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首页> 外文期刊>Journal of Electroanalytical Chemistry: An International Journal Devoted to All Aspects of Electrode Kinetics, Interfacial Structure, Properties of Electrolytes, Colloid and Biological Electrochemistry >From the anomalous diffusion impedance to the closed-form, infinite-series and integral formulations of the voltammetric response of thin-film insertion materials under restricted diffusion conditions. A modelling contribution based on the anomalous mass transfer function
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From the anomalous diffusion impedance to the closed-form, infinite-series and integral formulations of the voltammetric response of thin-film insertion materials under restricted diffusion conditions. A modelling contribution based on the anomalous mass transfer function

机译：从受限制扩散条件下的异常扩散阻抗到封闭式，无限串联和薄膜插入材料伏安响应的整体配方。 基于异常传质函数的建模贡献

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摘要

The voltammetric response of one-step reversible electrochemical reactions (involving dissolved redox species) to a linear potential ramp can be modelled using the calculation method proposed in our previous work (J. Electroanal. Chem. 818 (2018) 84) provided that the mass transfer function for the species involved in the electrochemical reaction is known in closed form under one-dimensional mass transport conditions. The above approach applies in this short communication to the direct insertion reaction in thin-film planar materials under both anomalous and spatially restricted (confined) diffusion conditions. The Faradaic current is obtained first as an alternating infinite series well suited to formal analysis, and then as an integral formulation well suited to numerical computation. Finally, closed-form expressions of the voltammograms are derived at very low or very high values of the potential sweep rate, respectively. Two anomalous diffusion models taken from the electrochemical literature are investigated and compared, based on their voltammetric responses. The voltammetric peak coordinates obtained from the best model are thoroughly examined, and closed-form approximations are proposed for the voltammetric peak current and potential at very low or very high potential sweep rates. A zone diagram is plotted to illustrate the conditions for observation of those limiting situations. Finally, following a referee's request, an alternative modelling approach is proposed in Appendix, which does not require the use of scientific computation software. This approach involves both the Integral Equation method formalism and numerical inversion of Laplace transform.
机译：一步可逆电化学反应（涉及溶解的氧化还原物种）对线性电位斜坡的伏安响应可以使用我们之前工作（J.Electronal.Chem.818（2018）84）中提出的计算方法建模，前提是电化学反应中所涉及物种的传质函数在一维质量条件下以闭合形式已知运输条件。上述方法适用于在反常和空间受限（受限）扩散条件下薄膜平面材料中的直接插入反应。法拉第电流首先是一个交流无穷级数，非常适合于形式分析，然后是一个积分公式，非常适合于数值计算。最后，分别在极低或极高的电位扫描率下，导出了伏安图的封闭形式表达式。根据电化学文献中的两种反常扩散模型的伏安响应，对它们进行了研究和比较。对从最佳模型得到的伏安峰坐标进行了全面的研究，并对极低或极高电位扫描速率下的伏安峰电流和电位提出了闭合形式近似。绘制了区域图，以说明观察这些极限情况的条件。最后，根据裁判的要求，附录中提出了一种替代建模方法，该方法不需要使用科学计算软件。这种方法包括积分方程法和拉普拉斯变换的数值反演。

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