Anion-Incorporation Model Proposed for Interpreting the Interfacial Physical Origin of the Faradaic Pseudocapacitance Observed on Anodized Valve Metals—with Anodized Titanium in Fluoride-Containing Perchloric Acid as an Example

Abstract

With anodized titanium in fluoride-containing perchloric acid solution as an example in the present Article, the physical origin of the faradaic pseudocapacitance C(0) frequently observed in electrochemical impedance spectroscopy (EIS) spectra at low frequencies was interpreted for the first time by the incorporation/insertion of some electrolyte anions (i.e., F(-)-ions in this work) into the oxide film under the electric field during film growth. It was shown that the emergence of the faradaic pseudocapacitive behavior not only indicates a significant incorporation of anions into the oxide films but also reflects the arrival of them at the metal/oxide interface. The anion incorporation/transfer process was depicted with a modified point-defect model and simulated by a blocking, restricted finite-length diffusion impedance model (which has been widely used for studying the ion-insertion electrodes). The fast inward migration of the incorporated electrolyte species, along with the accumulation of them at the metal/film interface (due to the blocking effect of this interface), is responsible for the low-frequency capacitance behavior revealed by a vertical capacitive line in EIS spectra at low frequencies for anodically growing oxide films on valve metals. Many related published results for anodized valve metals (such as Ti, Bi, Ta, Al, etc.) are in good accordance with the model predictions. This work also suggests that the electrochemical method for the preparation of F(-)-doped TiO(2) thin film materials should be an easy, low-cost, and even more effective one to be used.