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Title: Liquid Sulfur Impregnation of Microporous Carbon Accelerated by Nanoscale Interfacial Effects

Abstract

Impregnation of porous carbon matrices with liquid sulfur has been exploited to fabricate composite cathodes for lithium-sulfur batteries, aimed at confining soluble sulfur species near conducting carbon to prevent both loss of active material into the electrolyte and parasitic reactions at the lithium metal anode. Here, through extensive computer simulations, we uncover the strongly favorable interfacial free energy between liquid sulfur and graphitic surfaces that underlies this phenomenon. Previously unexplored curvature-dependent enhancements are shown to favor the filling of smaller pores first and effect a quasi-liquid sulfur phase in microporous domains (diameters <2 nm) that persists ~30° below the expected freezing point. Evidence of interfacial sulfur on carbon is shown to be a 0.3 eV red shift in the simulated and measured interfacial X-ray absorption spectra. Our results elucidate the critical morphology and thermodynamic properties necessary for future cathode design and highlight the importance of molecular-scale details in defining emergent properties of functional nanoscale interfaces.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [2];  [2];  [1];  [3]; ORCiD logo [2];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1379807
Grant/Contract Number:
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 17; Journal Issue: 4; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; battery; computer simulation; energy storage; entropy; free energy; molecular dynamics; nanoscale; spectroscopy; sulfur

Citation Formats

Pascal, Tod A., Villaluenga, Irune, Wujcik, Kevin H., Devaux, Didier, Jiang, Xi, Wang, Dunyang Rita, Balsara, Nitash, and Prendergast, David. Liquid Sulfur Impregnation of Microporous Carbon Accelerated by Nanoscale Interfacial Effects. United States: N. p., 2017. Web. doi:10.1021/acs.nanolett.7b00249.
Pascal, Tod A., Villaluenga, Irune, Wujcik, Kevin H., Devaux, Didier, Jiang, Xi, Wang, Dunyang Rita, Balsara, Nitash, & Prendergast, David. Liquid Sulfur Impregnation of Microporous Carbon Accelerated by Nanoscale Interfacial Effects. United States. doi:10.1021/acs.nanolett.7b00249.
Pascal, Tod A., Villaluenga, Irune, Wujcik, Kevin H., Devaux, Didier, Jiang, Xi, Wang, Dunyang Rita, Balsara, Nitash, and Prendergast, David. Tue . "Liquid Sulfur Impregnation of Microporous Carbon Accelerated by Nanoscale Interfacial Effects". United States. doi:10.1021/acs.nanolett.7b00249. https://www.osti.gov/servlets/purl/1379807.
@article{osti_1379807,
title = {Liquid Sulfur Impregnation of Microporous Carbon Accelerated by Nanoscale Interfacial Effects},
author = {Pascal, Tod A. and Villaluenga, Irune and Wujcik, Kevin H. and Devaux, Didier and Jiang, Xi and Wang, Dunyang Rita and Balsara, Nitash and Prendergast, David},
abstractNote = {Impregnation of porous carbon matrices with liquid sulfur has been exploited to fabricate composite cathodes for lithium-sulfur batteries, aimed at confining soluble sulfur species near conducting carbon to prevent both loss of active material into the electrolyte and parasitic reactions at the lithium metal anode. Here, through extensive computer simulations, we uncover the strongly favorable interfacial free energy between liquid sulfur and graphitic surfaces that underlies this phenomenon. Previously unexplored curvature-dependent enhancements are shown to favor the filling of smaller pores first and effect a quasi-liquid sulfur phase in microporous domains (diameters <2 nm) that persists ~30° below the expected freezing point. Evidence of interfacial sulfur on carbon is shown to be a 0.3 eV red shift in the simulated and measured interfacial X-ray absorption spectra. Our results elucidate the critical morphology and thermodynamic properties necessary for future cathode design and highlight the importance of molecular-scale details in defining emergent properties of functional nanoscale interfaces.},
doi = {10.1021/acs.nanolett.7b00249},
journal = {Nano Letters},
number = 4,
volume = 17,
place = {United States},
year = {Tue Mar 14 00:00:00 EDT 2017},
month = {Tue Mar 14 00:00:00 EDT 2017}
}

Journal Article:
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  • A three-dimensional hierarchical sandwich-type graphene sheet-sulfur/carbon (GS-S/C{sub ZIF8-D}) composite for use in a cathode for a lithium sulfur (Li-S) battery has been prepared by an ultrasonic method. The microporous carbon host was prepared by a one-step pyrolysis of Zeolitic Imidazolate Framework-8 (ZIF-8), a typical zinc-containing metal organic framework (MOF), which offers a tunable porous structure into which electro-active sulfur can be diffused. The thin graphene sheet, wrapped around the sulfur/zeolitic imidazolate framework-8 derived carbon (S/C{sub ZIF8-D}) composite, has excellent electrical conductivity and mechanical flexibility, thus facilitating rapid electron transport and accommodating the changes in volume of the sulfur electrode. Comparedmore » with the S/C{sub ZIF8-D} sample, Li-S batteries with the GS-S/C{sub ZIF8-D} composite cathode showed enhanced capacity, improved electrochemical stability, and relatively high columbic efficiency by taking advantage of the synergistic effects of the microporous carbon from ZIF-8 and a highly interconnected graphene network. Our results demonstrate that a porous MOF-derived scaffold with a wrapped graphene conductive network structure is a potentially efficient design for a battery electrode that can meet the challenge arising from low conductivity and volume change.« less
  • Following previous success with the use of activated carbon impregnated with sulfur at elevated temperatures for elemental mercury control, possible improvements in the impregnation procedure were evaluated in this study. Adsorbents prepared by thoroughly mixing sulfur and activated carbon in the furnace at the initial sulfur-to-carbon ratio (SCR) ranging from 4:1 to 1:2 showed similar adsorptive behavior in a fixed-bed system. Maintaining a stagnant inert atmosphere during the impregnation process improves sulfur deposition resulting in the enhanced dynamic capacity of the adsorbent when compared to other sulfur impregnated carbons. The fate of spent adsorbents was assessed using a toxicity characteristicsmore » leaching procedure (TCLP). Although mercury concentration in all leachates was below the TCLP limit, virgin activated carbon lost a significant fraction of the adsorbed elemental mercury during storage, while no loss was observed for sulfur-impregnated carbons. This finding suggests that virgin activated carbon may not be appropriate adsorbent for permanent sequestration of anthropogenic elemental mercury emissions.« less