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Derivative-extremum analysis of current-potential curves showing electrochemical kinetics in the full reversibility range
Yin, Fengjun1,2,3; Liu, Hong1,2
2023
摘要Derivative-extremum analysis (DEA) of j-E curves is a newly proposed method of half wave potential (E-1/2) and activation feature extraction from steady-state voltammetry. Here, the DEA is demonstrated to be valid in the full range of reversibility using numerical simulations with a derived universal electrode equation, providing a novel perspective of electrochemical kinetics in the reversibility domain. The results reveal that E-1/2 is a better choice of the reference potential instead of equilibrium potential (E-eq) in electrode equations, especially since E-eq is meaningless in an irreversible case. The equations referenced with standard potential, E-1/2 and E-eq, are summarized in three tables, and their applications in parameter determinations are specified. Finally, reversibility is proved to be a relative measure between kinetic slowness and mass transport of electroactive species, and the reversibility classifications are proposed according to the DEA feature in the reversibility domain. This work, based on the DEA principle, refines the electrode equation forms and generalizes their applicability in the full range of reversibility. (c) 2022 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
关键词Reversibility Electrochemical kinetics Half-wave potential Derivative-extremum analysis Parameter determinations
DOI10.1016/j.cclet.2022.01.078
发表期刊CHINESE CHEMICAL LETTERS
ISSN1001-8417
卷号34期号:1页码:6
通讯作者Liu, Hong(liuhong@cigit.ac.cn)
收录类别SCI
WOS记录号WOS:000900237000015
语种英语