Correlated Ion Transport and the Gel Phase in Room Temperature Ionic Liquids
Name
2010.02091.pdf
Description
Submitted version
Size
1.98 MB
Format
Adobe PDF
Checksum (MD5)
94548c41339c76275f3f2967384790cc
Author(s)
McEldrew, Michael
Goodwin, Zachary AH
Zhao, Hongbo
Bazant, Martin Z
Kornyshev, Alexei A
Date Issued
2021
Journal
Journal of Physical Chemistry B
Publisher
American Chemical Society (ACS)
Version
Original manuscript
Abstract
Here we present a theory of ion aggregation and gelation of room temperature ionic liquids (RTILs). Based on it, we investigate the effect of ion aggregation on correlated ion transport-ionic conductivity and transference numbers-obtaining closed-form expressions for these quantities. The theory depends on the maximum number of associations a cation and anion can form and the strength of their association. To validate the presented theory, we perform molecular dynamics simulations on several RTILs and a range of temperatures for one RTIL. The simulations indicate the formation of large clusters, even percolating through the system under certain circumstances, thus forming a gel, with the theory accurately describing the obtained cluster distributions in all cases. However, based on the strength and lifetime of associations in the simulated RTILs, we expect free ions to dominate ionic conductivity despite the presence of clusters, and we do not expect the percolating cluster to trigger structural arrest in the RTIL.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Terms of Use
Creative Commons Attribution-Noncommercial-Share Alike
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/acs.jpcb.0c09050
