Exploring nucleation modeling of the voltammetry of solid-to-solid-state redox processes with phase changes

Abstract

An operational description of the linear potential scan voltammetry of solids experiencing a solid-state redox transformation with phase changes is described. The modeling is based on the application of nucleation equations of solid-state reaction kinetics to express the transferred charge/applied potential relationships. The flexible use of Prout-Tompkins and Avrami-Erofe’ev kinetics permits a satisfactory description of the voltammetry of solid-to-solid redox transformations with phase segregation. The model satisfactorily applies to reproduce linear potential scan curves recorded for graphite electrodes modified with several lead compounds in contact with aqueous electrolyte solutions.

Logistic Approximation to Ion-Intercalation Electrochemistry: Application to Potassium–Copper(II) Hexacyanoferrate in DMSO Electrolytes

“…In previous works, the formal equivalence between the description of the electrochemistry of reagents strongly attached to the electrode surface and the description of solid-to-solid redox transformations under the assumption that the transferred charge is a logistic function of the applied potential was studied. , This model leads to a satisfactory description of solid-state electrochemical processes involving phase changes, such as the reduction of PbO to Pb. This model is consistent with several models to describe electroinsertion processes in inorganic films. , These formulations do not replace conventional electrodynamic equations, but they can be seen as operational approaches providing analytical solutions of general equations.…”