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Title: Effect of Solvent Motion on Ion Transport in Electrolytes

Abstract

We use concentrated solution theory to derive an equation governing solvent velocity in a binary electrolyte when a current passes through it. This equation, in combination with the material balance equation, enables the prediction of electrolyte concentration profiles and species velocities as a function of space and time. This framework is used to predict ion velocities in Li-Li symmetric cells containing a mixture of lithium bis(trifluoromethanesulfonyl)imide and poly(ethylene oxide) (LiTFSI/PEO), for which the cation transference number relative to the solvent velocity, t + 0 , can be either positive or negative, depending on salt concentration. Accounting for the solvent motion is increasingly important at higher concentrations. Especially for negative t + 0 , if solvent velocity is set to zero, the cation velocity, based on the electrode-electrolyte interface reference frame, is pointed opposite to the current flow. However, when solvent motion is taken into account, the cation velocity, based on the same reference frame, is in the same direction as the current. This analysismore » demonstrates the importance of accounting for solvent velocity rigorously in seemingly simple systems such as symmetric cells.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [3]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. University of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. University of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1879821
Alternate Identifier(s):
OSTI ID: 1961348
Grant/Contract Number:  
AC02-06CH11357; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 169; Journal Issue: 4; Journal ID: ISSN 0013-4651
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Mistry, Aashutosh, Grundy, Lorena S., Halat, David M., Newman, John, Balsara, Nitash P., and Srinivasan, Venkat. Effect of Solvent Motion on Ion Transport in Electrolytes. United States: N. p., 2022. Web. doi:10.1149/1945-7111/ac6329.
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Mistry, Aashutosh, Grundy, Lorena S., Halat, David M., Newman, John, Balsara, Nitash P., & Srinivasan, Venkat. Effect of Solvent Motion on Ion Transport in Electrolytes. United States. https://doi.org/10.1149/1945-7111/ac6329
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Mistry, Aashutosh, Grundy, Lorena S., Halat, David M., Newman, John, Balsara, Nitash P., and Srinivasan, Venkat. Thu . "Effect of Solvent Motion on Ion Transport in Electrolytes". United States. https://doi.org/10.1149/1945-7111/ac6329. https://www.osti.gov/servlets/purl/1879821.
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@article{osti_1879821,
title = {Effect of Solvent Motion on Ion Transport in Electrolytes},
author = {Mistry, Aashutosh and Grundy, Lorena S. and Halat, David M. and Newman, John and Balsara, Nitash P. and Srinivasan, Venkat},
abstractNote = {We use concentrated solution theory to derive an equation governing solvent velocity in a binary electrolyte when a current passes through it. This equation, in combination with the material balance equation, enables the prediction of electrolyte concentration profiles and species velocities as a function of space and time. This framework is used to predict ion velocities in Li-Li symmetric cells containing a mixture of lithium bis(trifluoromethanesulfonyl)imide and poly(ethylene oxide) (LiTFSI/PEO), for which the cation transference number relative to the solvent velocity, t + 0 , can be either positive or negative, depending on salt concentration. Accounting for the solvent motion is increasingly important at higher concentrations. Especially for negative t + 0 , if solvent velocity is set to zero, the cation velocity, based on the electrode-electrolyte interface reference frame, is pointed opposite to the current flow. However, when solvent motion is taken into account, the cation velocity, based on the same reference frame, is in the same direction as the current. This analysis demonstrates the importance of accounting for solvent velocity rigorously in seemingly simple systems such as symmetric cells.},
doi = {10.1149/1945-7111/ac6329},
journal = {Journal of the Electrochemical Society},
number = 4,
volume = 169,
place = {United States},
year = {Thu Apr 14 00:00:00 EDT 2022},
month = {Thu Apr 14 00:00:00 EDT 2022}
}
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https://doi.org/10.1149/1945-7111/ac6329
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