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

Yanfeng Xia, Chao Wang, Ruipeng Li, Masafumi Fukuto, Bryan Vogt

Research output: Contribution to journalArticle

1 Citation (Scopus)

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, 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. 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.

Original languageEnglish (US)
Pages (from-to)8767-8776
Number of pages10
JournalLangmuir
Volume34
Issue number30
DOIs
StatePublished - Jul 31 2018

Fingerprint

X ray scattering
Sulfur
Nitrogen
sulfur
Carbon
nitrogen
carbon
scattering
x rays
Doping (additives)
polysulfides
Polysulfides
infiltration
Infiltration
Molten materials
Scattering
Mesoporous materials
low conductivity
Surface chemistry
diffusivity

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry

Cite this

Xia, Yanfeng ; Wang, Chao ; Li, Ruipeng ; Fukuto, Masafumi ; Vogt, Bryan. / Sulfur Diffusion within Nitrogen-Doped Ordered Mesoporous Carbons Determined by in Situ X-ray Scattering. In: Langmuir. 2018 ; Vol. 34, No. 30. pp. 8767-8776.
@article{80c86772779f430088e15fcaa6dd84a3,
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, 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. 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.",
author = "Yanfeng Xia and Chao Wang and Ruipeng Li and Masafumi Fukuto and Bryan Vogt",
year = "2018",
month = "7",
day = "31",
doi = "10.1021/acs.langmuir.8b01375",
language = "English (US)",
volume = "34",
pages = "8767--8776",
journal = "Langmuir",
issn = "0743-7463",
publisher = "American Chemical Society",
number = "30",

}

Sulfur Diffusion within Nitrogen-Doped Ordered Mesoporous Carbons Determined by in Situ X-ray Scattering. / Xia, Yanfeng; Wang, Chao; Li, Ruipeng; Fukuto, Masafumi; Vogt, Bryan.

In: Langmuir, Vol. 34, No. 30, 31.07.2018, p. 8767-8776.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Sulfur Diffusion within Nitrogen-Doped Ordered Mesoporous Carbons Determined by in Situ X-ray Scattering

AU - Xia, Yanfeng

AU - Wang, Chao

AU - Li, Ruipeng

AU - Fukuto, Masafumi

AU - Vogt, Bryan

PY - 2018/7/31

Y1 - 2018/7/31

N2 - 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, 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. 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.

AB - 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, 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. 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.

UR - http://www.scopus.com/inward/record.url?scp=85049795422&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85049795422&partnerID=8YFLogxK

U2 - 10.1021/acs.langmuir.8b01375

DO - 10.1021/acs.langmuir.8b01375

M3 - Article

C2 - 29975064

AN - SCOPUS:85049795422

VL - 34

SP - 8767

EP - 8776

JO - Langmuir

JF - Langmuir

SN - 0743-7463

IS - 30

ER -