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Title: Lithium Solvation and Mobility in Ionic Liquid Electrolytes with Asymmetric Sulfonyl-Cyano Anion

Abstract

The solvation structure and transport properties of Li+ in ionic liquid (IL) electrolytes based on n-methyl-n-butylpyrrolidinium cyano(trifluoromethanesulfonyl)imide [PYR14][CTFSI] and [Li][CTFSI] (0 ≤ xLi ≤ 0.7) were studied by Raman and Nuclear Magnetic Resonance (NMR) diffusometry, and molecular dynamics (MD) simulations. At xLi < 0.3, Li+ coordination is dominated by the cyano group. As xLi is increased, free cyano-sites become limited, resulting in increased coordination via the sulfonyl group. Here, the 1:1 mixture of the symmetric anions bis(trifluoromethanesulfonyl)imide ([TFSI]) and dicyanamide ([DCA]) results in similar physical properties as the IL with [CTFSI]. However, anion asymmetry is shown to increase Li-salt solubility and promote Li+ transference. The lifetimes of Li+-cyano coordination for [CTFSI] are calculated to be shorter than those for [DCA], indicating that the competition from the sulfonyl group weakens its solvation with Li+. This resulted in higher Li+ transference for the electrolyte with [CTFSI]. In relation to the utility of these electrolytes in energy storage, the Li–LiFePO4 half cells assembled with IL electrolyte (xLi = 0.3, 0.5, and 0.7) demonstrated a nominal capacity of 140 mAh/g at 0.1C rate and 90 °C where the cell with xLi = 0.7 IL electrolyte demonstrated 61% capacity retention after 100 cycles and superiormore » rate capability owing to increased electrochemical stability.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1];  [3];  [1]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Case Western Reserve Univ., Cleveland, OH (United States)
  2. Univ. of Notre Dame, IN (United States)
  3. Hunter College, New York, NY (United States)
Publication Date:
Research Org.:
Case Western Reserve Univ., Cleveland, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1882218
Grant/Contract Number:  
SC0019409
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical and Engineering Data
Additional Journal Information:
Journal Volume: 67; Journal Issue: 8; Journal ID: ISSN 0021-9568
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Anions; Diffusion; Electrolytes; Solvation; Viscosity

Citation Formats

Penley, Drace, Wang, Xiaoyu, Lee, Yun-Yang, Garaga, Mounesha N., Ghahremani, Raziyeh, Greenbaum, Steve, Maginn, Edward J., and Gurkan, Burcu. Lithium Solvation and Mobility in Ionic Liquid Electrolytes with Asymmetric Sulfonyl-Cyano Anion. United States: N. p., 2022. Web. doi:10.1021/acs.jced.2c00294.
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Penley, Drace, Wang, Xiaoyu, Lee, Yun-Yang, Garaga, Mounesha N., Ghahremani, Raziyeh, Greenbaum, Steve, Maginn, Edward J., & Gurkan, Burcu. Lithium Solvation and Mobility in Ionic Liquid Electrolytes with Asymmetric Sulfonyl-Cyano Anion. United States. https://doi.org/10.1021/acs.jced.2c00294
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Penley, Drace, Wang, Xiaoyu, Lee, Yun-Yang, Garaga, Mounesha N., Ghahremani, Raziyeh, Greenbaum, Steve, Maginn, Edward J., and Gurkan, Burcu. Tue . "Lithium Solvation and Mobility in Ionic Liquid Electrolytes with Asymmetric Sulfonyl-Cyano Anion". United States. https://doi.org/10.1021/acs.jced.2c00294. https://www.osti.gov/servlets/purl/1882218.
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@article{osti_1882218,
title = {Lithium Solvation and Mobility in Ionic Liquid Electrolytes with Asymmetric Sulfonyl-Cyano Anion},
author = {Penley, Drace and Wang, Xiaoyu and Lee, Yun-Yang and Garaga, Mounesha N. and Ghahremani, Raziyeh and Greenbaum, Steve and Maginn, Edward J. and Gurkan, Burcu},
abstractNote = {The solvation structure and transport properties of Li+ in ionic liquid (IL) electrolytes based on n-methyl-n-butylpyrrolidinium cyano(trifluoromethanesulfonyl)imide [PYR14][CTFSI] and [Li][CTFSI] (0 ≤ xLi ≤ 0.7) were studied by Raman and Nuclear Magnetic Resonance (NMR) diffusometry, and molecular dynamics (MD) simulations. At xLi < 0.3, Li+ coordination is dominated by the cyano group. As xLi is increased, free cyano-sites become limited, resulting in increased coordination via the sulfonyl group. Here, the 1:1 mixture of the symmetric anions bis(trifluoromethanesulfonyl)imide ([TFSI]) and dicyanamide ([DCA]) results in similar physical properties as the IL with [CTFSI]. However, anion asymmetry is shown to increase Li-salt solubility and promote Li+ transference. The lifetimes of Li+-cyano coordination for [CTFSI] are calculated to be shorter than those for [DCA], indicating that the competition from the sulfonyl group weakens its solvation with Li+. This resulted in higher Li+ transference for the electrolyte with [CTFSI]. In relation to the utility of these electrolytes in energy storage, the Li–LiFePO4 half cells assembled with IL electrolyte (xLi = 0.3, 0.5, and 0.7) demonstrated a nominal capacity of 140 mAh/g at 0.1C rate and 90 °C where the cell with xLi = 0.7 IL electrolyte demonstrated 61% capacity retention after 100 cycles and superior rate capability owing to increased electrochemical stability.},
doi = {10.1021/acs.jced.2c00294},
journal = {Journal of Chemical and Engineering Data},
number = 8,
volume = 67,
place = {United States},
year = {Tue Jul 19 00:00:00 EDT 2022},
month = {Tue Jul 19 00:00:00 EDT 2022}
}
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https://doi.org/10.1021/acs.jced.2c00294
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