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Nonequilibrium Electrical Double Layer Effects on Unilateral Peak Suppression in Cyclic Voltammetry
Yupeng Qin1,2, Zhangquan Peng1, Jun Huang3,4
1Laboratory of Advanced Spectro-electrochemistry and Li-Ion Batteries, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
ACS Electrochemistry
|May 13, 2026
Summary
Nonequilibrium electrical double layer (EDL) effects in cyclic voltammetry (CV) are explored. The study reveals suppressed cathodic peaks due to transient EDL phenomena, particularly at higher scanning rates.
Area of Science:
- Electrochemistry
- Physical Chemistry
- Computational Chemistry
Background:
- Equilibrium electrical double layer (EDL) effects on steady-state voltammetry are understood.
- Nonequilibrium transient EDL effects on cyclic voltammetry (CV) are less understood.
Purpose of the Study:
- To investigate nonequilibrium transient EDL effects on CV.
- To understand their unequal influence on cathodic and anodic peaks.
Main Methods:
- Combined theoretical and experimental study.
- Coupling Poisson-Nernst-Planck (PNP) theory with electrode kinetic theories.
- Analysis of interfacial electron transfer, EDL formation, and mass transport.
Main Results:
- Model predicts suppressed cathodic peaks in CV for the [Fe(CN)6]3-/4- redox reaction.
- Correlated peak suppression with electrical potential and reactant concentration distributions in the EDL.
- Identified parametric regions for pronounced nonequilibrium EDL effects.
- Calculated and validated a regime diagram for nonequilibrium EDL effects on CV.
Conclusions:
- Nonequilibrium EDL effects significantly influence CV peak symmetry.
- Peak suppression is more pronounced when reactive ions are repelled from like-charged electrode surfaces at higher scanning rates.
- The theoretical model serves as an efficient tool for exploring these effects.
Keywords:
Frumkin correctionPoisson−Nernst−Planck equationcyclic voltammetryelectrode-reactant repellingnonequilibrium electrical double layer effectsMore Related Videos
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