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

Burgos, Juan C.; Balbuena, Perla B.; Montoya, Javier A.

doi:10.1021/acs.jpcc.7b05554

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

Journal Article · Thu Aug 17 04:00:00 EDT 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b05554· OSTI ID:1430484

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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; Texas A&M University
Texas A & M Univ., College Station, TX (United States). Dept. of Chemical Engineering
Univ. of Cartagena (Colombia). Doctorate in Physical Sciences. Faculty of Exact and Natural Sciences. Inst. of Applied Mathematics

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.

View Accepted Manuscript (DOE)

Research Organization:: Texas A&M Engineering Experiment Station, College Station, TX (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Grant/Contract Number:: EE0006832

OSTI ID:: 1430484

Alternate ID(s):: OSTI ID: 1606435

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 34 Vol. 121; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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