(General Student Poster Session Winner - 1st Place) An Algorithm for Fitting Tafel Data and Determining Kinetic Parameters

Abstract

Tafel analysis is widely used to characterize electrochemical kinetics and assess the properties of electrocatalysts for use in fuel cells, electrolyzers, and other applications. Conventional Tafel analysis is an extension of the Butler-Volmer equation at high overpotentials under conditions where mass transport is not significant and the reverse reaction rate is negligible compared to the studied half-reaction. Determination of kinetic parameters from a Tafel plot involves linear regression in regions of large overpotential. This method is limited in part by the subjective determination of linearity, as the kinetic parameters obtained by the regression may vary significantly depending on the chosen linear region.In an effort to increase measurement quality and decrease subjectivity, an algorithm has been developed that generates a Tafel plot from a linear sweep voltammogram (LSV) and determines the exchange current density j 0, charge transfer coefficient α, and Tafel slope of closest fit. Comparisons of kinetic parameters between conventional and algorithmic Tafel analysis are made for the hydrogen evolution reaction (HER, 2H+ + 2e- → H2) on different metal electrodes and Nafion® composite electrodes. The algorithmic Tafel analysis parameters correlate well with conventional methods. Similar agreement is observed between literature and algorithmically fitted kinetic parameters for different electrochemical systems. The developed algorithm allows for straightforward, rapid, and user bias independent Tafel analysis and can be easily used to increase measurement quality.