NEW METHOD FOR DETERMINATION OF THE ELECTROACTIVE AREA OF CYLINDRICAL ELECTRODES: THE GEOMETRICAL CHALLENGE

MARIO CESAR CASSETTARI FILHO; Luiza de Oliveira Salim José; Carleane Patrícia da Silva Reis; Maria Luisa Sartorelli

Todos os Trabalhos

Trabalho

Título do Trabalho

NEW METHOD FOR DETERMINATION OF THE ELECTROACTIVE AREA OF CYLINDRICAL ELECTRODES: THE GEOMETRICAL CHALLENGE

Autores

MARIO CESAR CASSETTARI FILHO
Luiza de Oliveira Salim José
Carleane Patrícia da Silva Reis
Maria Luisa Sartorelli

Modalidade

Pôster

Área temática

3) Design, Synthesis, and Characterization of Electronic/Optoelectronic Materials and Devices

Data de Publicação

17/05/2024

País da Publicação

Brasil

Idioma da Publicação

Inglês

Página do Trabalho

https://www.even3.com.br/anais/workshop-do-ineo-2024/803160-new-method-for-determination-of-the-electroactive-area-of-cylindrical-electrodes--the-geometrical-challenge

ISBN

978-65-272-0462-6

Palavras-Chave

electrochemical impedance spectroscopy; electroactive area of cylindrical electrodes; specific capacitance; rugosity of porous electrodes

Resumo

The determination of the electroactive area of porous or nanostructured electrodes is still not settled. The traditional method relies on voltammetric scans at distinct rates with the use of a redox probe [1,2]. However, depending on the electrode’s material and its degree of porosity, diffusive, adsorptive and absorptive limitations may hamper the correct area evaluation. Alternatively, the electroactive area may also be determined by the interfacial capacitance, which is directly proportional to the electroactive area. The latter method depends on the knowledge of the specific capacitance, i.e., the capacitance per unit area, which unfortunately it is also not known precisely, even for metallic substrates, because it is field dependent and suffers from frequency dispersion [3]. In this work we present a new method, developed by the LabSiN/UFSC, which is based on a generalized phase element (gpe) analysis of electrochemical impedance spectroscopy [4]. The method is based on successive electrolyte withdrawals and requires electrodes with an elongated area [5]. In this work the method will be applied to metallic rods. Despite its simplicity, the precision of the measurement strongly depends on accurate values of the cell geometry and the electrolyte physical parameters. The optimization of both geometrical and physical parameters is the aim of this study, which was taken by two of the undergraduate students of LabSiN/UFSC. In the present work, only the challenges related to the optimization of the geometrical parameters will be presented. A gold cylindrical electrode immersed in KOH solution at zero electrical field has been used as a validation system, due to its well stablished interface. A glass cell was prepared to enable a clear visualization of its interior, in order to estimate precisely the length of the immersed portion of the electrode. Specific Luggin capillaries have been developed for this set-up, and a precision ruler was used for the adjustment of the distance of the Luggin capillary tip to the working electrode. All the mentioned parameters must be considered in the final calculation of the electroactive area. The values of rugosity obtained with the new method for the gold electrode are between 1.1 and 1.3, in good agreement to the expected for polycrystalline gold. Work supported by CNPq, CAPES, FAPESC and INEO. References: [1] N. Elgrishi et al., A Practical Beginner’s Guide to Cyclic Voltammetry, J. Chem. Educ. 95, 197 (2018). [2] D. Coelho et al., Estimating the Electrochemically Active Area: Revisiting a Basic Concept in Electrochemistry, J. Braz. Chem. Soc. (2021). [3] O. Gharbi et al., From Frequency Dispersion to Ohmic Impedance: A New Insight on the High-Frequency Impedance Analysis of Electrochemical Systems, Electrochim. Acta 320, 134609 (2019). [4] M. L. Sartorelli et al., Model-Free Capacitance Analysis of Electrodes with a 2D+1D Dispersion of Time Constants, Electrochim. Acta 390, 138796 (2021). [5] C. P. da Silva Reis, Evolução Temporal Da Dupla Camada Elétrica Na Interface Ouro/Eletrólito, Universidade Federal de Santa Catarina, 2023.

Título do Evento: Workshop do INEO 2024
Cidade do Evento: Nazaré Paulista
Título dos Anais do Evento: Anais do Workshop INEO 2024
Nome da Editora: Even3
Meio de Divulgação: Meio Digital

Como citar

FILHO, MARIO CESAR CASSETTARI et al.. NEW METHOD FOR DETERMINATION OF THE ELECTROACTIVE AREA OF CYLINDRICAL ELECTRODES: THE GEOMETRICAL CHALLENGE.. In: Anais do Workshop INEO 2024. Anais...Nazaré Paulista(SP) Hotel Estância Atibainha, 2024. Disponível em: https//www.even3.com.br/anais/workshop-do-ineo-2024/803160-NEW-METHOD-FOR-DETERMINATION-OF-THE-ELECTROACTIVE-AREA-OF-CYLINDRICAL-ELECTRODES--THE-GEOMETRICAL-CHALLENGE. Acesso em: 14/06/2025