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Covalent Trapping of Cyclic-Polysulfides in Perfluorinated Vinylene-Linked Frameworks for Designing Lithium-Organosulfide Batteries

Haldar, Sattwick; Waentig, Albrecht L; Ramuglia, Anthony R; Bhauriyal, Preeti; Khan, Arafat H; Pastoetter, Dominik L; Isaacs, Mark A; ... Kaskel, Stefan; + view all (2023) Covalent Trapping of Cyclic-Polysulfides in Perfluorinated Vinylene-Linked Frameworks for Designing Lithium-Organosulfide Batteries. ACS Energy Letters , 8 pp. 5098-5106. 10.1021/acsenergylett.3c01548.

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Abstract

The strategic combination of redox-active triazine- or quinoxaline-based lithium-ion battery (LIB) mechanisms with the polysulfide ring-mediated lithium-sulfur battery (Li-SB) mechanism enabled the configuration of covalent organic-framework (COF)-derived lithium-organosulfide (Li-OrSB) battery systems. Two vinylene-linked frameworks were designed by enclosing polysulfide rings via postsynthetic framework sulfurization, allowing for the separate construction of triazine-polysulfide and quinoxaline-polysulfide redox couples that can readily interact with Li ions. The inverse vulcanization of the vinylene linking followed by the sulfurization-induced nucleophilic aromatic substitution reaction (SNAr) on the perfluorinated aromatic center of the COFs enabled the covalent trapping of cyclic-polysulfides. The experimentally observed reversible Li-interaction mechanism of these highly conjugated frameworks was computationally verified and supported by in situ Raman studies, demonstrating a significant reduction of polysulfide shuttle in a conventional Li-SB and opening the door for a COF-derived high-performing Li-OrSB.

Type: Article
Title: Covalent Trapping of Cyclic-Polysulfides in Perfluorinated Vinylene-Linked Frameworks for Designing Lithium-Organosulfide Batteries
DOI: 10.1021/acsenergylett.3c01548
Publisher version: https://doi.org/10.1021/acsenergylett.3c01548
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions.
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10183062
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