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

Kamphaus, Ethan P.; Balbuena, Perla B.

doi:10.1021/acs.jpcc.7b04822

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

Journal Article · Thu Sep 07 04:00:00 EDT 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b04822· OSTI ID:1430635

Kamphaus, Ethan P. ^[1]; ^[2]

Texas A & M Univ., College Station, TX (United States). Department of Chemical Engineering; Texas A&M University
Texas A & M Univ., College Station, TX (United States). Department of Chemical Engineering

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.

View Accepted Manuscript (DOE)

Research Organization:: Texas A&M Engineering Experiment Station, College Station, TX (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Grant/Contract Number:: EE0006832

OSTI ID:: 1430635

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 39 Vol. 121; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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