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Title: Lithium–sulfur battery with partially fluorinated ether electrolytes: Interplay between capacity, coulombic efficiency and Li anode protection

Abstract

Seven partially fluorinated ethers (PFE) were explored as co-solvents for lithium-sulfur battery with the goal to understand the interplay between the molecular structure and the electrochemical properties, including capacity, Coulombic efficiency and SEI formation on the Li anode. Electrochemical cycling suggests a loose correlation between the Coulombic efficiency observed over 200 cycles and the fluorination degree of the PFE, which correlates with the computed pKa of the C–H bond of the ethers. PFE with lower pKa (<36) tends to chemically react with lithium anode forming a solid-electrolyte-interphase (SEI) layer thus preventing the shuttling effect of the lithium polysulfides. The cycled lithium anodes with DOL/PFE electrolyte was discovered to produce a protective SEI analyzed by FT-IR and SEM/EDS. Computations of the interactions between the PFEs of interest and a lithium surface suggest the generation of LiF and unsaturated PFE derivatives which are easily reduced and polymerized on the Li surface. The PFE decomposition is more thermodynamically likely with increasing fluorination degree. This research sheds light on the role that fluorine substitution and structure play in the high Coulombic efficiencies observed for Li–S cells.

Authors:
ORCiD logo [1];  [2];  [1];  [1];  [1];  [3];  [4];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States); Ohio Univ., Athens, OH (United States)
  3. Mercedes-Benz Research & Development North America, Inc., Redford, MI (United States)
  4. Daimler AG (Mercedes-Benz Cars), Boeblingen (Germany)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1567739
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Power Sources
Additional Journal Information:
Journal Volume: 438; Journal Issue: C; Journal ID: ISSN 0378-7753
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Li–S battery; Fluorinated electrolytes; Coulombic efficiency; Electrolyte-Li interface; Metal reactivity computation

Citation Formats

Meisner, Quinton J., Rojas, Tomas, Dietz Rago, Nancy L., Cao, Jiayu, Bareño, Javier, Glossmann, Tobias, Hintennach, Andreas, Redfern, Paul C., Pahls, Dale, Zhang, Lu, Bloom, Ira D., Ngo, Anh T., Curtiss, Larry A., and Zhang, Zhengcheng. Lithium–sulfur battery with partially fluorinated ether electrolytes: Interplay between capacity, coulombic efficiency and Li anode protection. United States: N. p., 2019. Web. doi:10.1016/j.jpowsour.2019.226939.
Meisner, Quinton J., Rojas, Tomas, Dietz Rago, Nancy L., Cao, Jiayu, Bareño, Javier, Glossmann, Tobias, Hintennach, Andreas, Redfern, Paul C., Pahls, Dale, Zhang, Lu, Bloom, Ira D., Ngo, Anh T., Curtiss, Larry A., & Zhang, Zhengcheng. Lithium–sulfur battery with partially fluorinated ether electrolytes: Interplay between capacity, coulombic efficiency and Li anode protection. United States. doi:10.1016/j.jpowsour.2019.226939.
Meisner, Quinton J., Rojas, Tomas, Dietz Rago, Nancy L., Cao, Jiayu, Bareño, Javier, Glossmann, Tobias, Hintennach, Andreas, Redfern, Paul C., Pahls, Dale, Zhang, Lu, Bloom, Ira D., Ngo, Anh T., Curtiss, Larry A., and Zhang, Zhengcheng. Thu . "Lithium–sulfur battery with partially fluorinated ether electrolytes: Interplay between capacity, coulombic efficiency and Li anode protection". United States. doi:10.1016/j.jpowsour.2019.226939.
@article{osti_1567739,
title = {Lithium–sulfur battery with partially fluorinated ether electrolytes: Interplay between capacity, coulombic efficiency and Li anode protection},
author = {Meisner, Quinton J. and Rojas, Tomas and Dietz Rago, Nancy L. and Cao, Jiayu and Bareño, Javier and Glossmann, Tobias and Hintennach, Andreas and Redfern, Paul C. and Pahls, Dale and Zhang, Lu and Bloom, Ira D. and Ngo, Anh T. and Curtiss, Larry A. and Zhang, Zhengcheng},
abstractNote = {Seven partially fluorinated ethers (PFE) were explored as co-solvents for lithium-sulfur battery with the goal to understand the interplay between the molecular structure and the electrochemical properties, including capacity, Coulombic efficiency and SEI formation on the Li anode. Electrochemical cycling suggests a loose correlation between the Coulombic efficiency observed over 200 cycles and the fluorination degree of the PFE, which correlates with the computed pKa of the C–H bond of the ethers. PFE with lower pKa (<36) tends to chemically react with lithium anode forming a solid-electrolyte-interphase (SEI) layer thus preventing the shuttling effect of the lithium polysulfides. The cycled lithium anodes with DOL/PFE electrolyte was discovered to produce a protective SEI analyzed by FT-IR and SEM/EDS. Computations of the interactions between the PFEs of interest and a lithium surface suggest the generation of LiF and unsaturated PFE derivatives which are easily reduced and polymerized on the Li surface. The PFE decomposition is more thermodynamically likely with increasing fluorination degree. This research sheds light on the role that fluorine substitution and structure play in the high Coulombic efficiencies observed for Li–S cells.},
doi = {10.1016/j.jpowsour.2019.226939},
journal = {Journal of Power Sources},
number = C,
volume = 438,
place = {United States},
year = {2019},
month = {8}
}

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This content will become publicly available on August 1, 2020
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