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Title: Impact of Frictional Interactions on Conductivity, Diffusion, and Transference Number in Ether- and Perfluoroether-Based Electrolytes

Abstract

There is growing interest in fluorinated electrolytes due to their high-voltage stability. We use full electrochemical characterization based on concentrated solution theory to investigate the underpinnings of conductivity and transference number in tetraglyme/LiTFSI mixtures (H4) and a fluorinated analog, C8-DMC, mixed with LiFSI (F4). Conductivity is significantly lower in F4 than in H4, and F4 exhibits negative cation transference numbers, while that of H4 is positive at most salt concentrations. By relating Stefan-Maxwell diffusion coefficients, which quantify ion-solvent and cation-anion frictional interactions, to conductivity and transference number, we determine that at high salt concentrations, the origin of differences in transference number is differences in anion-solvent interactions. We also define new Nernst-Einstein-like equations relating conductivity to Stefan-Maxwell diffusion coefficients. In H4 at moderate to high salt concentrations, we find that all molecular interactions must be included. However, we demonstrate another regime, in which conductivity is controlled by cation-anion interactions. The applicability of this assumption is quantified by a pre-factor, β+-} which is similar to the "ionicity"pre-factor that is often included in the Nernst-Einstein equation. In F4, β+-} is unity at all salt concentrations, indicating that ionic conductivity is entirely controlled by the Stefan-Maxwell diffusion coefficient quantifying cation-anion frictional interactions.

Authors:
ORCiD logo; ORCiD logo; ; ORCiD logo; ; ; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH)
OSTI Identifier:
1659359
Alternate Identifier(s):
OSTI ID: 1760209
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357; S10OD024998; SC0012673
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society (Online)
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society (Online) Journal Volume: 167 Journal Issue: 12; Journal ID: ISSN 1945-7111
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Grundy, Lorena S., Shah, Deep B., Nguyen, Hien Q., Diederichsen, Kyle M., Celik, Hasan, DeSimone, Joseph M., McCloskey, Bryan D., and Balsara, Nitash P. Impact of Frictional Interactions on Conductivity, Diffusion, and Transference Number in Ether- and Perfluoroether-Based Electrolytes. United States: N. p., 2020. Web. https://doi.org/10.1149/1945-7111/abb34e.
Grundy, Lorena S., Shah, Deep B., Nguyen, Hien Q., Diederichsen, Kyle M., Celik, Hasan, DeSimone, Joseph M., McCloskey, Bryan D., & Balsara, Nitash P. Impact of Frictional Interactions on Conductivity, Diffusion, and Transference Number in Ether- and Perfluoroether-Based Electrolytes. United States. https://doi.org/10.1149/1945-7111/abb34e
Grundy, Lorena S., Shah, Deep B., Nguyen, Hien Q., Diederichsen, Kyle M., Celik, Hasan, DeSimone, Joseph M., McCloskey, Bryan D., and Balsara, Nitash P. Wed . "Impact of Frictional Interactions on Conductivity, Diffusion, and Transference Number in Ether- and Perfluoroether-Based Electrolytes". United States. https://doi.org/10.1149/1945-7111/abb34e.
@article{osti_1659359,
title = {Impact of Frictional Interactions on Conductivity, Diffusion, and Transference Number in Ether- and Perfluoroether-Based Electrolytes},
author = {Grundy, Lorena S. and Shah, Deep B. and Nguyen, Hien Q. and Diederichsen, Kyle M. and Celik, Hasan and DeSimone, Joseph M. and McCloskey, Bryan D. and Balsara, Nitash P.},
abstractNote = {There is growing interest in fluorinated electrolytes due to their high-voltage stability. We use full electrochemical characterization based on concentrated solution theory to investigate the underpinnings of conductivity and transference number in tetraglyme/LiTFSI mixtures (H4) and a fluorinated analog, C8-DMC, mixed with LiFSI (F4). Conductivity is significantly lower in F4 than in H4, and F4 exhibits negative cation transference numbers, while that of H4 is positive at most salt concentrations. By relating Stefan-Maxwell diffusion coefficients, which quantify ion-solvent and cation-anion frictional interactions, to conductivity and transference number, we determine that at high salt concentrations, the origin of differences in transference number is differences in anion-solvent interactions. We also define new Nernst-Einstein-like equations relating conductivity to Stefan-Maxwell diffusion coefficients. In H4 at moderate to high salt concentrations, we find that all molecular interactions must be included. However, we demonstrate another regime, in which conductivity is controlled by cation-anion interactions. The applicability of this assumption is quantified by a pre-factor, β+-} which is similar to the "ionicity"pre-factor that is often included in the Nernst-Einstein equation. In F4, β+-} is unity at all salt concentrations, indicating that ionic conductivity is entirely controlled by the Stefan-Maxwell diffusion coefficient quantifying cation-anion frictional interactions.},
doi = {10.1149/1945-7111/abb34e},
journal = {Journal of the Electrochemical Society (Online)},
number = 12,
volume = 167,
place = {United States},
year = {2020},
month = {9}
}

Journal Article:
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https://doi.org/10.1149/1945-7111/abb34e

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