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Apparent disagreement between cyclic voltammetry and electrochemical impedance spectroscopy explained by time-domain simulation of constant phase elements

Bill Gannon Orcid Logo, Charlie Dunnill Orcid Logo

International Journal of Hydrogen Energy, Volume: 45, Issue: 43, Pages: 22383 - 22393

Swansea University Authors: Bill Gannon Orcid Logo, Charlie Dunnill Orcid Logo

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DOI (Published version): 10.1016/j.ijhydene.2020.06.029

Abstract

A selection of electrodes was analysed using cyclic-voltammetry (CV) and electrochemical impedance spectroscopy (EIS), and a large apparent resistance was observed with CV that was absent with EIS. The explanation for this resistance anomaly was traced to the constant phase element (CPE) behaviour w...

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Published in: International Journal of Hydrogen Energy
ISSN: 0360-3199
Published: Elsevier BV 2020
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URI: https://cronfa.swan.ac.uk/Record/cronfa54975
first_indexed 2020-08-13T08:56:04Z
last_indexed 2020-09-19T03:17:58Z
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spelling 2020-09-18T15:33:46.9437881 v2 54975 2020-08-13 Apparent disagreement between cyclic voltammetry and electrochemical impedance spectroscopy explained by time-domain simulation of constant phase elements 98bbf039bdc4835b1cbee374c8acd399 0000-0003-1495-5839 Bill Gannon Bill Gannon true false 0c4af8958eda0d2e914a5edc3210cd9e 0000-0003-4052-6931 Charlie Dunnill Charlie Dunnill true false 2020-08-13 EAAS A selection of electrodes was analysed using cyclic-voltammetry (CV) and electrochemical impedance spectroscopy (EIS), and a large apparent resistance was observed with CV that was absent with EIS. The explanation for this resistance anomaly was traced to the constant phase element (CPE) behaviour which is exhibited by the electrode double-layer capacitance. Computer simulations of the transient-response of an RQ network (where Q represents a CPE) to a voltage ramp revealed bi-exponential behaviour, with two separate time-constants. One is equal to the product of R and Q, but the other is fixed at about 0.3 s. This finding is supported by observation, by mathematical derivation, and by a novel mixed-domain five-component equivalent circuit model. In addition, example code is provided as a basis for transient simulations of constant phase elements with arbitrary voltage waveforms. This explanation assists in the correct interpretation of potentially misleading cyclic voltammetry results. Journal Article International Journal of Hydrogen Energy 45 43 22383 22393 Elsevier BV 0360-3199 Cyclic voltammetry, Electrical impedance spectroscopy, Constant phase element, Equivalent circuit model 3 9 2020 2020-09-03 10.1016/j.ijhydene.2020.06.029 COLLEGE NANME Engineering and Applied Sciences School COLLEGE CODE EAAS Swansea University 2020-09-18T15:33:46.9437881 2020-08-13T09:54:04.3655964 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemical Engineering Bill Gannon 0000-0003-1495-5839 1 Charlie Dunnill 0000-0003-4052-6931 2 54975__17913__fa1990dcc7d44a0588c9743c2b93eb11.pdf 54975.pdf 2020-08-13T14:12:50.7905004 Output 795877 application/pdf Accepted Manuscript true 2021-07-30T00:00:00.0000000 © 2020. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ true English
title Apparent disagreement between cyclic voltammetry and electrochemical impedance spectroscopy explained by time-domain simulation of constant phase elements
spellingShingle Apparent disagreement between cyclic voltammetry and electrochemical impedance spectroscopy explained by time-domain simulation of constant phase elements
Bill Gannon
Charlie Dunnill
title_short Apparent disagreement between cyclic voltammetry and electrochemical impedance spectroscopy explained by time-domain simulation of constant phase elements
title_full Apparent disagreement between cyclic voltammetry and electrochemical impedance spectroscopy explained by time-domain simulation of constant phase elements
title_fullStr Apparent disagreement between cyclic voltammetry and electrochemical impedance spectroscopy explained by time-domain simulation of constant phase elements
title_full_unstemmed Apparent disagreement between cyclic voltammetry and electrochemical impedance spectroscopy explained by time-domain simulation of constant phase elements
title_sort Apparent disagreement between cyclic voltammetry and electrochemical impedance spectroscopy explained by time-domain simulation of constant phase elements
author_id_str_mv 98bbf039bdc4835b1cbee374c8acd399
0c4af8958eda0d2e914a5edc3210cd9e
author_id_fullname_str_mv 98bbf039bdc4835b1cbee374c8acd399_***_Bill Gannon
0c4af8958eda0d2e914a5edc3210cd9e_***_Charlie Dunnill
author Bill Gannon
Charlie Dunnill
author2 Bill Gannon
Charlie Dunnill
format Journal article
container_title International Journal of Hydrogen Energy
container_volume 45
container_issue 43
container_start_page 22383
publishDate 2020
institution Swansea University
issn 0360-3199
doi_str_mv 10.1016/j.ijhydene.2020.06.029
publisher Elsevier BV
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemical Engineering{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemical Engineering
document_store_str 1
active_str 0
description A selection of electrodes was analysed using cyclic-voltammetry (CV) and electrochemical impedance spectroscopy (EIS), and a large apparent resistance was observed with CV that was absent with EIS. The explanation for this resistance anomaly was traced to the constant phase element (CPE) behaviour which is exhibited by the electrode double-layer capacitance. Computer simulations of the transient-response of an RQ network (where Q represents a CPE) to a voltage ramp revealed bi-exponential behaviour, with two separate time-constants. One is equal to the product of R and Q, but the other is fixed at about 0.3 s. This finding is supported by observation, by mathematical derivation, and by a novel mixed-domain five-component equivalent circuit model. In addition, example code is provided as a basis for transient simulations of constant phase elements with arbitrary voltage waveforms. This explanation assists in the correct interpretation of potentially misleading cyclic voltammetry results.
published_date 2020-09-03T05:09:15Z
_version_ 1822105645203062784
score 11.048302

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