Colored Sulfur Species in Epd-Solvents

Seel, F.; Güttler, Hans‐Joachim; Simon, Georg; Wiȩckowski, Andrzej

doi:10.1016/b978-0-08-021202-9.50008-4

Cited by 6 publications

(10 citation statements)

References 21 publications

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“…A comprehensive list of each solution's g factor can be found in the Supporting Information. These g factors are similar to those previously obtained for the S 3 •− radical (2.029) 7,12,18,20,28,46 and the S 4…”

Section: ■ Experimental Sectionsupporting

confidence: 90%

“…10,11 It has been argued that the presence of radical species (here we refer to polysulfide radical anions as radicals or radical species for simplicity) in a particular lithium sulfur cell depends primarily on the electron pair donor (EPD) number of the electrolyte. 12,13 Solvents with high EPD numbers may stabilize radical polysulfides, while solvents with low EPD numbers do not.…”

Section: ■ Introductionmentioning

confidence: 99%

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Lithium Polysulfide Radical Anions in Ether-Based Solvents

et al. 2016

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Lithium sulfur batteries have a theoretical specific energy 5 times greater than current lithium ion battery standards, but suffer from the issue of lithium polysulfide dissolution. The reaction mechanisms that underlie the formation of lithium polysulfide reaction intermediates have been studied for over four decades, yet still elude researchers. Polysulfide radical anions formed during the redox processes have become a focal point of fundamental Li−S battery research. The formation of radical species has even been shown to be advantageous to the electrochemical pathways. However, whether polysulfide radical anions can form and be stabilized in common Li−S battery electrolytes that are ether-based is a point of contention in Li−S battery research. The goal of this work was to examine the presence of radical polysulfide species in ether-based solvents. Lithium polysulfide solutions in tetraethylene glycol dimethyl ether and poly(ethylene oxide) are probed using a combination of ultraviolet−visible (UV−vis) and electron paramagnetic resonance (EPR) spectroscopy. EPR results confirm the presence of radical species in ether-based electrolytes. Comparison of the UV−vis spectra to EPR spectra establishes that the UV−vis absorbance signature for radical species in ether-based solvents occurs at a wavelength of 617 nm, which is consistent with what is observed for high electron pair donor solvents such as dimethylformamide and dimethyl sulfoxide.

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Section: ■ Experimental Sectionsupporting

confidence: 90%

Section: ■ Introductionmentioning

confidence: 99%

Lithium Polysulfide Radical Anions in Ether-Based Solvents

et al. 2016

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“…The chemistry of polysulfides is closely related to that of the radical monoanions S x •– (eqs and ) in that they are in equilibrium with each other. In solution these radicals are formed by homolytic dissociation of the polysulfide anions, a process that is enhanced in solvents of lower polarity than water and/or by higher temperatures. , In aqueous solutions at room temperature, the reactions given in eqs and are shifted to the left. However, if the solutions are very dilute, then radical anions could be more abundant.…”

Section: Cellular Mechanisms Of Persulfide Formation and Removalmentioning

confidence: 99%

Chemical Biology of H₂S Signaling through Persulfidation

et al. 2017

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Signaling by HS is proposed to occur via persulfidation, a posttranslational modification of cysteine residues (RSH) to persulfides (RSSH). Persulfidation provides a framework for understanding the physiological and pharmacological effects of HS. Due to the inherent instability of persulfides, their chemistry is understudied. In this review, we discuss the biologically relevant chemistry of HS and the enzymatic routes for its production and oxidation. We cover the chemical biology of persulfides and the chemical probes for detecting them. We conclude by discussing the roles ascribed to protein persulfidation in cell signaling pathways.

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“…First, sodium polysulfides of different lengths were synthesized by mixing sodium sulfide and elemental sulfur at different ratios in a polar high boiling solvent such as N -methyl pyrrolidone (NMP). This is known to result in a complex equilibrium of different polysulfide dianionic species . Next, 1,5-chloroanthraquinone was added to this mixture and reacted under magnetic stirring overnight at 120 °C.…”

mentioning

confidence: 99%

“…This is known to result in a complex equilibrium of different polysulfide dianionic species. 12 Next, 1,5-chloroanthraquinone was added to this mixture and reacted under magnetic stirring overnight at 120 °C. As a result, a colored precipitate appeared in high yield, which was recovered by filtration, washed, and dried under high vacuum.…”

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confidence: 99%

Poly(anthraquinonyl sulfides): High Capacity Redox Polymers for Energy Storage

et al. 2018

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Redox polymers with high energy storage capacity are searched in order to diminish the weight to the actual batteries. Poly(anthraquinonyl sulfide) PAQS is a popular redox polymer which has shown a high performance cathode for lithium, sodium and magnesium batteries. Although PAQS cathodes show high cycling stability it has a relatively low theoretical specific capacity of 225 mAh/g. In this paper we show the synthesis and characterization of new poly(anthraquinonyl sulfides) PAQxS in an attempt to improve the specific capacity of PAQS. Thus, a series of PAQxS polymers with different polysulfide segment lengths (x between 2 and 9 sulfur atoms) have been synthesized in high yields by reacting in situ formed sodium polysulfides with 1,5-dicholoroanthraquinone. The poly(anthraquinonyl sulfides) powders were characterized by ATR-FTIR, solid state 13C NMR for the organic part and Raman spectroscopy for the chalcogenide part. This characterization confirmed the chemical structure of the PAQxS based on an anthraquinone moiety bind together by polysulfide segments. The electrochemical characterization showed a dual reversible redox mechanism associated with both the anthraquinone and polysulfide electrochemistry. Finally, lithium coin cell battery test of the PAQxS redox polymers as cathodes indicated that the capacity of poly(anthraquinonyl sulfides) showed very high experimental initial capacity values above 600 mAh/g, less capacity loss than sulfur cathodes, and higher steady state capacity than PAQS.

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Colored Sulfur Species in Epd-Solvents

Cited by 6 publications

References 21 publications

Lithium Polysulfide Radical Anions in Ether-Based Solvents

Lithium Polysulfide Radical Anions in Ether-Based Solvents

Chemical Biology of H₂S Signaling through Persulfidation

Poly(anthraquinonyl sulfides): High Capacity Redox Polymers for Energy Storage

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Colored Sulfur Species in Epd-Solvents

Cited by 6 publications

References 21 publications

Lithium Polysulfide Radical Anions in Ether-Based Solvents

Lithium Polysulfide Radical Anions in Ether-Based Solvents

Chemical Biology of H2S Signaling through Persulfidation

Poly(anthraquinonyl sulfides): High Capacity Redox Polymers for Energy Storage

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Chemical Biology of H₂S Signaling through Persulfidation