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Title: Operando Spectromicroscopy of Sulfur Species in Lithium-Sulfur Batteries

Abstract

Here, a novel cross-sectional battery cell was developed to characterize lithium-sulfur batteries using X-ray spectromicroscopy. Chemically sensitive X-ray maps were collected operando at energies relevant to the expected sulfur species and were used to correlate changes in sulfur species with electrochemistry. Significant changes in the sulfur/carbon composite electrode were observed from cycle to cycle including rearrangement of the elemental sulfur matrix and PEO10LiTFSI binder. Polysulfide concentration and area of spatial diffusion increased with cycling, indicating that some polysulfide dissolution is irreversible, leading to polysulfide shuttle. Fitting of the maps using standard sulfur and polysulfide XANES spectra indicated that upon subsequent discharge/charge cycles, the initial sulfur concentration was not fully recovered; polysulfides and lithium sulfide remained at the cathodes with higher order polysulfides as the primary species in the region of interest. Quantification of the polysulfide concentration across the electrolyte and electrode interfaces shows that the polysulfide concentration before the first discharge and after the third charge is constant within the electrolyte, but while cycling, a significant increase in polysulfides and a gradient toward the lithium metal anode forms. Finally, this chemically and spatially sensitive characterization and analysis provides a foundation for further operando spectromicroscopy of lithium-sulfur batteries.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [3]; ORCiD logo [1]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource; Stanford Univ., CA (United States). Dept. of Materials Science and Engineering
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Joint Center for Energy Storage Research
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1407716
Alternate Identifier(s):
OSTI ID: 1472266
Report Number(s):
SAND2018-9772J
Journal ID: ISSN 0013-4651
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 165; Journal Issue: 1; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; lithium-sulfur batteries; x-ray absorption spectroscopy; x-ray spectromicroscopy

Citation Formats

Miller, Elizabeth C., Kasse, Robert M., Heath, Khloe N., Perdue, Brian R., and Toney, Michael F. Operando Spectromicroscopy of Sulfur Species in Lithium-Sulfur Batteries. United States: N. p., 2017. Web. doi:10.1149/2.0091801jes.
Miller, Elizabeth C., Kasse, Robert M., Heath, Khloe N., Perdue, Brian R., & Toney, Michael F. Operando Spectromicroscopy of Sulfur Species in Lithium-Sulfur Batteries. United States. doi:10.1149/2.0091801jes.
Miller, Elizabeth C., Kasse, Robert M., Heath, Khloe N., Perdue, Brian R., and Toney, Michael F. Fri . "Operando Spectromicroscopy of Sulfur Species in Lithium-Sulfur Batteries". United States. doi:10.1149/2.0091801jes. https://www.osti.gov/servlets/purl/1407716.
@article{osti_1407716,
title = {Operando Spectromicroscopy of Sulfur Species in Lithium-Sulfur Batteries},
author = {Miller, Elizabeth C. and Kasse, Robert M. and Heath, Khloe N. and Perdue, Brian R. and Toney, Michael F.},
abstractNote = {Here, a novel cross-sectional battery cell was developed to characterize lithium-sulfur batteries using X-ray spectromicroscopy. Chemically sensitive X-ray maps were collected operando at energies relevant to the expected sulfur species and were used to correlate changes in sulfur species with electrochemistry. Significant changes in the sulfur/carbon composite electrode were observed from cycle to cycle including rearrangement of the elemental sulfur matrix and PEO10LiTFSI binder. Polysulfide concentration and area of spatial diffusion increased with cycling, indicating that some polysulfide dissolution is irreversible, leading to polysulfide shuttle. Fitting of the maps using standard sulfur and polysulfide XANES spectra indicated that upon subsequent discharge/charge cycles, the initial sulfur concentration was not fully recovered; polysulfides and lithium sulfide remained at the cathodes with higher order polysulfides as the primary species in the region of interest. Quantification of the polysulfide concentration across the electrolyte and electrode interfaces shows that the polysulfide concentration before the first discharge and after the third charge is constant within the electrolyte, but while cycling, a significant increase in polysulfides and a gradient toward the lithium metal anode forms. Finally, this chemically and spatially sensitive characterization and analysis provides a foundation for further operando spectromicroscopy of lithium-sulfur batteries.},
doi = {10.1149/2.0091801jes},
journal = {Journal of the Electrochemical Society},
number = 1,
volume = 165,
place = {United States},
year = {2017},
month = {11}
}

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