4 research outputs found
Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium-Sulfur Battery Cathodes
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
Covalent Trapping of Cyclic-Polysulfides in Perfluorinated Vinylene-Linked Frameworks for Designing Lithium-Organosulfide Batteries
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
Tuning the Planarity of an Aromatic Thianthrene-Based Molecule on Au(111)
Nonplanar aromatic molecules are interesting systems
for organic
electronics and optoelectronics applications due to their high stability
and electronic properties. By using scanning tunneling microscopy
and spectroscopy, we investigated thianthrene-based molecules adsorbed
on Au(111), which are nonplanar in the gas phase and the bulk solid
state. Varying the molecular coverage leads to the formation of two
different kinds of self-assembled structures: close-packed islands
and quasi-one-dimensional chains. We found that the molecules are
nonplanar within the close-packed islands, while the configuration
is planar in the molecular chain and for single adsorbed molecules.
Using vertical tip manipulation to isolate a molecule from the island,
we demonstrate the conversion of a nonplanar molecule to its planar
configuration. We discuss the two different geometries and their electronic
properties with the support of density functional theory calculations
Sulfide Bridged Covalent Quinoxaline Frameworks for Lithium-Organo-Sulfide Battery
The chelating ability of quinoxaline cores and the redox activity of organo-sulfide bridges in layered covalent-organic frameworks (COFs) offer dual active sites for reversible lithium (Li)-storage. The designed COFs combining these properties feature disulfide and polysulfide-bridged networks showcasing an intriguing lithium-storage mechanism, which can be considered as a lithium-organo-sulfide (Li-OrS) battery. The experimental-computational elucidation of three quinoxaline COFs containing systematically enhanced sulfur atoms in sulfide bridging demonstrates fast kinetics during Li interactions with the quinoxaline core. Meanwhile, bilateral covalent bonding of sulfide bridges to quinoxaline core enables a redox-mediated reversible cleavage of the sulfur-sulfur bond and the formation of covalently anchored lithium-sulfide chains or clusters during Li-interactions, accompanied by a marked reduction of Li-polysulfide (Li-PS) dissolution into the electrolyte, a frequent drawback of lithium-sulfur (Li-S) batteries. The electrochemical behavior of model compounds mimicking the sulfide linkages of the COFs and operando Raman studies on the framework structure unravels the reversibility of the profound Li-ion-organo-sulfide interactions. As a result, nearly 84% retention of specific capacity was observed at 100Â mA/g for the polysulfide-bridged COF after 500 charge-discharge cycles. Thus, integrating redox-active organic-framework materials with covalently anchored sulfides enables a stable Li-OrS battery mechanism which shows benefits over a typical Li-S battery. This article is protected by copyright. All rights reserved