Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium-Sulfur Battery Cathodes

Sattwick Haldar; Mingchao Wang; Preeti Bhauriyal; Arpan Hazra; Arafat H. Khan; Volodymyr Bon; Mark A. Isaacs; Ankita De; Leonid Shupletsov; Tom Boenke; Julia Grothe; Thomas Heine; Eike Brunner; Xinliang Feng; Renhao Dong; Andreas Schneemann; Stefan Kaskel

doi:10.1021/jacs.2c02346

Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium-Sulfur Battery Cathodes

Sattwick Haldar, Mingchao Wang, Preeti Bhauriyal, Arpan Hazra, Arafat H. Khan, Volodymyr Bon, Mark A. Isaacs, Ankita De, Leonid Shupletsov, Tom Boenke, Julia Grothe, Thomas Heine, Eike Brunner, Xinliang Feng, Renhao Dong, Andreas Schneemann, Stefan Kaskel

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

27 Citations (Scopus)

Abstract

Dithiine linkage formation via a dynamic and self-correcting nucleophilic aromatic substitution reaction enables the de novo synthesis of a porous thianthrene-based two-dimensional covalent organic framework (COF). For the first time, this organo-sulfur moiety is integrated as a structural building block into a crystalline layered COF. The structure of the new material deviates from the typical planar interlayer π-stacking of the COF to form undulated layers caused by bending along the C-S-C bridge, without loss of aromaticity and crystallinity of the overall COF structure. Comprehensive experimental and theoretical investigations of the COF and a model compound, featuring the thianthrene moiety, suggest partial delocalization of sulfur lone pair electrons over the aromatic backbone of the COF decreasing the band gap and promoting redox activity. Postsynthetic sulfurization allows for direct covalent attachment of polysulfides to the carbon backbone of the framework to afford a molecular-designed cathode material for lithium-sulfur (Li-S) batteries with a minimized polysulfide shuttle. The fabricated coin cell delivers nearly 77% of the initial capacity even after 500 charge-discharge cycles at 500 mA/g current density. This novel sulfur linkage in COF chemistry is an ideal structural motif for designing model materials for studying advanced electrode materials for Li-S batteries on a molecular level.

Original language	English
Pages (from-to)	9101-9112
Number of pages	12
Journal	Journal of the American Chemical Society
Volume	144
Issue number	20
DOIs	https://doi.org/10.1021/jacs.2c02346
Publication status	Published - 2022 May 25

Bibliographical note

Funding Information:
This work was supported by the DFG Priority Programme “Polymer-based Batteries” (SPP 2248). The authors are grateful for the support from collaborative research center “Chemistry of Synthetic 2D Materials” funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation)─SFB-1415-417590517. P.B. acknowledges the Alexander von Humboldt Foundation for funding. A.S. gratefully acknowledges the Fonds der Chemischen Industrie for a Liebig Fellowship. The X-ray photoelectron (XPS) data collection was performed at the EPSRC National Facility for XPS (“HarwellXPS”), operated by Cardiff University and UCL, under contract no. PR16195. Single-crystal X-ray diffraction data have been collected on BL14.2 at the BESSY II electron storage ring operated by the Helmholtz-Zentrum Berlin. We would particularly like to acknowledge the help and support of Dr. U. Mueller and Dr. Th. Hauß during the experiment. We thank the Center for Information Services and High-Performance Computing (ZIH) at TU Dresden for generous allocations of computer time. We also acknowledge the use of the facilities in the Dresden Center for Nanoanalysis (DCN) at the Technische Universität Dresden.

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.2c02346

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Haldar, S., Wang, M., Bhauriyal, P., Hazra, A., Khan, A. H., Bon, V., Isaacs, M. A., De, A., Shupletsov, L., Boenke, T., Grothe, J., Heine, T., Brunner, E., Feng, X., Dong, R., Schneemann, A., & Kaskel, S. (2022). Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium-Sulfur Battery Cathodes. Journal of the American Chemical Society, 144(20), 9101-9112. https://doi.org/10.1021/jacs.2c02346

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title = "Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium-Sulfur Battery Cathodes",

abstract = "Dithiine linkage formation via a dynamic and self-correcting nucleophilic aromatic substitution reaction enables the de novo synthesis of a porous thianthrene-based two-dimensional covalent organic framework (COF). For the first time, this organo-sulfur moiety is integrated as a structural building block into a crystalline layered COF. The structure of the new material deviates from the typical planar interlayer π-stacking of the COF to form undulated layers caused by bending along the C-S-C bridge, without loss of aromaticity and crystallinity of the overall COF structure. Comprehensive experimental and theoretical investigations of the COF and a model compound, featuring the thianthrene moiety, suggest partial delocalization of sulfur lone pair electrons over the aromatic backbone of the COF decreasing the band gap and promoting redox activity. Postsynthetic sulfurization allows for direct covalent attachment of polysulfides to the carbon backbone of the framework to afford a molecular-designed cathode material for lithium-sulfur (Li-S) batteries with a minimized polysulfide shuttle. The fabricated coin cell delivers nearly 77% of the initial capacity even after 500 charge-discharge cycles at 500 mA/g current density. This novel sulfur linkage in COF chemistry is an ideal structural motif for designing model materials for studying advanced electrode materials for Li-S batteries on a molecular level.",

author = "Sattwick Haldar and Mingchao Wang and Preeti Bhauriyal and Arpan Hazra and Khan, {Arafat H.} and Volodymyr Bon and Isaacs, {Mark A.} and Ankita De and Leonid Shupletsov and Tom Boenke and Julia Grothe and Thomas Heine and Eike Brunner and Xinliang Feng and Renhao Dong and Andreas Schneemann and Stefan Kaskel",

note = "Funding Information: This work was supported by the DFG Priority Programme “Polymer-based Batteries” (SPP 2248). The authors are grateful for the support from collaborative research center “Chemistry of Synthetic 2D Materials” funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation)─SFB-1415-417590517. P.B. acknowledges the Alexander von Humboldt Foundation for funding. A.S. gratefully acknowledges the Fonds der Chemischen Industrie for a Liebig Fellowship. The X-ray photoelectron (XPS) data collection was performed at the EPSRC National Facility for XPS (“HarwellXPS”), operated by Cardiff University and UCL, under contract no. PR16195. Single-crystal X-ray diffraction data have been collected on BL14.2 at the BESSY II electron storage ring operated by the Helmholtz-Zentrum Berlin. We would particularly like to acknowledge the help and support of Dr. U. Mueller and Dr. Th. Hau{\ss} during the experiment. We thank the Center for Information Services and High-Performance Computing (ZIH) at TU Dresden for generous allocations of computer time. We also acknowledge the use of the facilities in the Dresden Center for Nanoanalysis (DCN) at the Technische Universit{\"a}t Dresden. Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

year = "2022",

month = may,

day = "25",

doi = "10.1021/jacs.2c02346",

language = "English",

volume = "144",

pages = "9101--9112",

journal = "Journal of the American Chemical Society",

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publisher = "American Chemical Society",

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Haldar, S, Wang, M, Bhauriyal, P, Hazra, A, Khan, AH, Bon, V, Isaacs, MA, De, A, Shupletsov, L, Boenke, T, Grothe, J, Heine, T, Brunner, E, Feng, X, Dong, R, Schneemann, A & Kaskel, S 2022, 'Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium-Sulfur Battery Cathodes', Journal of the American Chemical Society, vol. 144, no. 20, pp. 9101-9112. https://doi.org/10.1021/jacs.2c02346

TY - JOUR

T1 - Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium-Sulfur Battery Cathodes

AU - Haldar, Sattwick

AU - Wang, Mingchao

AU - Bhauriyal, Preeti

AU - Hazra, Arpan

AU - Khan, Arafat H.

AU - Bon, Volodymyr

AU - Isaacs, Mark A.

AU - De, Ankita

AU - Shupletsov, Leonid

AU - Boenke, Tom

AU - Grothe, Julia

AU - Heine, Thomas

AU - Brunner, Eike

AU - Feng, Xinliang

AU - Dong, Renhao

AU - Schneemann, Andreas

AU - Kaskel, Stefan

N1 - Funding Information: This work was supported by the DFG Priority Programme “Polymer-based Batteries” (SPP 2248). The authors are grateful for the support from collaborative research center “Chemistry of Synthetic 2D Materials” funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation)─SFB-1415-417590517. P.B. acknowledges the Alexander von Humboldt Foundation for funding. A.S. gratefully acknowledges the Fonds der Chemischen Industrie for a Liebig Fellowship. The X-ray photoelectron (XPS) data collection was performed at the EPSRC National Facility for XPS (“HarwellXPS”), operated by Cardiff University and UCL, under contract no. PR16195. Single-crystal X-ray diffraction data have been collected on BL14.2 at the BESSY II electron storage ring operated by the Helmholtz-Zentrum Berlin. We would particularly like to acknowledge the help and support of Dr. U. Mueller and Dr. Th. Hauß during the experiment. We thank the Center for Information Services and High-Performance Computing (ZIH) at TU Dresden for generous allocations of computer time. We also acknowledge the use of the facilities in the Dresden Center for Nanoanalysis (DCN) at the Technische Universität Dresden. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/5/25

Y1 - 2022/5/25

N2 - Dithiine linkage formation via a dynamic and self-correcting nucleophilic aromatic substitution reaction enables the de novo synthesis of a porous thianthrene-based two-dimensional covalent organic framework (COF). For the first time, this organo-sulfur moiety is integrated as a structural building block into a crystalline layered COF. The structure of the new material deviates from the typical planar interlayer π-stacking of the COF to form undulated layers caused by bending along the C-S-C bridge, without loss of aromaticity and crystallinity of the overall COF structure. Comprehensive experimental and theoretical investigations of the COF and a model compound, featuring the thianthrene moiety, suggest partial delocalization of sulfur lone pair electrons over the aromatic backbone of the COF decreasing the band gap and promoting redox activity. Postsynthetic sulfurization allows for direct covalent attachment of polysulfides to the carbon backbone of the framework to afford a molecular-designed cathode material for lithium-sulfur (Li-S) batteries with a minimized polysulfide shuttle. The fabricated coin cell delivers nearly 77% of the initial capacity even after 500 charge-discharge cycles at 500 mA/g current density. This novel sulfur linkage in COF chemistry is an ideal structural motif for designing model materials for studying advanced electrode materials for Li-S batteries on a molecular level.

AB - Dithiine linkage formation via a dynamic and self-correcting nucleophilic aromatic substitution reaction enables the de novo synthesis of a porous thianthrene-based two-dimensional covalent organic framework (COF). For the first time, this organo-sulfur moiety is integrated as a structural building block into a crystalline layered COF. The structure of the new material deviates from the typical planar interlayer π-stacking of the COF to form undulated layers caused by bending along the C-S-C bridge, without loss of aromaticity and crystallinity of the overall COF structure. Comprehensive experimental and theoretical investigations of the COF and a model compound, featuring the thianthrene moiety, suggest partial delocalization of sulfur lone pair electrons over the aromatic backbone of the COF decreasing the band gap and promoting redox activity. Postsynthetic sulfurization allows for direct covalent attachment of polysulfides to the carbon backbone of the framework to afford a molecular-designed cathode material for lithium-sulfur (Li-S) batteries with a minimized polysulfide shuttle. The fabricated coin cell delivers nearly 77% of the initial capacity even after 500 charge-discharge cycles at 500 mA/g current density. This novel sulfur linkage in COF chemistry is an ideal structural motif for designing model materials for studying advanced electrode materials for Li-S batteries on a molecular level.

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DO - 10.1021/jacs.2c02346

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JO - Journal of the American Chemical Society

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ER -

Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium-Sulfur Battery Cathodes

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