Mechanism of overscreening breakdown by molecular-scale electrode surface morphology in asymmetric ionic liquids

The interfacial nature of the electric double layer (EDL) assumes that electrode surface morphology significantly impacts the EDL properties. Since molecular-scale roughness modifies the structure of EDL, it is expected to disturb the overscreening effect and alter differential capacitance (DC). In...

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Veröffentlicht in:Journal of colloid and interface science Jg. 677; H. Pt B; S. 396 - 405
Hauptverfasser: Nesterova, Irina, Evstigneev, Nikolay M., Ryabkov, Oleg I., Gerke, Kirill M., Khlyupin, Aleksey
Format: Journal Article
Sprache:Englisch
Veröffentlicht: United States Elsevier Inc 01.01.2025
Schlagworte:
Asymmetric ionic liquids
asymmetry
capacitance
Electric double layer
Electrode surface morphology
Electrode-electrolyte interface
electrodes
Molecular-scale roughness
Overscreening regime
roughness
surface roughness
Electric double layer
Electrode-electrolyte interface
Molecular-scale roughness
Electrode surface morphology
Asymmetric ionic liquids
Overscreening regime
ISSN:0021-9797, 1095-7103, 1095-7103
Online-Zugang:Volltext
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Zusammenfassung:The interfacial nature of the electric double layer (EDL) assumes that electrode surface morphology significantly impacts the EDL properties. Since molecular-scale roughness modifies the structure of EDL, it is expected to disturb the overscreening effect and alter differential capacitance (DC). In this paper, we present a model that describes EDL near atomically rough electrodes with account for short-range electrostatic correlations. We provide numerical and analytical solutions for the analysis of conditions for the overscreening breakdown and DC shift estimation. Our findings reveal that electrode surface structure leads to DC decrease and can both break or enhance overscreening depending on the relation of surface roughness to electrostatic correlation length and ion size asymmetry.
Bibliographie:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0021-9797
1095-7103
1095-7103
DOI:10.1016/j.jcis.2024.08.040