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Title: Structural Dependence of the Sulfur Reduction Mechanism in Carbon-Based Cathodes for Lithium–Sulfur Batteries

We report lithium-sulfur batteries are promising non-conventional sources of energy due to their high theoretical capacity and energy density. However, the successful implementation of this technology has been hindered due to the low cycling life of the battery, caused by long chain polysulfide shuttling between electrodes during charge/discharge, among other issues. Quantum chemical calculations are used to study the reactivity of sulfur in the porous cathode of lithium-sulfur batteries, and the retention capabilities of porous carbon materials to avoid long chain polysulfide diffusion. Ab initio molecular dynamics (AIMD) simulations are initially employed to evaluate sulfur reduction mechanisms and kinetics, and to identify main reduction products. A porous cathode architecture is modeled through parallel graphene layers with elemental sulfur rings in the interlayer, and filled with 1,3-dioxolane (DOL) organic solvent and lithium ions. AIMD simulations showed fast reduction of elemental sulfur and formation of short chain polysulfide. Furthermore, the effect of dangling carbon bonds of graphene on the reactivity of the cathode was confirmed. Adsorption calculations through density functional theory (DFT) proved the capacity of small pores to retain long polysulfide chains. An analysis of the effect of the specific current on the chemical behavior of sulfur reveals an influence ofmore » current on the amount of sulfur utilization and practical specific capacity of the battery. In conclusion, this work illustrates the physical-chemical behavior of the sulfur/polysulfide in the porous cathode system at atomistic level.« less
Authors:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [3]
  1. Univ. of Cartagena (Colombia). Doctorate in Physical Sciences. Faculty of Exact and Natural Sciences; Texas A & M Univ., College Station, TX (United States). Dept. of Chemical Engineering
  2. Texas A & M Univ., College Station, TX (United States). Dept. of Chemical Engineering
  3. Univ. of Cartagena (Colombia). Doctorate in Physical Sciences. Faculty of Exact and Natural Sciences. Inst. of Applied Mathematics
Publication Date:
Grant/Contract Number:
EE0006832
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 34; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Texas A&M Engineering Experiment Station, College Station, TX (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE
OSTI Identifier:
1430484

Burgos, Juan C., Balbuena, Perla B., and Montoya, Javier A.. Structural Dependence of the Sulfur Reduction Mechanism in Carbon-Based Cathodes for Lithium–Sulfur Batteries. United States: N. p., Web. doi:10.1021/acs.jpcc.7b05554.
Burgos, Juan C., Balbuena, Perla B., & Montoya, Javier A.. Structural Dependence of the Sulfur Reduction Mechanism in Carbon-Based Cathodes for Lithium–Sulfur Batteries. United States. doi:10.1021/acs.jpcc.7b05554.
Burgos, Juan C., Balbuena, Perla B., and Montoya, Javier A.. 2017. "Structural Dependence of the Sulfur Reduction Mechanism in Carbon-Based Cathodes for Lithium–Sulfur Batteries". United States. doi:10.1021/acs.jpcc.7b05554. https://www.osti.gov/servlets/purl/1430484.
@article{osti_1430484,
title = {Structural Dependence of the Sulfur Reduction Mechanism in Carbon-Based Cathodes for Lithium–Sulfur Batteries},
author = {Burgos, Juan C. and Balbuena, Perla B. and Montoya, Javier A.},
abstractNote = {We report lithium-sulfur batteries are promising non-conventional sources of energy due to their high theoretical capacity and energy density. However, the successful implementation of this technology has been hindered due to the low cycling life of the battery, caused by long chain polysulfide shuttling between electrodes during charge/discharge, among other issues. Quantum chemical calculations are used to study the reactivity of sulfur in the porous cathode of lithium-sulfur batteries, and the retention capabilities of porous carbon materials to avoid long chain polysulfide diffusion. Ab initio molecular dynamics (AIMD) simulations are initially employed to evaluate sulfur reduction mechanisms and kinetics, and to identify main reduction products. A porous cathode architecture is modeled through parallel graphene layers with elemental sulfur rings in the interlayer, and filled with 1,3-dioxolane (DOL) organic solvent and lithium ions. AIMD simulations showed fast reduction of elemental sulfur and formation of short chain polysulfide. Furthermore, the effect of dangling carbon bonds of graphene on the reactivity of the cathode was confirmed. Adsorption calculations through density functional theory (DFT) proved the capacity of small pores to retain long polysulfide chains. An analysis of the effect of the specific current on the chemical behavior of sulfur reveals an influence of current on the amount of sulfur utilization and practical specific capacity of the battery. In conclusion, this work illustrates the physical-chemical behavior of the sulfur/polysulfide in the porous cathode system at atomistic level.},
doi = {10.1021/acs.jpcc.7b05554},
journal = {Journal of Physical Chemistry. C},
number = 34,
volume = 121,
place = {United States},
year = {2017},
month = {8}
}