Here, we report development of the galvanostatic Fourier transform electrochemical impedance spectroscopy (FTEIS), which monitors impedance of electrochemical reactions activated by current steps. We first derive relevant relations for potential change upon application of a step current, obtain impedances theoretically from the relations by simulation, and verify them with experimental results. The validity of the galvanostatic FTEIS technique is demonstrated by measuring impedances of a semiconductive silicon wafer using the conventional frequency response analysis (FRA), the potentiostatic FTEIS, and the galvanostatic FTEIS methods, and the results are in excellent agreement with each other. This work is significant in that the galvanostatic FTEIS would allow one to record impedance changes during charge/discharge cycles of secondary batteries and fuel cells as well as electrochemically irreversible systems which may produce noise level chronoamperometric currents by potentiostatic techniques.
When the electric potential is applied at the electrode to activate electrochemical reactions, part of the applied potential is dropped by the overpotentials and the rate of the reaction is determined by the potential difference at the interface between the electrode and the outer Helmholtz plane. Here we present a new method to measure the interfacial potential using the combination of the molecular probe and the electrochemical impedance spectroscopy. Using this method, we observed that the potential drop across the Helmholtz plane decreases logarithmically along with the concentration of the supporting electrolyte in the solution. As our method is available to any kind of electrochemical cells, it can be used to obtain information and control the properties of interfaces on the modified electrodes.
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