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

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [1];  [2];  [1];  [3];  [3];  [3];  [3];  [1]
  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)
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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.
Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1374850
Journal Information:
ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 50 Vol. 8; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (9)

Directing the Lithium–Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries journal May 2017
Development and Challenges of Functional Electrolytes for High-Performance Lithium-Sulfur Batteries journal July 2018
Incorporating Solvate and Solid Electrolytes for All‐Solid‐State Li 2 S Batteries with High Capacity and Long Cycle Life journal May 2019
High Sulfur Content Material with Stable Cycling in Lithium-Sulfur Batteries journal October 2017
High Sulfur Content Material with Stable Cycling in Lithium-Sulfur Batteries journal October 2017
Polysulfide Shuttle Suppression by Electrolytes with Low‐Density for High‐Energy Lithium–Sulfur Batteries journal May 2019
An Aggregate Cluster-Dispersed Electrolyte Guides the Uniform Nucleation and Growth of Lithium at Lithium Metal Anodes journal November 2018
In Situ Techniques for Developing Robust Li-S Batteries journal August 2018
Tuning the electrolyte network structure to invoke quasi-solid state sulfur conversion and suppress lithium dendrite formation in Li–S batteries journal August 2018

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Related Subjects

25 ENERGY STORAGE
36 MATERIALS SCIENCE
hydrofluoroether cosolvent
in situ Raman spectroscopy
lithium−sulfur battery
solvate electrolyte
sulfur reduction kinetics