Theory of ion aggregation and gelation in super-concentrated electrolytes
File(s)Gelation_Revision-AK.pdf (1.16 MB)
Accepted version
Author(s)
McEldrew, Michael
Goodwin, Zachary AH
Bi, Sheng
Bazant, Martin Z
Kornyshev, Alexei A
Type
Journal Article
Abstract
In concentrated electrolytes with asymmetric or irregular ions, such as ionic liquids and solvent-in-salt electrolytes, ion association is more complicated than simple ion-pairing. Large branched aggregates can form at significant concentrations at even moderate salt concentrations. When the extent of ion association reaches a certain threshold, a percolating ionic gel network can form spontaneously. Gelation is a phenomenon that is well known in polymer physics, but it is practically unstudied in concentrated electrolytes. However, despite this fact, the ion-pairing description is often applied to these systems for the sake of simplicity. In this work, drawing strongly from established theories in polymer physics, we develop a simple thermodynamic model of reversible ionic aggregation and gelation in concentrated electrolytes accounting for the competition between ion solvation and ion association. Our model describes, with the use of several phenomenological parameters, the populations of ionic clusters of different sizes as a function of salt concentration; it captures the onset of ionic gelation and also the post-gel partitioning of ions into the gel. We discuss the applicability of our model, as well as the implications of its predictions on thermodynamic, transport, and rheological properties.
Date Issued
2020-06-21
Date Acceptance
2020-05-01
Citation
Journal of Chemical Physics, 2020, 152 (23), pp.1-19
ISSN
0021-9606
Publisher
American Institute of Physics
Start Page
1
End Page
19
Journal / Book Title
Journal of Chemical Physics
Volume
152
Issue
23
Copyright Statement
© 2020 Author(s). This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in J. Chem. Phys. 152, 234506 (2020); https://doi.org/10.1063/5.0006197
Sponsor
MIT-Imperial Seed Fund
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000543489300001&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Grant Number
Collaboration between the groups of Prof. M. Bazant at MIT and Prof. A. Kornyshev at Imperial College
Subjects
Science & Technology
Physical Sciences
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Chemistry
Physics
MOLECULAR-SIZE DISTRIBUTION
IN-SALT ELECTROLYTE
THERMOREVERSIBLE GELATION
MAXWELL-STEFAN
ELECTROCHEMICAL CHARACTERIZATION
3-DIMENSIONAL POLYMERS
TRANSFERENCE NUMBER
GEL FORMATION
WATER
TRANSPORT
Publication Status
Published
Date Publish Online
2020-06-19