Liquid Sulfur Impregnation of Microporous Carbon Accelerated by Nanoscale Interfacial Effects

Pascal, Tod A.; Villaluenga, Irune; Wujcik, Kevin H.; Devaux, Didier; Jiang, Xi; Wang, Dunyang Rita; Balsara, Nitash; Prendergast, David

doi:10.1021/acs.nanolett.7b00249

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

Journal Article · Tue Mar 14 00:00:00 EDT 2017 · Nano Letters

DOI: https://doi.org/10.1021/acs.nanolett.7b00249 · OSTI ID:1379807

^[1];

^[2]; Wujcik, Kevin H. ^[2]; Devaux, Didier ^[2]; Jiang, Xi ^[1]; Wang, Dunyang Rita ^[3];

^[2]; Prendergast, David ^[1]

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)

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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

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

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1379807

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 4 Vol. 17; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (34)

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 Wujcik, Kevin H.; Pascal, Tod A.; Pemmaraju, C. D. Advanced Energy Materials, Vol. 5, Issue 16 https://doi.org/10.1002/aenm.201500285	journal	June 2015
Li-S Battery Analyzed by UV/Vis in Operando Mode Patel, Manu U. M.; Demir-Cakan, Rezan; Morcrette, Mathieu ChemSusChem, Vol. 6, Issue 7 https://doi.org/10.1002/cssc.201300142	journal	June 2013
Wettability and work of adhesion of liquid sulfur on carbon materials for electrical energy storage applications Kaban, Ivan; Nowak, Rafał; Bruzda, Grzegorz Carbon, Vol. 98 https://doi.org/10.1016/j.carbon.2015.11.022	journal	March 2016
Li/S fundamental chemistry and application to high-performance rechargeable batteries Akridge, J. Solid State Ionics, Vol. 175, Issue 1-4 https://doi.org/10.1016/j.ssi.2004.07.070	journal	November 2004
Lithium/Sulfur Cell Discharge Mechanism: An Original Approach for Intermediate Species Identification Barchasz, Céline; Molton, Florian; Duboc, Carole Analytical Chemistry, Vol. 84, Issue 9 https://doi.org/10.1021/ac2032244	journal	April 2012
Distribution of Sulfur in Carbon/Sulfur Nanocomposites Analyzed by Small-Angle X-ray Scattering Petzold, Albrecht; Juhl, Anika; Scholz, Jonas Langmuir, Vol. 32, Issue 11 https://doi.org/10.1021/acs.langmuir.5b04734	journal	March 2016
Polysulfide-Blocking Microporous Polymer Membrane Tailored for Hybrid Li-Sulfur Flow Batteries Li, Changyi; Ward, Ashleigh L.; Doris, Sean E. Nano Letters, Vol. 15, Issue 9 https://doi.org/10.1021/acs.nanolett.5b02078	journal	August 2015
Hierarchically Structured Sulfur/Carbon Nanocomposite Material for High-Energy Lithium Battery Liang, Chengdu; Dudney, Nancy J.; Howe, Jane Y. Chemistry of Materials, Vol. 21, Issue 19, p. 4724-4730 https://doi.org/10.1021/cm902050j	journal	October 2009
Elemental sulfur Meyer, Beat Chemical Reviews, Vol. 76, Issue 3 https://doi.org/10.1021/cr60301a003	journal	June 1976
The Surface Tension of Sulfur Fanelli, R. Journal of the American Chemical Society, Vol. 72, Issue 9 https://doi.org/10.1021/ja01165a050	journal	September 1950
Graphene Oxide as a Sulfur Immobilizer in High Performance Lithium/Sulfur Cells Ji, Liwen; Rao, Mumin; Zheng, Haimei Journal of the American Chemical Society, Vol. 133, Issue 46, p. 18522-18525 https://doi.org/10.1021/ja206955k	journal	November 2011
Sulfur Speciation in Li–S Batteries Determined by Operando X-ray Absorption Spectroscopy Cuisinier, Marine; Cabelguen, Pierre-Etienne; Evers, Scott The Journal of Physical Chemistry Letters, Vol. 4, Issue 19 https://doi.org/10.1021/jz401763d	journal	September 2013
X-ray Absorption Spectra of Dissolved Polysulfides in Lithium–Sulfur Batteries from First-Principles Pascal, Tod A.; Wujcik, Kevin H.; Velasco-Velez, Juan The Journal of Physical Chemistry Letters, Vol. 5, Issue 9 https://doi.org/10.1021/jz500260s	journal	April 2014
Phase Transitions in Pores: Experimental and Simulation Studies of Melting and Freezing ^† Sliwinska-Bartkowiak, Malgorzata; Gras, Jolanta; Sikorski, Roman Langmuir, Vol. 15, Issue 18 https://doi.org/10.1021/la9814642	journal	August 1999
Graphene-Wrapped Sulfur Particles as a Rechargeable Lithium–Sulfur Battery Cathode Material with High Capacity and Cycling Stability Wang, Hailiang; Yang, Yuan; Liang, Yongye Nano Letters, Vol. 11, Issue 7, p. 2644-2647 https://doi.org/10.1021/nl200658a	journal	July 2011
Sulphur–TiO₂ yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries Wei Seh, Zhi; Li, Weiyang; Cha, Judy J. Nature Communications, Vol. 4, Article No. 1331 https://doi.org/10.1038/ncomms2327	journal	January 2013
A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries Ji, Xiulei; Lee, Kyu Tae; Nazar, Linda F. Nature Materials, Vol. 8, Issue 6, p. 500-506 https://doi.org/10.1038/nmat2460	journal	May 2009
Observation of extreme phase transition temperatures of water confined inside isolated carbon nanotubes Agrawal, Kumar Varoon; Shimizu, Steven; Drahushuk, Lee W. Nature Nanotechnology, Vol. 12, Issue 3 https://doi.org/10.1038/nnano.2016.254	journal	November 2016
X-ray spectroscopy as a probe for lithium polysulfide radicals Pascal, Tod A.; Pemmaraju, C. D.; Prendergast, David Physical Chemistry Chemical Physics, Vol. 17, Issue 12 https://doi.org/10.1039/C4CP05316H	journal	January 2015
Unique behaviour of nonsolvents for polysulphides in lithium–sulphur batteries Cuisinier, M.; Cabelguen, P. -E.; Adams, B. D. Energy Environ. Sci., Vol. 7, Issue 8 https://doi.org/10.1039/C4EE00372A	journal	January 2014
Carbon–sulfur composites for Li–S batteries: status and prospects Wang, Da-Wei; Zeng, Qingcong; Zhou, Guangmin Journal of Materials Chemistry A, Vol. 1, Issue 33 https://doi.org/10.1039/c3ta11045a	journal	January 2013
Density functional and Monte Carlo studies of sulfur. II. Equilibrium polymerization of the liquid phase Ballone, P.; Jones, R. O. The Journal of Chemical Physics, Vol. 119, Issue 16 https://doi.org/10.1063/1.1611475	journal	October 2003
Quantum mechanics based force field for carbon (QMFF-Cx) validated to reproduce the mechanical and thermodynamics properties of graphite Pascal, Tod A.; Karasawa, Naoki; Goddard, William A. The Journal of Chemical Physics, Vol. 133, Issue 13 https://doi.org/10.1063/1.3456543	journal	October 2010
Phase equilibria and solvation forces for fluids confined between parallel walls Evans, R.; Marini Bettolo Marconi, U. The Journal of Chemical Physics, Vol. 86, Issue 12 https://doi.org/10.1063/1.452363	journal	June 1987
High-performance hollow sulfur nanostructured battery cathode through a scalable, room temperature, one-step, bottom-up approach Li, W.; Zheng, G.; Yang, Y. Proceedings of the National Academy of Sciences, Vol. 110, Issue 18 https://doi.org/10.1073/pnas.1220992110	journal	April 2013
Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries Villaluenga, Irune; Wujcik, Kevin H.; Tong, Wei Proceedings of the National Academy of Sciences, Vol. 113, Issue 1 https://doi.org/10.1073/pnas.1520394112	journal	December 2015
III. An essay on the cohesion of fluids Young, Thomas Philosophical Transactions of the Royal Society of London, Vol. 95, p. 65-87 https://doi.org/10.1098/rstl.1805.0005	journal	January 1805
Higher-accuracy van der Waals density functional Lee, Kyuho; Murray, Éamonn D.; Kong, Lingzhu Physical Review B, Vol. 82, Issue 8 https://doi.org/10.1103/PhysRevB.82.081101	journal	August 2010
The structure of interfacial water on gold electrodes studied by x-ray absorption spectroscopy Velasco-Velez, J. -J.; Wu, C. H.; Pascal, T. A. Science, Vol. 346, Issue 6211 https://doi.org/10.1126/science.1259437	journal	October 2014
A Solid Sulfur Cathode for Aqueous Batteries Peramunage, D.; Licht, S. Science, Vol. 261, Issue 5124 https://doi.org/10.1126/science.261.5124.1029	journal	August 1993
Capillarity and Wetting of Carbon Nanotubes Dujardin, E.; Ebbesen, T. W.; Hiura, H. Science, Vol. 265, Issue 5180 https://doi.org/10.1126/science.265.5180.1850	journal	September 1994
Polysulfide Shuttle Study in the Li/S Battery System Mikhaylik, Yuriy V.; Akridge, James R. Journal of The Electrochemical Society, Vol. 151, Issue 11, p. A1969-A1976 https://doi.org/10.1149/1.1806394	journal	January 2004
Lithium Sulfur Battery: Oxidation/Reduction Mechanisms of Polysulfides in THF Solutions Yamin, H.; Gorenshtein, A.; Penciner, J. Journal of The Electrochemical Society, Vol. 135, Issue 5, p. 1045-1048 https://doi.org/10.1149/1.2095868	journal	January 1988
A Mathematical Model for a Lithium–Sulfur Cell Kumaresan, Karthikeyan; Mikhaylik, Yuriy; White, Ralph E. Journal of The Electrochemical Society, Vol. 155, Issue 8 https://doi.org/10.1149/1.2937304	journal	January 2008

Cited By (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 Kong, Chui-Peng; Gao, Xin; Jia, Ran Journal of Computational Chemistry, Vol. 40, Issue 10 https://doi.org/10.1002/jcc.25593	journal	October 2018
Review of Carbon Materials for Lithium-Sulfur Batteries Li, Shanshan; Jin, Bo; Zhai, Xiaojie ChemistrySelect, Vol. 3, Issue 8 https://doi.org/10.1002/slct.201703112	journal	February 2018
Rate Constants of Electrochemical Reactions in a Lithium-Sulfur Cell Determined by Operando X-ray Absorption Spectroscopy Wang, Dunyang Rita; Shah, Deep B.; Maslyn, Jacqueline A. Journal of The Electrochemical Society, Vol. 165, Issue 14 https://doi.org/10.1149/2.0981814jes	journal	January 2018
Brush-structured sulfur–polyaniline–graphene composite as cathodes for lithium–sulfur batteries Liu, Heguang; Jing, Ruixuan; You, Caiyin MRS Communications, Vol. 9, Issue 4 https://doi.org/10.1557/mrc.2019.149	journal	November 2019

Similar Records

Compositions and Formation Mechanisms of Solid-Electrolyte Interphase on Microporous Carbon/Sulfur Cathodes

Journal Article · Thu Apr 02 00:00:00 EDT 2020 · Chemistry of Materials · OSTI ID:1634803

Wang, Luning; Lin, Yuxiao; DeCarlo, Samantha; +6 more

Graphene-wrapped sulfur/metal organic framework-derived microporous carbon composite for lithium sulfur batteries

Journal Article · Sun Nov 30 23:00:00 EST 2014 · APL materials · OSTI ID:22415228

Chen, Renjie; Zhao, Teng; Tian, Tian; +6 more

Sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries

Patent · Tue May 05 00:00:00 EDT 2015 · OSTI ID:1179030

Liang, Chengdu; Dudney, Nancy J; Howe, Jane Y

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
battery
computer simulation
energy storage
entropy
free energy
molecular dynamics
nanoscale
spectroscopy
sulfur

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

Citation Formats

References (34)

Cited By (4)

Similar Records

Related Subjects