Electrochemical impedance spectroscopy of thin films with two mobile charge carriers: effects of the interfacial charging

In the electrochemical systems containing an excess of the background electrolyte, the faradaic process and the interfacial (‘double-layer’) charging are coupled to the fluxes of different charge carriers, the former being related to the diffusional transport of electroactive entities while the latter being realized mostly by ions of the supporting electrolyte. As a result, the interfacial capacitance Cdl may simply be added in parallel to the faradaic impedance specific for each particular system (Randles & Ershler). This simple treatment is not justified in the absence of an indifferent electrolyte, if the same charged species take part in both the electrode reaction and the double layer …