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Impact of fluorination on Li+ solvation and dynamics in ionic liquid-hydrofluoroether locally concentrated electrolytes

Journal Article · · Journal of Power Sources
 [1];  [2];  [3];  [2];  [3];  [4];  [4];  [2]
  1. Case Western Reserve University, Cleveland, OH (United States); Case Western Reserve University
  2. Case Western Reserve University, Cleveland, OH (United States)
  3. Hunter College, New York, NY (United States)
  4. University of Notre Dame, IN (United States)
+ Show Author Affiliations
The thermal, physical, structural, and transport properties of ionic liquid (IL) electrolytes based on n-methyl-n-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide [PYR14][TFSI] and Li-salts of lithium (nonafluorobutane)(trifluoromethanesulfonyl)imide [Li][IM14] and [Li][TFSI] (0 ≤ xLi ≤ 0.3), with addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) (0 ≤ xTTE ≤ 0.45) were studied. While [IM14] increases glass transition, TTE improves conductivity over a wider liquidus range. Li+ is solvated primarily by [TFSI] with some contribution by [IM14]. However, both 7Li- 19F HOESY NMR and spatial distribution functions (SDFs) derived from molecular dynamics (MD) indicate short contacts between the fluorines of TTE and Li+. This is a result of tighter anion-solvated Li+ without aggregation of the Li+ solvates, consistent with Raman measurements, thus confirming the existence of fluorous domains in the bulk which leads to improved fluidity and a Li+ diffusivity of 1.26 x 10–12 m2/s at 0 °C (xLi = 0.20) with a Li+ transference of 0.16. Improved transport properties translated to a higher capacity of the TTE/IL electrolyte in a Li||LiFePO4 half-cell with 95mAh/g at 0.1C, compared to the IL electrolyte without TTE (60 mAh/g). Furthermore, this study demonstrates the tunability of solvation and transport properties in IL electrolytes by asymmetric fluorinated anions and hydrofluoroether co-solvents for low temperature Li-ion batteries.
Research Organization:
Case Western Reserve University, Cleveland, OH (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0019409
OSTI ID:
2329453
Journal Information:
Journal of Power Sources, Journal Name: Journal of Power Sources Vol. 593; ISSN 0378-7753
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

25 ENERGY STORAGE
2D NMR
Fluoroether
Lithium-ion
Nonflammable electrolyte
Transference