Ion clusters and networks in water-in-salt electrolytes
File(s)JES_WiSE.pdf (2.04 MB)
Accepted version
OA Location
Author(s)
McEldrew, Michael
Goodwin, Zachary AH
Bi, Sheng
Kornyshev, Alexei A
Bazant, Martin Z
Type
Journal Article
Abstract
Water-in-salt electrolytes (WiSEs) are a class of super-concentrated electrolytes that have shown much promise in replacing organic electrolytes in lithium-ion batteries. At the extremely high salt concentrations of WiSEs, ionic association is more complicated than the simple ion pair description. In fact, large branched clusters can be present in WiSEs, and past a critical salt concentration, an infinite percolating ionic network can form spontaneously. In this work, we simplify our recently developed thermodynamic model of reversible ionic aggregation and gelation, tailoring it specifically for WiSEs. Our simplified theory only has a handful of parameters, all of which can be readily determined from simulations. Our model is able to quantitatively reproduce the populations of ionic clusters of different sizes as a function of salt concentration, the critical salt concentration for ionic gelation, and the fraction of ions incorporated into the ionic gel, as observed from molecular simulations of three different lithium-based WiSEs. The extent of ionic association and gelation greatly affects the effective ionic strength of solution, the coordination environment of active cations that is known to govern the chemistry of the solid-electrolyte interface, and the thermodynamic activity of all species in the electrolyte.
Date Issued
2021-05-01
Date Acceptance
2021-04-19
Citation
Journal of The Electrochemical Society, 2021, 168 (5), pp.1-12
ISSN
0013-4651
Publisher
Electrochemical Society
Start Page
1
End Page
12
Journal / Book Title
Journal of The Electrochemical Society
Volume
168
Issue
5
Copyright Statement
© 2021 The Electrochemical Society (“ECS”). Published on behalf of ECS by IOP Publishing Limited. This is an author-created, un-copyedited version of an article accepted for publication in the Journal of the Electrochemical Society. IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from it. The definitive publisher authenticated version is available online at https://doi.org/10.1149/1945-7111/abf975.
Sponsor
MIT-Imperial Seed Fund
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000649118400001&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
Technology
Electrochemistry
Materials Science, Coatings & Films
Materials Science
Theory and Modelling
Batteries Li-ion
ion clustering
ion network
water-in-salt electrolytes
ion transport
Thermodynamics
MOLECULAR-SIZE DISTRIBUTION
SOLVATION SHEATH STRUCTURE
THERMOREVERSIBLE GELATION
ELECTROCHEMICAL STABILITY
GRAPHITE/ELECTROLYTE INTERFACE
TRANSFERENCE NUMBER
BATTERY
LI+
AGGREGATION
ASSOCIATION
Publication Status
Published
Article Number
ARTN 050514
Date Publish Online
2021-05-07