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Title: In Situ X-ray Absorption Spectroscopy Studies of Discharge Reactions in a Thick Cathode of a Lithium Sulfur Battery

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/2.1441614jes· OSTI ID:1440947
 [1];  [2];  [3];  [3];  [4]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  4. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division and Environmental Energy Technologies Division
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Lithium sulfur (Li-S) batteries are well known for their high theoretical specific capacities, but are plagued with scientific obstacles that make practical implementation of the technology impossible. The success of Li-S batteries will likely necessitate the use of thick sulfur cathodes that enable high specific energy densities. However, little is known about the fundamental reaction mechanisms and chemical processes that take place in thick cathodes, as most research has focused on studying thinner cathodes that enable high performance. In this study, in situ X-ray absorption spectroscopy at the sulfur K-edge is used to examine the back of a 115 μm thick Li-S cathode during discharge. Our results show that in such systems, where electrochemical reactions between sulfur and lithium are likely to proceed preferentially toward the front of the cathode, lithium polysulfide dianions formed in this region diffuse to the back of the cathode during discharge. We show that high conversion of elemental sulfur is achieved by chemical reactions between elemental sulfur and polysulfide dianions of intermediate chain length (Li2Sx, 4 ≤ x ≤ 6). Our work suggests that controlling the formation and diffusion of intermediate chain length polysulfide dianions is crucial for insuring full utilization of thick sulfur cathodes.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Grant/Contract Number:
AC02-05CH11231; AC02-76SF00515
OSTI ID:
1440947
Journal Information:
Journal of the Electrochemical Society, Vol. 164, Issue 2; Related Information: © The Author(s) 2016. Published by ECS. All rights reserved.; ISSN 0013-4651
Publisher:
The Electrochemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 24 works
Citation information provided by
Web of Science

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Cited By (9)

Advanced Characterization Techniques in Promoting Mechanism Understanding for Lithium-Sulfur Batteries journal March 2018
A Comprehensive Understanding of Lithium–Sulfur Battery Technology journal June 2019
The Progress of Li-S Batteries-Understanding of the Sulfur Redox Mechanism: Dissolved Polysulfide Ions in the Electrolytes journal June 2018
Deciphering the Reaction Mechanism of Lithium–Sulfur Batteries by In Situ/Operando Synchrotron‐Based Characterization Techniques journal March 2019
Understanding the Reaction Mechanism of Lithium–Sulfur Batteries by In Situ/Operando X-ray Absorption Spectroscopy journal March 2019
Tuning the electrolyte network structure to invoke quasi-solid state sulfur conversion and suppress lithium dendrite formation in Li–S batteries journal August 2018
Multi-functional nanowall arrays with unrestricted Li + transport channels and an integrated conductive network for high-areal-capacity Li–S batteries journal January 2018
Exploring reaction dynamics in lithium–sulfur batteries by time-resolved operando sulfur K-edge X-ray absorption spectroscopy journal January 2019
Rate Constants of Electrochemical Reactions in a Lithium-Sulfur Cell Determined by Operando X-ray Absorption Spectroscopy journal January 2018

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25 ENERGY STORAGE
battery
in situ
lithium sulfur
polymer electrolyte
polysulfide
x-ray absorption spectroscopy