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Title: Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li–S Battery

Abstract

Li-S batteries are a promising next-generation battery technology. Due to the formation of soluble polysulfides during cell operation, the electrolyte composition of the cell plays an active role in directing the formation and speciation of the soluble lithium polysulfides. Recently, new classes of electrolytes termed "solvates" that contain stoichiometric quantities of salt and solvent and form a liquid at room temperature have been explored due to their sparingly solvating properties with respect to polysulfides. The viscosity of the solvate electrolytes is understandably high limiting their viability; however, hydrofluoroether cosolvents, thought to be inert to the solvate structure itself, can be introduced to reduce viscosity and enhance diffusion. Nazar and co-workers previously reported that addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) to the LiTFSI in acetonitrile solvate, (MeCN)2-LiTFSI, results in enhanced capacity retention compared to the neat solvate. Here, we evaluate the effect of TTE addition on both the electrochemical behavior of the Li-S cell and the solvation structure of the (MeCN)2-LiTFSI electrolyte. Contrary to previous suggestions, Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that TTE coordinates to Li+ at the expense of MeCN coordination, thereby producing a higher content of free MeCN, a good polysulfide solvent,more » in the electrolyte. Furthermore, the electrolytes containing a higher free MeCN content facilitate faster polysulfide formation kinetics during the electrochemical reduction of S in a Li-S cell likely as a result of the solvation power of the free MeCN.« less

Authors:
 [1];  [1];  [2];  [1];  [3];  [3];  [3];  [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Joint Center for Energy Storage Research, Argonne, IL (United States); Univ. of Illinois at Urbana - Champaign, Urbana, IL (United States)
  2. Joint Center for Energy Storage Research, Argonne, IL (United States); California State Univ., Northridge, CA (United States)
  3. Joint Center for Energy Storage Research, Argonne, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1374850
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 8; Journal Issue: 50; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; hydrofluoroether cosolvent; in situ Raman spectroscopy; lithium−sulfur battery; solvate electrolyte; sulfur reduction kinetics

Citation Formats

See, Kimberly A., Wu, Heng -Liang, Lau, Kah Chun, Shin, Minjeong, Cheng, Lei, Balasubramanian, Mahalingam, Gallagher, Kevin G., Curtiss, Larry A., and Gewirth, Andrew A. Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li–S Battery. United States: N. p., 2016. Web. doi:10.1021/acsami.6b11358.
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See, Kimberly A., Wu, Heng -Liang, Lau, Kah Chun, Shin, Minjeong, Cheng, Lei, Balasubramanian, Mahalingam, Gallagher, Kevin G., Curtiss, Larry A., & Gewirth, Andrew A. Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li–S Battery. United States. https://doi.org/10.1021/acsami.6b11358
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See, Kimberly A., Wu, Heng -Liang, Lau, Kah Chun, Shin, Minjeong, Cheng, Lei, Balasubramanian, Mahalingam, Gallagher, Kevin G., Curtiss, Larry A., and Gewirth, Andrew A. Wed . "Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li–S Battery". United States. https://doi.org/10.1021/acsami.6b11358. https://www.osti.gov/servlets/purl/1374850.
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@article{osti_1374850,
title = {Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li–S Battery},
author = {See, Kimberly A. and Wu, Heng -Liang and Lau, Kah Chun and Shin, Minjeong and Cheng, Lei and Balasubramanian, Mahalingam and Gallagher, Kevin G. and Curtiss, Larry A. and Gewirth, Andrew A.},
abstractNote = {Li-S batteries are a promising next-generation battery technology. Due to the formation of soluble polysulfides during cell operation, the electrolyte composition of the cell plays an active role in directing the formation and speciation of the soluble lithium polysulfides. Recently, new classes of electrolytes termed "solvates" that contain stoichiometric quantities of salt and solvent and form a liquid at room temperature have been explored due to their sparingly solvating properties with respect to polysulfides. The viscosity of the solvate electrolytes is understandably high limiting their viability; however, hydrofluoroether cosolvents, thought to be inert to the solvate structure itself, can be introduced to reduce viscosity and enhance diffusion. Nazar and co-workers previously reported that addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) to the LiTFSI in acetonitrile solvate, (MeCN)2-LiTFSI, results in enhanced capacity retention compared to the neat solvate. Here, we evaluate the effect of TTE addition on both the electrochemical behavior of the Li-S cell and the solvation structure of the (MeCN)2-LiTFSI electrolyte. Contrary to previous suggestions, Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that TTE coordinates to Li+ at the expense of MeCN coordination, thereby producing a higher content of free MeCN, a good polysulfide solvent, in the electrolyte. Furthermore, the electrolytes containing a higher free MeCN content facilitate faster polysulfide formation kinetics during the electrochemical reduction of S in a Li-S cell likely as a result of the solvation power of the free MeCN.},
doi = {10.1021/acsami.6b11358},
journal = {ACS Applied Materials and Interfaces},
number = 50,
volume = 8,
place = {United States},
year = {Wed Nov 16 00:00:00 EST 2016},
month = {Wed Nov 16 00:00:00 EST 2016}
}
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