Thermodynamic origins of the solvent-dependent stability of lithium polysulfides from first principles

Pascal, Tod A.; Wujcik, Kevin H.; Wang, Dunyang Rita; Balsara, Nitash P.; Prendergast, David

doi:10.1039/c6cp06889h

Thermodynamic origins of the solvent-dependent stability of lithium polysulfides from first principles

Journal Article · Wed Nov 30 04:00:00 EST 2016 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c6cp06889h· OSTI ID:1475012

Pascal, Tod A. ^[1]; Wujcik, Kevin H. ^[2]; Wang, Dunyang Rita ^[3]; Balsara, Nitash P. ^[4]; Prendergast, David ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
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
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
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. Energy Technologies Area

An understanding of the complex solution phase chemistry of dissolved lithium polysulfides is critical to approaches aimed at improving the cyclability and commercial viability of lithium sulfur batteries. Experimental measurements are frustrated by the versatile sulfur–sulfur bond, with spontaneous disproportionation and interconversion leading to unknown equilibrium distributions of polysulfides with varying lengths and charge states. The solubility of isolated lithium polysulfides is calculated from first-principles molecular dynamics simulations. We explore the associated changes in the dissolution free energy, enthalpy and entropy in two regimes: liquid-phase monodentate solvation in dimethylformamide (DMF) and polymer-like chelation in bis(2-methoxyethyl) ether (diglyme). In both of these technologically relevant solvents, we show that the competition between enthalpy and entropy, related to specific interfacial atomic interactions, conspires to increase the relative stability of long chain dianionic species, which exist as Li⁺–LiS_x^- contact-ion-pairs. Further, we propose a mechanism of radical polysulfide stabilization in simple solvents through the reorientation of the 1^st shell solvent molecules to screen electrostatic fields emanating from the solute and explain nonmonotonicity of the dissolution entropy with polysulfide length in terms of a three-shell solvation model. Finally, our analysis provides statistical dynamics insights into polylsulfide stability, useful to understand or predict the relevant chemical species present in the solvent at low concentrations.

Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

DOE Contract Number:: AC02-05CH11231

OSTI ID:: 1475012

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 2 Vol. 19; ISSN 1463-9076

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

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