Theory of electrosorption of water from ionic liquids
File(s)Budkov et al resubmitted.pdf (16.42 MB)
Accepted version
Author(s)
Budkov, Yury A
Kolesnikov, Andrei L
Goodwin, Zachary AH
Kiselev, Mikhail G
Kornyshev, Alexei A
Type
Journal Article
Abstract
We propose and develop a classical density functional theory for the description of a minor amount of water dissolved in ionic liquid in the vicinity of an electrode. In addition to the electrostatic energy and lattice-gas mixing entropy terms, the utilised grand canonical potential contains several phenomenological terms/parameters that describe short-range interactions between ions, water molecules and the electrode. Here we investigate: (i) specific interaction of ions and molecules with the electrode, which are responsible for their specific adsorption; (ii) hydrophilicity/hydrophobicity of ions. We obtain water electrosorption isotherms as a function of the potential drop across the electrical double layer, investigate its asymmetry with respect to the sign of electrode potential, and establish the relationship between the sign of this asymmetry and hydrophobicity/hydrophilicity of cations and anions. We also calculate the effect of water electrosorption on the double layer differential capacitance which brings clear new features to its voltage dependence, some of which have been already experimentally observed.
Date Issued
2018-09-10
Date Acceptance
2018-07-19
Citation
Electrochimica Acta, 2018, 284, pp.346-354
ISSN
0013-4686
Publisher
Elsevier
Start Page
346
End Page
354
Journal / Book Title
Electrochimica Acta
Volume
284
Copyright Statement
© 2018 Elsevier Ltd. All rights reserved. This manuscript is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International Licence http://creativecommons.org/licenses/by-nc-nd/4.0/
Subjects
Science & Technology
Physical Sciences
Electrochemistry
Ionic liquid
Water
Electrical double layer
Electrosorption
Differential capacitance
DOUBLE-LAYER CAPACITANCE
ELECTRIC DOUBLE-LAYER
INTERFACES
MOLECULES
SOLVENTS
SURFACE
Publication Status
Published
Date Publish Online
2018-07-27