Correlation between Tafel Analysis and Electrochemical Impedance Spectroscopy by Prediction of Amperometric Response from EIS

Abstract

Tafel analysis and electrochemical impedance spectroscopy (EIS) have been widely used to characterize many kinds of electrocatalysts. The former provides the kinetic information of an electrochemical reaction with the exchange current while the latter does with the charge transfer resistance closely related to the exchange current. Both techniques, however, suffer from practical troubles which often decrease their reliabilities. In order to circumvent those troubles, an alternative was suggested that Tafel analysis was combined with EIS, even though its theoretical background was not clearly established. Tafel analysis is based on dc measurement, and EIS is on an ac one, respectively. Here, inspired by the second generation of EIS from chronoamperometry, we try to find how those techniques are correlated by investigating an amperometric response from EIS. The first step is Fourier transform of an arbitrary dc potential signal in the time domain to obtain the amplitudes and phases of the Fourier series which are equivalent to ac signals of each frequency. Second, with the Fourier series being applied onto the impedance data, the responding currents of each frequency are calculated by Ohm's law. Third, the current in the frequency domain is transferred back to the time domain by inverse Fourier transform to yield chronoamperometric or Tafel plots depending on the type of the applied dc potential. Finally, we can study Tafel plots based on EIS at different conditions and their correlations which are expected to be a better indicator for characterizing electrocatalysts instead of the slope of the classical Tafel analysis.