Conventionally, Tafel analysis is an extension of the Butler-Volmer equation applied at high overpotentials but where mass transport is not significant and the reverse reaction rate is negligible. Applicable at high 𝛈 when electron transfer rates are slow, kinetic parameters are extracted by linear regression. The conventional method is, however, subject to inaccuracies because the linear region is often determined subjectively, without attention to the constraints on overpotential range, no mass transport limitations, and low jo.
An algorithm is developed to automate Tafel analysis with the objective to increase measurement accuracy and decrease subjective identification of the linear region. From linear sweep voltammograms (LSVs), jo and α are determined from Tafel slopes in the best fit, linear range.
Comparisons of kinetic parameters between conventional and algorithmic Tafel analyses are made for the hydrogen evolution reaction (HER, 2H+ + 2e- ⇌ H2) on various unmodified electrodes and electrodes modified with Nafion® composites. The algorithmic Tafel analysis parameters correlate well with conventional Tafel analyses that respect constraints on mass transport, 𝛈, and jo. Similar agreement is observed between literature and algorithmically fitted kinetic parameters for different electrochemical systems. The algorithm allows for straightforward, rapid Tafel analysis for improved measurement of rate parameters that is independent of user bias in selection of the linear region.
Acknowledgments
This work was supported by the Army Research Office.