Reactions of Elemental Sulfur. I. The Uncatalyzed Reaction of Sulfur with Triarylphosphines<sup>1</sup>

Bartlett, Paul D.; Meguerian, G. H.

doi:10.1021/ja01596a043

Cited by 147 publications

(79 citation statements)

References 2 publications

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“…9a). 95 Transmission electron microscopy (TEM) was used to analyze the generation of the wrapping layer: the original CMK-3/S particles displayed a clean surface; a coating layer with a thickness of ∼40 nm or less was found on the surface of CMK-3/S@PANS particles; after soaking in TPP-added electrolyte, an additional coating layer as thin as ∼15 nm was observed in the CMK-3/S@PANS@TPS sample ( Fig. 9b-9d).…”

Section: In Situ Wrapping Approach To Build Li-s Cathode With Better mentioning

confidence: 99%

Review—From Nano Size Effect to In Situ Wrapping: Rational Design of Cathode Structure for High Performance Lithium−Sulfur Batteries

Chen

Shen

Wang

et al. 2017

J. Electrochem. Soc.

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Rechargeable Li-S batteries have become attractive for next-generation energy storage technology due to their high specific energy, low cost, and materials earth abundance. However, the Li-S technology has not been successfully commercialized because of several outstanding challenges including fast capacity fading, low Coulombic efficiency, and limited rate capability. Over the past few years, considerable efforts have been devoted to solving the challenges associated with the sulfur cathode. In this mini review, we summarize our recent advances in Li-S cathodes, such as the understanding of the nano-size effect in sulfur materials, the design of polymer functional additives, and the realization of a novel in situ wrapping approach for Li-S cathodes. The current Li-S technology calls for a rational design of the Li-S cathode that can lead to excellent overall performance of Li-S batteries. Sulfur is a promising cathode material, which is highly earth abundant and with a theoretical specific capacity as high as 1672 mAh g −1 . When the sulfur cathode couples with a lithium metal anode to assemble rechargeable lithium-sulfur (Li-S) batteries, their theoretical specific energy density can reach 2600 Wh kg −1 , which is 3-5 folds higher than those of state-of-the-art Li-ion batteries.1-3 Because of the high energy density and low cost, rechargeable Li-S batteries are promising for applications not only in consumer electronics but also in energy storage and electric vehicles. [4][5][6] Although the research on Li-S batteries has been ongoing for over three decades, two major challenges still remain in this field: one is the low specific capacity due to high electrical resistivity of elementary S and the solid reduction products ((Li 2 S 2 and Li 2 S)) in the cathodes; the other is the fast capacity fading owing to the shuttle effect, i.e. polysulfide intermediates formed during discharge/charge cycles dissolve in the electrolyte, diffuse to the anode, react with Li metal, and form insoluble Li 2 S 2 and Li 2 S at the anodic region, leading to the loss of lithium metal and sulfur cathodic materials. 7,8 In the past few years, researches have mainly focused on designing nanostructured sulfur host materials to address challenges related to poor electrical conductivity of S/Li 2 S 2 /Li 2 S.9-19 A quantum leap for the nanostructure approach was the utilization of ordered mesoporous carbon CMK-3 to trap sulfur, as reported by Nazar et al. in 2009. 20 The conductive mesoporous carbon framework precisely constrains the growth of sulfur within its channels and thus enables fast electronic and ionic transport. Following this work, Cui et al. designed a series of sulfur nanostructures with complicated host materials demonstrating excellent electrochemical performances.9 Various nanostructured host materials, including but not limited to carbon/sulfur, 11,14,16,17,21 polymer/sulfur, [22][23][24] and metal oxide/sulfur composites 12,25,26 have been investigated. These nanostructures provide new merits and opportunities: (1)...

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Section: In Situ Wrapping Approach To Build Li-s Cathode With Better mentioning

confidence: 99%

Review—From Nano Size Effect to In Situ Wrapping: Rational Design of Cathode Structure for High Performance Lithium−Sulfur Batteries

Chen

Shen

Wang

et al. 2017

J. Electrochem. Soc.

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“…This is in line with the studies of Bartlett et al on the catalytic effects of amines on the reaction of sulfur with triphenylphosphine (PPh 3 ) as well as of Mathey et al for the generation and trapping of a phosphinine sulfide. [24,25] Crystals of 5 and 6 suitable for X-ray diffraction were obtained by slowly cooling the reaction media to room temperature, and the molecular plots of the structures are shown in Figures 6 and 7, respectively, along with selected bond lengths and angles.…”

Section: P{mentioning

confidence: 99%

Reactivity of Aromatic Phosphorus Heterocycles – Differences Between Nonfunctionalized and Pyridyl‐Substituted 2,4,6‐Triarylphosphinines

et al. 2014

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Detailed studies on the reactivity of 2‐(2′‐pyridyl)‐4,6‐diphenylphosphinine (2) towards CF3SO3H and sulfur have been performed, and the results were compared with those for nonfunctionalized 2,4,6‐triphenylphosphinine derivatives. Substantial differences between these heterocycles were observed, and the reaction products could be characterized crystallographically. The reactions of 2,4,6‐triarylphosphinine sulfides with methanol led to different products, which could be characterized by NMR spectroscopy and X‐ray crystal structure analysis. Interestingly, the outcomes of these transformations strongly depend on the presence of an additional donor functionality within the phosphorus heterocycle as well as the nature of the solvent and the reaction temperature. DFT calculations were performed to rationalize the different reaction pathways.

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“…The reactions of triarylphosphine with thiosulfates and disulfides yield triarylphosphine sulfide 17) . Triarylphosphines are thiophilic, and they are known to react with elemental sulfur to produce triphenylphosphine sulfides 18) . In these reactions, hydrogen sulfide or sulfur dioxide in trace quantities acts as powerful catalysts.…”

Section: Investigation Of Secondary Reactions Of Sodium Sulfide Nonahmentioning

confidence: 99%

Preparation and properties of novel aromatic poly(thioethers) derived from 4,4′-thiobisbenzenethiol

Allam

Liu

McGrath

et al. 1999

Macromol. Chem. Phys.

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SUMMARY: A series of amorphous and semicrystalline aromatic poly(thioethers) have been prepared by the reactions of 4,49-thiobisbenzenethiol and activated dihalides. Azo group activated dihalide monomer was prepared by the reactions of 4-fluoronitrosobenzene with a suitable diamine. The keto and phosphine sulfide containing monomers were synthesized by Friedel-Crafts acylation reactions of suitable halobenzenes with appropriate acid chlorides. Potassium carbonate mediated reactions in dimethylacetamide afforded moderate to high molecular weight polymers. Polymers with high melting points were prepared by using diphenyl sulfone as a co-solvent. The poly(thioethers) exhibit high glass transition temperatures and/or high melting points. In addition, the polymers exhibit excellent thermal stability.

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Reactions of Elemental Sulfur. I. The Uncatalyzed Reaction of Sulfur with Triarylphosphines¹

Cited by 147 publications

References 2 publications

Review—From Nano Size Effect to In Situ Wrapping: Rational Design of Cathode Structure for High Performance Lithium−Sulfur Batteries

Review—From Nano Size Effect to In Situ Wrapping: Rational Design of Cathode Structure for High Performance Lithium−Sulfur Batteries

Reactivity of Aromatic Phosphorus Heterocycles – Differences Between Nonfunctionalized and Pyridyl‐Substituted 2,4,6‐Triarylphosphinines

Preparation and properties of novel aromatic poly(thioethers) derived from 4,4′-thiobisbenzenethiol

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Reactions of Elemental Sulfur. I. The Uncatalyzed Reaction of Sulfur with Triarylphosphines1

Cited by 147 publications

References 2 publications

Review—From Nano Size Effect to In Situ Wrapping: Rational Design of Cathode Structure for High Performance Lithium−Sulfur Batteries

Review—From Nano Size Effect to In Situ Wrapping: Rational Design of Cathode Structure for High Performance Lithium−Sulfur Batteries

Reactivity of Aromatic Phosphorus Heterocycles – Differences Between Nonfunctionalized and Pyridyl‐Substituted 2,4,6‐Triarylphosphinines

Preparation and properties of novel aromatic poly(thioethers) derived from 4,4′-thiobisbenzenethiol

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Reactions of Elemental Sulfur. I. The Uncatalyzed Reaction of Sulfur with Triarylphosphines¹