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

Journal Article · · Journal of Physical Chemistry. C
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
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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.

Research Organization:
Texas A & M Univ., College Station, TX (United States). Texas A & M Engineering Experiment Station
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Grant/Contract Number:
EE0006832
OSTI ID:
1430484
Journal Information:
Journal of Physical Chemistry. C, Vol. 121, Issue 34; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science

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Cited By (3)

Rational Design of Nanostructured Functional Interlayer/Separator for Advanced Li-S Batteries journal February 2018
Formation of Multilayer Graphene Domains with Strong Sulfur–Carbon Interaction and Enhanced Sulfur Reduction Zones for Lithium–Sulfur Battery Cathodes journal March 2018
Rate Constants of Electrochemical Reactions in a Lithium-Sulfur Cell Determined by Operando X-ray Absorption Spectroscopy journal January 2018

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