Universal Algorithm for Simulating and Evaluating Cyclic Voltammetry at Macroporous Electrodes by Considering Random...

Area of Science:

• Electrochemistry
• Computational Chemistry
• Materials Science

Background:

• Cyclic voltammetry (CV) is a crucial technique for studying electrochemical reactions.
• Simulating CV at macroporous electrodes (felts, foams) presents challenges due to complex diffusion domains.
• Existing models often lack the flexibility to handle diverse electrode geometries and reaction kinetics.

Purpose of the Study:

• To develop a universal algorithm for simulating and evaluating cyclic voltammetry (CV) at macroporous electrodes.
• To approximate internal diffusion domains in various 1D, 2D, and 3D electrode structures.
• To provide an open-source computational tool for CV data analysis.

Main Methods:

• Developed a simulation algorithm based on Laplace integral transformation techniques.
• Employed a modified Talbot contour for inverse Laplace transformation.
• Incorporated 1D, 2D, and 3D electrode arrays, microelectrodes, and hollow structures.
• Included first-order homogeneous chemical kinetics and non-equal diffusion coefficients.

Main Results:

• Successfully simulated time-dependent surface concentrations for various electrode geometries.
• Validated the algorithm using experimental CV data for [Fe(CN)6]4- oxidation at platinum and VO2+ oxidation at carbon felt.
• Demonstrated the algorithm's capability to handle complex electrochemical reactions with preceding/following chemical kinetics.

Conclusions:

• The presented algorithm provides a powerful and versatile tool for simulating and evaluating CV data from macroporous electrodes.
• The open-source Python GUI facilitates accessibility and application in research and development.
• This work advances the understanding and computational modeling of electrochemical processes in complex electrode architectures.