CaltechAUTHORS
  A Caltech Library Service

Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li^+ Solvation Structure and Li–S Battery Performance

Shin, Minjeong and Wu, Heng-Liang and Narayanan, Badri and See, Kimberly A. and Assary, Rajeev S. and Zhu, Lingyang and Haasch, Richard T. and Zhang, Shuo and Zhang, Zhengcheng and Curtiss, Larry A. and Gewirth, Andrew A. (2017) Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li^+ Solvation Structure and Li–S Battery Performance. ACS Applied Materials & Interfaces, 9 (45). pp. 39357-39370. ISSN 1944-8244. https://resolver.caltech.edu/CaltechAUTHORS:20180607-160246396

[img] PDF (Electrochemical performance of Li–S cells cycled in solvate:HFE (1:1) electrolytes, physicochemical properties of solvate:HFE (1:1) electrolytes, assignments of Raman modes in (MeCN)2–LiTFSI/HFE electrolytes, low-wavenumber region Raman spectra of...) - Supplemental Material
See Usage Policy.

1009Kb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20180607-160246396

Abstract

We evaluate hydrofluoroether (HFE) cosolvents with varying degrees of fluorination in the acetonitrile-based solvate electrolyte to determine the effect of the HFE structure on the electrochemical performance of the Li–S battery. Solvates or sparingly solvating electrolytes are an interesting electrolyte choice for the Li–S battery due to their low polysulfide solubility. The solvate electrolyte with a stoichiometric ratio of LiTFSI salt in acetonitrile, (MeCN)_2–LiTFSI, exhibits limited polysulfide solubility due to the high concentration of LiTFSI. We demonstrate that the addition of highly fluorinated HFEs to the solvate yields better capacity retention compared to that of less fluorinated HFE cosolvents. Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that HFEs exhibiting a higher degree of fluorination coordinate to Li+ at the expense of MeCN coordination, resulting in higher free MeCN content in solution. However, the polysulfide solubility remains low, and no crossover of polysulfides from the S cathode to the Li anode is observed.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acsami.7b11566DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/acsami.7b11566PublisherSupporting Information
ORCID:
AuthorORCID
Shin, Minjeong0000-0002-9656-2651
See, Kimberly A.0000-0002-0133-9693
Assary, Rajeev S.0000-0002-9571-3307
Haasch, Richard T.0000-0001-9479-2595
Curtiss, Larry A.0000-0001-8855-8006
Gewirth, Andrew A.0000-0003-4400-9907
Alternate Title:Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li+ Solvation Structure and Li–S Battery Performance
Additional Information:© 2017 American Chemical Society. Received: August 3, 2017; Accepted: October 18, 2017; Published: October 18, 2017. We acknowledge Dr. Kevin Zavadil, Dr. Mali Balasubramanian, Dr. Chang-Wook Lee, Dr. Lei Cheng, Dr. Tylan Watkins, and Dr. Kah Chun Lau for helpful discussions. We thank Professor Catherine Murphy and Xi Zhang of the Department of Chemistry at the University of Illinois at Urbana-Champaign for assistance with teh UV–vis measurements. We thank Dr. Chengsi Pan for assistance with the conductivity measurements. This work was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. The submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract DE-AC02-06CH11357. This research used resources of the Argonne Leadership Computing Facility, which is a DOE Office of Science User Facility supported under Contract DE-AC02-06CH11357. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). Author Contributions: M.S. and H.-L.W. contributed equally to this work. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC02-06CH11357
Issue or Number:45
Record Number:CaltechAUTHORS:20180607-160246396
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180607-160246396
Official Citation:Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li+ Solvation Structure and Li–S Battery Performance. Minjeong Shin, Heng-Liang Wu, Badri Narayanan, Kimberly A. See, Rajeev S. Assary, Lingyang Zhu, Richard T. Haasch, Shuo Zhang, Zhengcheng Zhang, Larry A. Curtiss, and Andrew A. Gewirth. ACS Applied Materials & Interfaces 2017 9 (45), 39357-39370 DOI: 10.1021/acsami.7b11566
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86904
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:08 Jun 2018 14:57
Last Modified:03 Oct 2019 19:49

Repository Staff Only: item control page