Simulation of cyclic voltammograms for 3D diffusion-controlled growth and dissolution of new phase nuclei

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL Journal of Electroanalytical Chemistry Pub Date : 2025-02-16 DOI:10.1016/j.jelechem.2025.119020

Olga V. Grishenkova , Alexander V. Kosov

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Abstract

The regularities of diffusion-controlled growth and dissolution of a large random ensemble of hemispherical nuclei on an indifferent macroelectrode surface are analyzed using the proposed model under potential sweep conditions. The model considers the relationship between the concentration profiles to the nucleus due to spherical diffusion and to the electrode due to planar diffusion, and the distribution function of Voronoi cell areas. The simulated cyclic voltammograms (CVs) reproduce all the characteristic features of experimental CVs for 3D nucleation/growth processes. The influence of the number density of nuclei and scan parameters on the calculated CVs is studied. It is shown that an increase in the scan rate and a decrease in the number density of nuclei can lead to a significant transformation of the CV cathodic part up to the formation of a current loop. Furthermore, a shift of the peak potential in the cathodic direction can be observed as the scan rate increases in the case of 3D diffusion-controlled growth. The discrepancy with the Berzins-Delahay model is discussed and an approach is proposed for determining the diffusion coefficient of depositing ions in the case of a nonlinear dependence of the peak current density on the square root of the scan rate. The influence of the Voronoi cell area and scan parameters on the nucleus size evolution and size distribution is analyzed.

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来源期刊

Journal of Electroanalytical Chemistry 化学-电化学

CiteScore

7.80

自引率

6.70%

发文量

912

审稿时长

2.4 months

期刊介绍： The Journal of Electroanalytical Chemistry is the foremost international journal devoted to the interdisciplinary subject of electrochemistry in all its aspects, theoretical as well as applied. Electrochemistry is a wide ranging area that is in a state of continuous evolution. Rather than compiling a long list of topics covered by the Journal, the editors would like to draw particular attention to the key issues of novelty, topicality and quality. Papers should present new and interesting electrochemical science in a way that is accessible to the reader. The presentation and discussion should be at a level that is consistent with the international status of the Journal. Reports describing the application of well-established techniques to problems that are essentially technical will not be accepted. Similarly, papers that report observations but fail to provide adequate interpretation will be rejected by the Editors. Papers dealing with technical electrochemistry should be submitted to other specialist journals unless the authors can show that their work provides substantially new insights into electrochemical processes.