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Title: Sulfur Diffusion within Nitrogen-Doped Ordered Mesoporous Carbons Determined by in Situ X-ray Scattering

Abstract

The low intrinsic conductivity of sulfur necessitates conductive additives, such as mesoporous carbons, to the cathode to enable high-performance metal–sulfur batteries. Simultaneous efforts to address polysulfide shuttling have introduced nitrogen-doped carbons to provide both conductivity and suppressed shuttling because of their strong interaction with sulfur. The strength of this interaction will impact the ability to fill the mesopores with sulfur via melt infusion. Here in this study, we systematically investigate how nitrogen doping influences the rate that molten sulfur can infiltrate the mesopores and the overall extent of pore filling of highly ordered mesoporous doped carbons using in situ small angle X-ray scattering (SAXS). The similarity in electron density between molten sulfur and the soft carbon framework of the mesoporous material leads to a precipitous decrease in the scattered intensity associated with the ordered structure as voids are filled with sulfur. As the nitrogen doping increases from 1 to 20 at. %, the effective diffusivity of sulfur in the mesopores decreases by an order of magnitude (2.7 × 10 –8 to 2.3 × 10 –9 cm/s). The scattering becomes nearly invariant within 20 min of melt infiltration at 155 °C for all but the most doped carbon, which indicates thatmore » submicron-sized mesoporous carbon particles can be filled rapidly. Additionally, the nitrogen doping decreases the sulfur content that can be accommodated within the mesopores from 95% of the mesopores filled without doping to only 64% filled with 20 at. % N as determined by the residual scattering intensity. Sulfur does not crystallize within the mesopores of the nitrogen-doped carbons, which is further indicative of the strong interactions between the nitrogen species and sulfur that can inhibit polysulfide shuttling. Lastly, in situ SAXS provides insights into the diffusion of sulfur in mesopores and how the surface chemistry of nitrogen-doped carbon appears to significantly hinder the infiltration by sulfur.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [3]; ORCiD logo [2]
  1. The University of Akron, OH (United States). Department of Polymer Science, Goodyear Polymer Center
  2. The University of Akron, OH (United States). Department of Polymer Engineering
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1473640
Report Number(s):
BNL-209078-2018-JAAM
Journal ID: ISSN 0743-7463
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 34; Journal Issue: 30; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Xia, Yanfeng, Wang, Chao, Li, Ruipeng, Fukuto, Masafumi, and Vogt, Bryan D. Sulfur Diffusion within Nitrogen-Doped Ordered Mesoporous Carbons Determined by in Situ X-ray Scattering. United States: N. p., 2018. Web. doi:10.1021/acs.langmuir.8b01375.
Xia, Yanfeng, Wang, Chao, Li, Ruipeng, Fukuto, Masafumi, & Vogt, Bryan D. Sulfur Diffusion within Nitrogen-Doped Ordered Mesoporous Carbons Determined by in Situ X-ray Scattering. United States. doi:10.1021/acs.langmuir.8b01375.
Xia, Yanfeng, Wang, Chao, Li, Ruipeng, Fukuto, Masafumi, and Vogt, Bryan D. Thu . "Sulfur Diffusion within Nitrogen-Doped Ordered Mesoporous Carbons Determined by in Situ X-ray Scattering". United States. doi:10.1021/acs.langmuir.8b01375. https://www.osti.gov/servlets/purl/1473640.
@article{osti_1473640,
title = {Sulfur Diffusion within Nitrogen-Doped Ordered Mesoporous Carbons Determined by in Situ X-ray Scattering},
author = {Xia, Yanfeng and Wang, Chao and Li, Ruipeng and Fukuto, Masafumi and Vogt, Bryan D.},
abstractNote = {The low intrinsic conductivity of sulfur necessitates conductive additives, such as mesoporous carbons, to the cathode to enable high-performance metal–sulfur batteries. Simultaneous efforts to address polysulfide shuttling have introduced nitrogen-doped carbons to provide both conductivity and suppressed shuttling because of their strong interaction with sulfur. The strength of this interaction will impact the ability to fill the mesopores with sulfur via melt infusion. Here in this study, we systematically investigate how nitrogen doping influences the rate that molten sulfur can infiltrate the mesopores and the overall extent of pore filling of highly ordered mesoporous doped carbons using in situ small angle X-ray scattering (SAXS). The similarity in electron density between molten sulfur and the soft carbon framework of the mesoporous material leads to a precipitous decrease in the scattered intensity associated with the ordered structure as voids are filled with sulfur. As the nitrogen doping increases from 1 to 20 at. %, the effective diffusivity of sulfur in the mesopores decreases by an order of magnitude (2.7 × 10–8 to 2.3 × 10–9 cm/s). The scattering becomes nearly invariant within 20 min of melt infiltration at 155 °C for all but the most doped carbon, which indicates that submicron-sized mesoporous carbon particles can be filled rapidly. Additionally, the nitrogen doping decreases the sulfur content that can be accommodated within the mesopores from 95% of the mesopores filled without doping to only 64% filled with 20 at. % N as determined by the residual scattering intensity. Sulfur does not crystallize within the mesopores of the nitrogen-doped carbons, which is further indicative of the strong interactions between the nitrogen species and sulfur that can inhibit polysulfide shuttling. Lastly, in situ SAXS provides insights into the diffusion of sulfur in mesopores and how the surface chemistry of nitrogen-doped carbon appears to significantly hinder the infiltration by sulfur.},
doi = {10.1021/acs.langmuir.8b01375},
journal = {Langmuir},
number = 30,
volume = 34,
place = {United States},
year = {2018},
month = {7}
}

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