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Lithium Polysulfide Radical Anions in Ether-Based Solvents

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [1];  [3];  [4];  [4];  [5]
  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. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  3. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  5. 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. Environmental Energy Technologies Division
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Lithium sulfur batteries have a theoretical specific energy 5 times greater than current lithium ion battery standards, but suffer from the issue of lithium polysulfide dissolution. The reaction mechanisms that underlie the formation of lithium polysulfide reaction intermediates have been studied for over four decades, yet still elude researchers. Polysulfide radical anions formed during the redox processes have become a focal point of fundamental Li–S battery research. The formation of radical species has even been shown to be advantageous to the electrochemical pathways. However, whether polysulfide radical anions can form and be stabilized in common Li–S battery electrolytes that are ether-based is a point of contention in Li–S battery research. The goal of this paper was to examine the presence of radical polysulfide species in ether-based solvents. Lithium polysulfide solutions in tetraethylene glycol dimethyl ether and poly(ethylene oxide) are probed using a combination of ultraviolet–visible (UV–vis) and electron paramagnetic resonance (EPR) spectroscopy. EPR results confirm the presence of radical species in ether-based electrolytes. Finally, comparison of the UV–vis spectra to EPR spectra establishes that the UV–vis absorbance signature for radical species in ether-based solvents occurs at a wavelength of 617 nm, which is consistent with what is observed for high electron pair donor solvents such as dimethylformamide and dimethyl sulfoxide.
Research Organization:
Lawrence Berkeley National Laboratory (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
OSTI ID:
1474959
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 33 Vol. 120; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (9)

Advanced Characterization Techniques in Promoting Mechanism Understanding for Lithium-Sulfur Batteries journal March 2018
The Progress of Li-S Batteries-Understanding of the Sulfur Redox Mechanism: Dissolved Polysulfide Ions in the Electrolytes journal June 2018
Highly Solvating Electrolytes for Lithium–Sulfur Batteries journal December 2018
On the Factors Affecting Aging and Self‐Discharge of Lithium–Sulfur Cells. Effect of Positive Electrode Composition journal May 2019
A Sodium Polysulfide Battery with Liquid/Solid Electrolyte: Improving Sulfur Utilization Using P 2 S 5 as Additive and Tetramethylurea as Catholyte Solvent journal December 2019
Carbon nitride creates thioamides in high yields by the photocatalytic Kindler reaction journal January 2018
The role of polysulfide dianions and radical anions in the chemical, physical and biological sciences, including sulfur-based batteries journal January 2019
Solution-based synthesis of lithium thiophosphate superionic conductors for solid-state batteries: a chemistry perspective 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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