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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}
}

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