NUMERICAL MODELING OF CYCLIC VOLTAMMOGRAMS FOR ELECTROCHEMICAL GROWTH AND DISSOLUTION OF AN ARRAY OF NEW-PHASE NUCLEI

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Abstract

The development of methods for studying the initial stages of electrocrystallization is important both for the development of fundamental ideas about the mechanisms and kinetics of phase formation and for determining the optimal electrodeposition conditions. However, most theoretical models designed to study the patterns of nucleation/ growth processes under variable supersaturation (overpotential) do not take into account the mutual influence of nuclei during multiple nucleation. To recreate conditions close to practice, models are required that more realistically reproduce the competition of nuclei for depositing ions. This paper presents a mathematical model and numerical simulation results for diffusion-controlled growth and dissolution of a hemispherical nucleus inside a large hexagonal ensemble under cyclic potential sweep conditions. Concentration profiles at different time points, cyclic voltammograms (CV) and overpotential dependences of the nucleus size are calculated. Non-stationary effects and changes in the current response when varying process parameters are theoretically substantiated. It is shown that a decrease in the scan rate, an increase in the reverse potential and the number density of nuclei on the electrode leads to a gradual transformation of the cathode part of CVs from the nucleation loop to the cathode peak. The indicated changes are caused by the increase in the mutual influence of neighboring nuclei and the approach to the conditions of semi-infinite linear diffusion to the entire electrode surface. At a constant reverse potential value, the maximum size of nuclei is greater, the lower their number density and the scan rate. The calculation results are in qualitative agreement with those typically recorded in experimental studies of the initial stages of metal electrocrystallization.

About the authors

O. V. Grishenkova

Institute of High Temperature Electrochemistry of the Ural Branch of the Russian Academy of Sciences

Email: olagris@mail.ru
Ekaterinburg, Russia

A. V. Kosov

Institute of High Temperature Electrochemistry of the Ural Branch of the Russian Academy of Sciences

Ekaterinburg, Russia

O. L. Semerikova

Institute of High Temperature Electrochemistry of the Ural Branch of the Russian Academy of Sciences

Ekaterinburg, Russia

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