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Title: Rate Constants of Electrochemical Reactions in a Lithium-Sulfur Cell Determined by Operando X-ray Absorption Spectroscopy

Abstract

The reduction of sulfur during discharge in a lithium-sulfur (Li-S) cell is known to occur in a series of reaction steps that involve lithium polysulfide intermediates. We present an operando study of the discharge of a solid-state Li-S cell using X-ray absorption spectroscopy (XAS). In theory, the average chain length of the polysulfides, x avg,cell, at a given depth of discharge is determined by the number of electrons delivered to the sulfur cathode. The dependence of x avg,cell measured by XAS on the depth of discharge is in excellent agreement with theoretical predictions. XAS is also used to track the formation of Li 2S, the final discharge product, as a function of depth of discharge. The XAS measurements were used to estimate rate constants of a series of simple reactions commonly accepted in literature.

Authors:
 [1]; ORCiD logo [1];  [1];  [2];  [1];  [3];  [3];  [4];  [4];  [4]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1490458
Alternate Identifier(s):
OSTI ID: 1604654
Grant/Contract Number:  
AC02-76SF00515; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 165; Journal Issue: 14; Journal ID: ISSN 0013-4651
Publisher:
IOP Publishing - The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Wang, Dunyang Rita, Shah, Deep B., Maslyn, Jacqueline A., Loo, Whitney S., Wujcik, Kevin H., Nelson, Erik J., Latimer, Matthew J., Feng, Jun, Prendergast, David, Pascal, Tod A., and Balsara, Nitash P. Rate Constants of Electrochemical Reactions in a Lithium-Sulfur Cell Determined by Operando X-ray Absorption Spectroscopy. United States: N. p., 2018. Web. doi:10.1149/2.0981814jes.
Wang, Dunyang Rita, Shah, Deep B., Maslyn, Jacqueline A., Loo, Whitney S., Wujcik, Kevin H., Nelson, Erik J., Latimer, Matthew J., Feng, Jun, Prendergast, David, Pascal, Tod A., & Balsara, Nitash P. Rate Constants of Electrochemical Reactions in a Lithium-Sulfur Cell Determined by Operando X-ray Absorption Spectroscopy. United States. doi:10.1149/2.0981814jes.
Wang, Dunyang Rita, Shah, Deep B., Maslyn, Jacqueline A., Loo, Whitney S., Wujcik, Kevin H., Nelson, Erik J., Latimer, Matthew J., Feng, Jun, Prendergast, David, Pascal, Tod A., and Balsara, Nitash P. Fri . "Rate Constants of Electrochemical Reactions in a Lithium-Sulfur Cell Determined by Operando X-ray Absorption Spectroscopy". United States. doi:10.1149/2.0981814jes. https://www.osti.gov/servlets/purl/1490458.
@article{osti_1490458,
title = {Rate Constants of Electrochemical Reactions in a Lithium-Sulfur Cell Determined by Operando X-ray Absorption Spectroscopy},
author = {Wang, Dunyang Rita and Shah, Deep B. and Maslyn, Jacqueline A. and Loo, Whitney S. and Wujcik, Kevin H. and Nelson, Erik J. and Latimer, Matthew J. and Feng, Jun and Prendergast, David and Pascal, Tod A. and Balsara, Nitash P.},
abstractNote = {The reduction of sulfur during discharge in a lithium-sulfur (Li-S) cell is known to occur in a series of reaction steps that involve lithium polysulfide intermediates. We present an operando study of the discharge of a solid-state Li-S cell using X-ray absorption spectroscopy (XAS). In theory, the average chain length of the polysulfides, xavg,cell, at a given depth of discharge is determined by the number of electrons delivered to the sulfur cathode. The dependence of xavg,cell measured by XAS on the depth of discharge is in excellent agreement with theoretical predictions. XAS is also used to track the formation of Li2S, the final discharge product, as a function of depth of discharge. The XAS measurements were used to estimate rate constants of a series of simple reactions commonly accepted in literature.},
doi = {10.1149/2.0981814jes},
journal = {Journal of the Electrochemical Society},
issn = {0013-4651},
number = 14,
volume = 165,
place = {United States},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Figure 1 Figure 1: Schematic of a Li-S cell used for operando XAS study.

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.