The model of the nonlinear capacitor for the electrode phase is described by a theory of electron donors and acceptors present in conductive solids as a result of thermal fluctuations. Both the differential capacitance and the surface concentration of the electrical charge in the electrode are evaluated as functions of the applied potential and related to the capacity of the electrode phase to accumulate charge and its ability to form electron donors and acceptors. The knowledge of capacitive properties of both phases allows to predict electrochemical characteristics of ideal polarizable interfaces, e.g., current responses in linear sweep voltammetry. The coupled model also shows significant potential drops in the electrode comparable to those in the electrolyte phase for materials with low charge carrier concentrations.
authors.affiliation: University of Chemistry and Technology, Prague, Department of Chemical Engineering, Technická 5, 166 28 Praha 6, Czech Republic.
authors.forename: Michal
authors.initials: M
authors.lastname: Přibyl
authors.affiliation: University of Chemistry and Technology, Prague, Department of Chemical Engineering, Technická 5, 166 28 Praha 6, Czech Republic.
authors.forename: Zdeněk
authors.initials: Z
authors.lastname: Slouka