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Title: First-Principles Investigation of Lithium Polysulfide Structure and Behavior in Solution

We present the Lithium-Sulfur battery is a promising next generation energy storage technology that could meet the demands of modern society with a theoretical specific energy near 2500 W h kg -1. However, this battery chemistry faces unique problems such as the parasitic polysulfide shuttle reaction which hinders battery performance severely. This shuttle phenomenon is caused by solubilities of intermediate reaction products in the electrolyte during the reduction chemistry of the battery. With molecular simulation and computational chemistry tools, we studied the thermodynamics, solvation structure, and dynamics of the long-chain lithium polysulfide species Li 2S 6 and Li 2S 8 in dimethoxyethane and 1,3-dioxolane to gain a deeper fundamental understanding of this process. We determined the structure of the 1st solvation shell for Li + as well as those of Li 2S 6, Li 2S 8 closed and Li 2S 8 linear in pure solvents and solvents with extra Li + added. Finally, the lithium polysulfide species were found not to favor dissociation and would most likely exist as fully lithiated species in solution.
Authors:
 [1] ; ORCiD logo [1]
  1. Texas A & M Univ., College Station, TX (United States). Department of Chemical Engineering
Publication Date:
Grant/Contract Number:
EE0006832
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 39; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Texas A&M Engineering Experiment Station, College Station, TX (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
OSTI Identifier:
1430635

Kamphaus, Ethan P., and Balbuena, Perla B.. First-Principles Investigation of Lithium Polysulfide Structure and Behavior in Solution. United States: N. p., Web. doi:10.1021/acs.jpcc.7b04822.
Kamphaus, Ethan P., & Balbuena, Perla B.. First-Principles Investigation of Lithium Polysulfide Structure and Behavior in Solution. United States. doi:10.1021/acs.jpcc.7b04822.
Kamphaus, Ethan P., and Balbuena, Perla B.. 2017. "First-Principles Investigation of Lithium Polysulfide Structure and Behavior in Solution". United States. doi:10.1021/acs.jpcc.7b04822. https://www.osti.gov/servlets/purl/1430635.
@article{osti_1430635,
title = {First-Principles Investigation of Lithium Polysulfide Structure and Behavior in Solution},
author = {Kamphaus, Ethan P. and Balbuena, Perla B.},
abstractNote = {We present the Lithium-Sulfur battery is a promising next generation energy storage technology that could meet the demands of modern society with a theoretical specific energy near 2500 W h kg-1. However, this battery chemistry faces unique problems such as the parasitic polysulfide shuttle reaction which hinders battery performance severely. This shuttle phenomenon is caused by solubilities of intermediate reaction products in the electrolyte during the reduction chemistry of the battery. With molecular simulation and computational chemistry tools, we studied the thermodynamics, solvation structure, and dynamics of the long-chain lithium polysulfide species Li2S6 and Li2S8 in dimethoxyethane and 1,3-dioxolane to gain a deeper fundamental understanding of this process. We determined the structure of the 1st solvation shell for Li+ as well as those of Li2S6, Li2S8 closed and Li2S8 linear in pure solvents and solvents with extra Li+ added. Finally, the lithium polysulfide species were found not to favor dissociation and would most likely exist as fully lithiated species in solution.},
doi = {10.1021/acs.jpcc.7b04822},
journal = {Journal of Physical Chemistry. C},
number = 39,
volume = 121,
place = {United States},
year = {2017},
month = {9}
}