Molecular structure and stability of dissolved lithium polysulfide species

M. Vijayakumar, Niranjan Govind, Eric Walter, Sarah D. Burton, Anil Shukla, Arun Devaraj, Jie Xiao, Jun Liu, Chongmin Wang, Ayman Karim, S. Thevuthasan

Research output: Contribution to journalArticle

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Abstract

The ability to predict the solubility and stability of lithium polysulfide is vital in realizing longer lasting lithium-sulfur batteries. Herein we report combined experimental and computational analyses to understand the dissolution mechanism of lithium polysulfide species in an aprotic solvent medium. Multinuclear NMR, variable temperature ESR and sulfur K-edge XAS analyses reveal that the lithium exchange between polysulfide species and solvent molecules constitutes the first step in the dissolution process. Lithium exchange leads to de-lithiated polysulfide ions (Sn2-) which subsequently form highly reactive free radicals through dissociation reaction (S n2- → 2Sn/2-). The energy required for the dissociation and possible dimer formation reactions of the polysulfide species is analyzed using density functional theory (DFT) based calculations. Based on these findings, we discuss approaches to optimize the electrolyte in order to control the polysulfide solubility. This journal is

Original languageEnglish
Pages (from-to)10923-10932
Number of pages10
JournalPhysical Chemistry Chemical Physics
Volume16
Issue number22
DOIs
Publication statusPublished - 14 Jun 2014
Externally publishedYes

Fingerprint

polysulfides
Molecular Structure
Lithium
Molecular structure
molecular structure
lithium
Sulfur
Solubility
dissolving
Dissolution
solubility
lithium sulfur batteries
dissociation
Biomolecular Nuclear Magnetic Resonance
Dimers
free radicals
Electrolytes
Free Radicals
Density functional theory
Paramagnetic resonance

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Physics and Astronomy(all)

Cite this

Vijayakumar, M., Govind, N., Walter, E., Burton, S. D., Shukla, A., Devaraj, A., ... Thevuthasan, S. (2014). Molecular structure and stability of dissolved lithium polysulfide species. Physical Chemistry Chemical Physics, 16(22), 10923-10932. https://doi.org/10.1039/c4cp00889h

Molecular structure and stability of dissolved lithium polysulfide species. / Vijayakumar, M.; Govind, Niranjan; Walter, Eric; Burton, Sarah D.; Shukla, Anil; Devaraj, Arun; Xiao, Jie; Liu, Jun; Wang, Chongmin; Karim, Ayman; Thevuthasan, S.

In: Physical Chemistry Chemical Physics, Vol. 16, No. 22, 14.06.2014, p. 10923-10932.

Research output: Contribution to journalArticle

Vijayakumar, M, Govind, N, Walter, E, Burton, SD, Shukla, A, Devaraj, A, Xiao, J, Liu, J, Wang, C, Karim, A & Thevuthasan, S 2014, 'Molecular structure and stability of dissolved lithium polysulfide species', Physical Chemistry Chemical Physics, vol. 16, no. 22, pp. 10923-10932. https://doi.org/10.1039/c4cp00889h
Vijayakumar M, Govind N, Walter E, Burton SD, Shukla A, Devaraj A et al. Molecular structure and stability of dissolved lithium polysulfide species. Physical Chemistry Chemical Physics. 2014 Jun 14;16(22):10923-10932. https://doi.org/10.1039/c4cp00889h
Vijayakumar, M. ; Govind, Niranjan ; Walter, Eric ; Burton, Sarah D. ; Shukla, Anil ; Devaraj, Arun ; Xiao, Jie ; Liu, Jun ; Wang, Chongmin ; Karim, Ayman ; Thevuthasan, S. / Molecular structure and stability of dissolved lithium polysulfide species. In: Physical Chemistry Chemical Physics. 2014 ; Vol. 16, No. 22. pp. 10923-10932.
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