The Tafel equation, which serves as a linearized representation of the Butler–Volmer expression, permits the extraction of fundamental parameters of electrochemical systems, such as exchange current densities and Tafel slopes. However, the application of these linear fitting procedures become problematic in the cases of experimental data featuring nonlinearities in the Tafel (log(J) – V) response. This is especially troubling in low-overpotential regimes, where charge transfer kinetics generally dominate electrode behavior (as opposed to diffusion-limited currents at higher overpotentials) and linearization is expected to be most applicable. As a response to this complication and the ad-hoc forms of fitting that may arise from it, this report outlines a systematic method for the determination of Tafel slopes through a rigorous, quantitative framework. The algorithm’s performance is benchmarked using electrochemical measurements of well-characterized reactions for water splitting, hydrogen evolution, and dioxygen reduction at iridium and platinum electrodes. As a final validation test, we show that the exchange currents extracted through this automated fitting procedure, used in conjunction with the Butler–Volmer model, are capable of reproducing the original electrochemical data in kinetically controlled regimes.

中文翻译：

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塔菲尔坡度提取算法

Tafel方程可作为Butler-Volmer表达式的线性表示，可以提取电化学系统的基本参数，例如交换电流密度和Tafel斜率。但是，在具有Tafel（log（J）– V） 回复。这在低过电势状态下尤其令人不安，在这种情况下，电荷转移动力学通常会主导电极行为（与更高的过电势下的扩散限制电流相反），并且线性化有望最适用。为了应对这种复杂性以及由此产生的临时拟合形式，本报告概述了通过严格的定量框架确定塔菲尔斜率的系统方法。该算法的性能通过对表征良好的反应的电化学测量进行基准测试，这些反应用于在铱和铂电极上进行水分解，放出氢气和还原双氧。作为最终的验证测试，我们证明了通过这种自动拟合程序提取的交换电流，并与Butler-Volmer模型一起使用，