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Lithium Polysulfide Speciation in Lithium–Sulfur Batteries: A First-Principles Benchmark of Thermodynamics, Bonding, and Solvent Control

  • Rafael Ferreira Ferreira de Menezes
  • Tiago Cassiano1,2
  • Lydia Meyer3
  • Jason Porter4
  • Flavio O. Sanches-Neto5,6,7
  • Benjamin Diehl4
  • Joanna Maratos4
  • Tristan Schiess4
  • Jared Landetta Espinoza4
  • Ana Costa
  • Andrew Colclasure3
  • Ricardo Gargano8,9,10,11
1 more authors
  • Kayla G. Sprenger8,9,10,11
11 affiliations
  1. 1International Center of Physics
  2. 2Institute of Physics, University of Brasília
  3. 3National Laboratory of the Rockies
  4. 4Brigham Young University
  5. 5Federal Institute of Education, Science and Technology of Goiás
  6. 6Theoretical and Structural Chemistry Group of Anápolis
  7. 7State University of Goiás
  8. 8Department of Chemical Engineering
  9. 9University of Colorado Boulder
  10. 10Institute of Physics
  11. 11University of Brasília
Open at sourceDOICite

Abstract

Lithium–sulfur cycle life is limited by dissolved LiyS q x polysulfides whose speciation remains disputed. We benchmark the complete matrix (y = 0–2, q = 0 to −2, x = 1–8) in the gas phase, tetraglyme and dimethyl sulfoxide: 248 M06-2X/SMD thermochemistries, 132 refined by single-point CCSD. The convex hull, S8 → Li2S6 → Li2S4 → Li2S3 → Li2S2 → Li2S, is identical in both solvents, and every exergonic long-chain comproportionation delivers Li2S6. QTAIM analysis of the CCSD densities separates covalent S–S from electrostatic Li–S bonding, transferably between solvents. Solvation makes S 2–x the dominant lithium-free 1 charge state and places both legs of the shuttle on that branch. Infrared and Raman spectra of prepared solutions test the vibrational predictions and track the chain-length distribution through one band envelope. The open dataset is a calibrated reference for force-field, machine-learned and continuum battery models.

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Cite

BibTeXRIS
BibTeX
@misc{menezes2026lithium,
  title = {{Lithium Polysulfide Speciation in Lithium–Sulfur Batteries: A First-Principles Benchmark of Thermodynamics, Bonding, and Solvent Control}},
  author = {Rafael Ferreira Ferreira de Menezes and Tiago Cassiano and Lydia Meyer and Jason Porter and Flavio O. Sanches-Neto and Benjamin Diehl and Joanna Maratos and Tristan Schiess and Jared Landetta Espinoza and Ana Costa and Andrew Colclasure and Ricardo Gargano and Kayla G. Sprenger},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010681/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010681/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Lithium Polysulfide Speciation in Lithium–Sulfur Batteries: A First-Principles Benchmark of Thermodynamics, Bonding, and Solvent Control
AU  - Rafael Ferreira Ferreira de Menezes
AU  - Tiago Cassiano
AU  - Lydia Meyer
AU  - Jason Porter
AU  - Flavio O. Sanches-Neto
AU  - Benjamin Diehl
AU  - Joanna Maratos
AU  - Tristan Schiess
AU  - Jared Landetta Espinoza
AU  - Ana Costa
AU  - Andrew Colclasure
AU  - Ricardo Gargano
AU  - Kayla G. Sprenger
PY  - 2026
DA  - 2026/10/19
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010681/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010681/v1
AB  - Lithium–sulfur cycle life is limited by dissolved LiyS q x polysulfides whose speciation remains disputed. We benchmark the complete matrix (y = 0–2, q = 0 to −2, x = 1–8) in the gas phase, tetraglyme and dimethyl sulfoxide: 248 M06-2X/SMD thermochemistries, 132 refined by single-point CCSD. The convex hull, S8 → Li2S6 → Li2S4 → Li2S3 → Li2S2 → Li2S, is identical in both solvents, and every exergonic long-chain comproportionation delivers Li2S6. QTAIM analysis of the CCSD densities separates covalent S–S from electrostatic Li–S bonding, transferably between solvents. Solvation makes S 2–x the dominant lithium-free 1 charge state and places both legs of the shuttle on that branch. Infrared and Raman spectra of prepared solutions test the vibrational predictions and track the chain-length distribution through one band envelope. The open dataset is a calibrated reference for force-field, machine-learned and continuum battery models.
ER  -