Cracking Ion Pairs in the electrical double layer of ionic liquids
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Published version
Author(s)
Goodwin, Zachary AH
Kornyshev, Alexei A
Type
Journal Article
Abstract
Here we investigate a limiting case of the theory for aggregation and gelation in the electrical double layer (EDL) of ionic liquids (ILs). The limiting case investigated only accounts for ion pairs, ignoring the possibility of larger clusters and a percolating ionic network. This simplification, permits analytical solutions for the properties of the EDL. The resulting equations demonstrate the competition between the free energy of an association and the electrostatic potential in the EDL. For small electrostatic potentials and large negative free energies of associations, ion pairs dominate in the EDL. Whereas, for electrostatic potential energies larger than the free energy of an association, electric-field-induced cracking of ion pairs occurs. The differential capacitance for this consistent ion pairing theory has a propensity to have a “double hump camel” shape. We compare this theory against previous free ion approaches, which do not consistently treat the reversible associations in the EDL.
Date Issued
2022-12-01
Date Acceptance
2022-09-07
Citation
Electrochimica Acta, 2022, 434, pp.1-9
ISSN
0013-4686
Publisher
Elsevier
Start Page
1
End Page
9
Journal / Book Title
Electrochimica Acta
Volume
434
Copyright Statement
Crown Copyright © 2022 Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
License URL
Identifier
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000877715500006&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=a2bf6146997ec60c407a63945d4e92bb
Subjects
Science & Technology
Physical Sciences
Electrochemistry
MOLECULAR-SIZE DISTRIBUTION
THERMOREVERSIBLE GELATION
DIFFERENTIAL CAPACITANCE
3-DIMENSIONAL POLYMERS
GEL FORMATION
SOLVENT-FREE
HETEROGENEITY
TRANSPORT
DYNAMICS
ORGANIZATION
Publication Status
Published
Article Number
ARTN 141163
Date Publish Online
2022-09-16