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:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- 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:
- 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. https://doi.org/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. https://doi.org/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}
}
Web of Science
Works referenced in this record:
A Solid Sulfur Cathode for Aqueous Batteries
journal, August 1993
- Peramunage, D.; Licht, S.
- Science, Vol. 261, Issue 5124
A Mathematical Model for a Lithium–Sulfur Cell
journal, January 2008
- Kumaresan, Karthikeyan; Mikhaylik, Yuriy; White, Ralph E.
- Journal of The Electrochemical Society, Vol. 155, Issue 8
Li/S fundamental chemistry and application to high-performance rechargeable batteries
journal, November 2004
- Akridge, J.
- Solid State Ionics, Vol. 175, Issue 1-4
Lithium Sulfur Battery: Oxidation/Reduction Mechanisms of Polysulfides in THF Solutions
journal, January 1988
- Yamin, H.; Gorenshtein, A.; Penciner, J.
- Journal of The Electrochemical Society, Vol. 135, Issue 5, p. 1045-1048
Lithium/Sulfur Cell Discharge Mechanism: An Original Approach for Intermediate Species Identification
journal, April 2012
- Barchasz, Céline; Molton, Florian; Duboc, Carole
- Analytical Chemistry, Vol. 84, Issue 9
Li-S Battery Analyzed by UV/Vis in Operando Mode
journal, June 2013
- Patel, Manu U. M.; Demir-Cakan, Rezan; Morcrette, Mathieu
- ChemSusChem, Vol. 6, Issue 7
Unique behaviour of nonsolvents for polysulphides in lithium–sulphur batteries
journal, January 2014
- Cuisinier, M.; Cabelguen, P. -E.; Adams, B. D.
- Energy Environ. Sci., Vol. 7, Issue 8
Graphene-Wrapped Sulfur Particles as a Rechargeable Lithium–Sulfur Battery Cathode Material with High Capacity and Cycling Stability
journal, July 2011
- Wang, Hailiang; Yang, Yuan; Liang, Yongye
- Nano Letters, Vol. 11, Issue 7, p. 2644-2647
Sulfur Speciation in Li–S Batteries Determined by Operando X-ray Absorption Spectroscopy
journal, September 2013
- Cuisinier, Marine; Cabelguen, Pierre-Etienne; Evers, Scott
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 19
Characterization of Polysulfide Radicals Present in an Ether-Based Electrolyte of a Lithium-Sulfur Battery During Initial Discharge Using In Situ X-Ray Absorption Spectroscopy Experiments and First-Principles Calculations
journal, June 2015
- Wujcik, Kevin H.; Pascal, Tod A.; Pemmaraju, C. D.
- Advanced Energy Materials, Vol. 5, Issue 16
Polysulfide Shuttle Study in the Li/S Battery System
journal, January 2004
- Mikhaylik, Yuriy V.; Akridge, James R.
- Journal of The Electrochemical Society, Vol. 151, Issue 11, p. A1969-A1976
Carbon–sulfur composites for Li–S batteries: status and prospects
journal, January 2013
- Wang, Da-Wei; Zeng, Qingcong; Zhou, Guangmin
- Journal of Materials Chemistry A, Vol. 1, Issue 33
A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries
journal, May 2009
- Ji, Xiulei; Lee, Kyu Tae; Nazar, Linda F.
- Nature Materials, Vol. 8, Issue 6, p. 500-506
Graphene Oxide as a Sulfur Immobilizer in High Performance Lithium/Sulfur Cells
journal, November 2011
- Ji, Liwen; Rao, Mumin; Zheng, Haimei
- Journal of the American Chemical Society, Vol. 133, Issue 46, p. 18522-18525
Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries
journal, January 2013
- Wei Seh, Zhi; Li, Weiyang; Cha, Judy J.
- Nature Communications, Vol. 4, Article No. 1331
High-performance hollow sulfur nanostructured battery cathode through a scalable, room temperature, one-step, bottom-up approach
journal, April 2013
- Li, W.; Zheng, G.; Yang, Y.
- Proceedings of the National Academy of Sciences, Vol. 110, Issue 18
Hierarchically Structured Sulfur/Carbon Nanocomposite Material for High-Energy Lithium Battery
journal, October 2009
- Liang, Chengdu; Dudney, Nancy J.; Howe, Jane Y.
- Chemistry of Materials, Vol. 21, Issue 19, p. 4724-4730
Polysulfide-Blocking Microporous Polymer Membrane Tailored for Hybrid Li-Sulfur Flow Batteries
journal, August 2015
- Li, Changyi; Ward, Ashleigh L.; Doris, Sean E.
- Nano Letters, Vol. 15, Issue 9
Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries
journal, December 2015
- Villaluenga, Irune; Wujcik, Kevin H.; Tong, Wei
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 1
Distribution of Sulfur in Carbon/Sulfur Nanocomposites Analyzed by Small-Angle X-ray Scattering
journal, March 2016
- Petzold, Albrecht; Juhl, Anika; Scholz, Jonas
- Langmuir, Vol. 32, Issue 11
Density functional and Monte Carlo studies of sulfur. II. Equilibrium polymerization of the liquid phase
journal, October 2003
- Ballone, P.; Jones, R. O.
- The Journal of Chemical Physics, Vol. 119, Issue 16
Quantum mechanics based force field for carbon (QMFF-Cx) validated to reproduce the mechanical and thermodynamics properties of graphite
journal, October 2010
- Pascal, Tod A.; Karasawa, Naoki; Goddard, William A.
- The Journal of Chemical Physics, Vol. 133, Issue 13
Higher-accuracy van der Waals density functional
journal, August 2010
- Lee, Kyuho; Murray, Éamonn D.; Kong, Lingzhu
- Physical Review B, Vol. 82, Issue 8
The Surface Tension of Sulfur
journal, September 1950
- Fanelli, R.
- Journal of the American Chemical Society, Vol. 72, Issue 9
Wettability and work of adhesion of liquid sulfur on carbon materials for electrical energy storage applications
journal, March 2016
- Kaban, Ivan; Nowak, Rafał; Bruzda, Grzegorz
- Carbon, Vol. 98
Phase Transitions in Pores: Experimental and Simulation Studies of Melting and Freezing †
journal, August 1999
- Sliwinska-Bartkowiak, Malgorzata; Gras, Jolanta; Sikorski, Roman
- Langmuir, Vol. 15, Issue 18
Phase equilibria and solvation forces for fluids confined between parallel walls
journal, June 1987
- Evans, R.; Marini Bettolo Marconi, U.
- The Journal of Chemical Physics, Vol. 86, Issue 12
Observation of extreme phase transition temperatures of water confined inside isolated carbon nanotubes
journal, November 2016
- Agrawal, Kumar Varoon; Shimizu, Steven; Drahushuk, Lee W.
- Nature Nanotechnology, Vol. 12, Issue 3
Capillarity and Wetting of Carbon Nanotubes
journal, September 1994
- Dujardin, E.; Ebbesen, T. W.; Hiura, H.
- Science, Vol. 265, Issue 5180
X-ray spectroscopy as a probe for lithium polysulfide radicals
journal, January 2015
- Pascal, Tod A.; Pemmaraju, C. D.; Prendergast, David
- Physical Chemistry Chemical Physics, Vol. 17, Issue 12
X-ray Absorption Spectra of Dissolved Polysulfides in Lithium–Sulfur Batteries from First-Principles
journal, April 2014
- Pascal, Tod A.; Wujcik, Kevin H.; Velasco-Velez, Juan
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 9
The structure of interfacial water on gold electrodes studied by x-ray absorption spectroscopy
journal, October 2014
- Velasco-Velez, J. -J.; Wu, C. H.; Pascal, T. A.
- Science, Vol. 346, Issue 6211
Works referencing / citing this record:
Review of Carbon Materials for Lithium-Sulfur Batteries
journal, February 2018
- Li, Shanshan; Jin, Bo; Zhai, Xiaojie
- ChemistrySelect, Vol. 3, Issue 8
Brush-structured sulfur–polyaniline–graphene composite as cathodes for lithium–sulfur batteries
journal, November 2019
- Liu, Heguang; Jing, Ruixuan; You, Caiyin
- MRS Communications, Vol. 9, Issue 4
Investigating detailed mechanism of hydrogen molecules adsorbing on single-wall carbon nanotubes using fitted force field parameters containing carbon-carbon interactions: Investigating Detailed Mechanism of Hydrogen Molecules Adsorbing on Single-Wall Carbon Nanotubes Using Fitted Force Field Parameters Containing Carbon
journal, October 2018
- Kong, Chui-Peng; Gao, Xin; Jia, Ran
- Journal of Computational Chemistry, Vol. 40, Issue 10
Rate Constants of Electrochemical Reactions in a Lithium-Sulfur Cell Determined by Operando X-ray Absorption Spectroscopy
journal, January 2018
- Wang, Dunyang Rita; Shah, Deep B.; Maslyn, Jacqueline A.
- Journal of The Electrochemical Society, Vol. 165, Issue 14