title: Thermodynamic origins of the solvent-dependent stability of lithium polysulfides from first principles.
abstract: 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. Here, 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+-LiSx-contact-ion-pairs. Further, we propose a mechanism of radical polysulfide stabilization in simple solvents through the reorientation of the 1stshell 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. 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.
authors.affiliation: Molecular Foundry, Lawrence Berkeley National Lab, Berkeley, CA 94720, USA. tapascal@lbl.gov dgprendergast@lbl.gov.
authors.forename: Tod A
authors.initials: TA
authors.lastname: Pascal
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, USA and Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
authors.forename: Kevin H
authors.initials: KH
authors.lastname: Wujcik
authors.affiliation: Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA and Department of Materials Science and Engineering, University of California, Berkeley, California 94720, USA.
authors.forename: Dunyang Rita
authors.initials: DR
authors.lastname: Wang
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, USA and Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA and Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley California 94720, USA.
authors.forename: Nitash P
authors.initials: NP
authors.lastname: Balsara
authors.affiliation: Molecular Foundry, Lawrence Berkeley National Lab, Berkeley, CA 94720, USA. tapascal@lbl.gov dgprendergast@lbl.gov.
authors.forename: David
authors.initials: D
authors.lastname: Prendergast