Amorphous Precursors for Low-Temperature Preparation of Chevrel Phases MxMo6S8 and Their Tungsten Analogues

McCarley, Robert E.; Hilsenbeck, Shane J.; Xie, Xiaoning

doi:10.1006/jssc.1995.1273

Cited by 30 publications

(29 citation statements)

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“…While we also observe the disappearance of the A 1g mode, the broad sloping peaks are not observed by Xiong et al The set of three peaks could be attributed to Chevrel-based Mo 6 S 8 moieties consisting of S 2− species. 68,69 The as-prepared chalcogel is formed again upon charging to 3.5 V (Figure 2).…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

Molybdenum Polysulfide Chalcogels as High-Capacity, Anion-Redox-Driven Electrode Materials for Li-Ion Batteries

Subrahmanyam²,

et al. 2016

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Sulfur cathodes in conversion reaction batteries offer high gravimetric capacity but suffer from parasitic polysulfide shuttling. We demonstrate here that transition metal chalcogels of approximate formula MoS 3.4 achieve high gravimetric capacity close to 600 mAh g −1 (close to 1000 mAh g −1 on a sulfur-basis), as electrode materials for lithium-ion batteries. Transition metal chalcogels are amorphous, and comprise polysulfide chains connected by inorganic linkers. The linkers appear to act as a "glue" in the electrode to prevent polysulfide shuttling. The Mo chalcogels function as electrodes in carbonate-as well as ether-based electrolytes, which further provides evidence for polysulfide solubility not being a limiting issue. We employ X-ray spectroscopy and operando pair distribution function techniques to elucidate the structural evolution of the electrode. Raman and X-ray photoelectron spectroscopy track the chemical moieties that arise during the anion-redox-driven processes. We find the redox state of Mo remains unchanged across the electrochemical cycling and correspondingly, the redox

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Section: ■ Materials and Methodsmentioning

confidence: 99%

Molybdenum Polysulfide Chalcogels as High-Capacity, Anion-Redox-Driven Electrode Materials for Li-Ion Batteries

Subrahmanyam²,

et al. 2016

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“…In this study, we calculated 17 M-W-S ternary phase diagrams at room temperature (298 K) based on published thermodynamic data, where M = Zr, Cr, Mn, Fe, Ru, Os, Co, Rh, Ni, Pd, Pt, Cu, Ag, than in the M-Mo-S systems [16], and attempts to produce some of the analogues of the ubiquitous M-Mo-S Chevrel phases using W have been unsuccessful [31].…”

Section: Source Of Thermodynamic Datamentioning

confidence: 99%

“…Figure 8a shows a periodic table depicting the ternary phase diagram types of the M-Mo-S systems, and Figure 8b shows a similar periodic table for the M-W-S systems from groups 4 through 11 to match the earlier work. Lastly, there are many more ternary phases in the M-Mo-S systems than in the M-W-S systems due to the lack of stable W analogues of the ubiquitous M-Mo-S Chevrel phases [31].…”

Section: Comparison Between the M-w-s And M-mo-s Systemsmentioning

confidence: 99%

Condensed phase diagrams for the metal–W–S systems and their relevance for contacts to WS2

Zeng

Domask

Mohney

2016

Materials Science and Engineering: B

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Motivated by interest in contacts to the layered semiconductor WS 2 , this study investigates condensed phase equilibria in M-W-S systems (M = transition or post-transition metal) and relates the findings to earlier work on M-Mo-W systems. Thermodynamic data were collected or estimated for the binary phases bearing M, W, and/or S; and a literature search for existing ternary phases was performed.Condensed phase M-W-S isothermal phase diagrams were calculated where sufficient data was available.These phase diagrams reflected three general forms. The early transition metals and group 13 posttransition metals were mostly reactive with WS 2 , with the resulting diagrams being either metal sulfide dominant or ternary/solid solution dominant. The late transition metals were all WS 2 dominant, where the metal is in equilibrium with WS 2 . These findings are similar to those from our earlier study on the M-Mo-S phase diagrams and can be used to guide studies on contacts to WS 2 .

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“…[8][9][10][11] Molecular Mo 6 S 8 L 6 clusters (L = PEt 3 , nitrogen Lewis base ligands) were prepared independently by Saito and coworkers 12, 13 and by McCarley et al 14 to study their structural relation to the solid-state Chevrel phases and to use these molecular precursors to prepare Chevrel phases. 15, 16 However, these two synthetic procedures are not ideal for further studies of the solution chemistry of the clusters. It is very hard to replace the PEt 3 ligand in Saito's synthetic product, Mo 6 S 8 -(PEt 3 ) 6 , and the direct product in McCarley's route, Mo 6 S 8 -(pyridine) 6 , is insoluble in most solvents.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and properties of Mo6S8(4-tert-butylpyridine)6 and related M6S8L6 cluster complexes (M = Mo, W)

Jin

Popp

Boettcher

et al. 2002

J. Chem. Soc., Dalton Trans.

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Octahedral molybdenum chalcogenide clusters are the building blocks of the well-known Chevrel phases. Although the synthesis of molecular Mo 6 S 8 L 6 (L = PEt 3 and pyridine) clusters has been previously reported, a high yield and larger scale synthetic procedure is needed to produce soluble Mo 6 S 8 L 6 (L = Lewis base ligand) clusters, so that they can be used as precursors for the construction of novel network structures. Using the previously developed W 6 S 8 (4tert-butylpyridine) 6 synthesis as a starting point, a facile, high yield (70%) synthesis of Mo 6 S 8 (4-tert-butylpyridine) 6 from (Bu 4 N) 2 Mo 6 Cl 8 Cl 6 was developed. This general sulfidation reaction scheme can be extended to the direct preparation of many M 6 S 8 L 6 (M = W, Mo; L = Lewis base ligand) complexes. Three Mo 6 S 8 L 6 complexes (L = PEt 3 , methylamine, 4,4Ј-bipyridine) were also prepared via ligand exchange reactions with Mo 6 S 8 (4-tert-butylpyridine) 6 . The above Mo 6 S 8 L 6 complexes were characterized and their reactivity was compared with their tungsten counterparts. Crystal structures were found for Mo 6 S 8 (4-tert-butylpyridine) 6 , Mo 6 S 8 (4,4Ј-bipyridine) 6 , and Mo 6 S 8 (methylamine) 6 .

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Amorphous Precursors for Low-Temperature Preparation of Chevrel Phases MxMo6S8 and Their Tungsten Analogues

Cited by 30 publications

References 0 publications

Molybdenum Polysulfide Chalcogels as High-Capacity, Anion-Redox-Driven Electrode Materials for Li-Ion Batteries

Molybdenum Polysulfide Chalcogels as High-Capacity, Anion-Redox-Driven Electrode Materials for Li-Ion Batteries

Condensed phase diagrams for the metal–W–S systems and their relevance for contacts to WS2

Synthesis, characterization and properties of Mo6S8(4-tert-butylpyridine)6 and related M6S8L6 cluster complexes (M = Mo, W)

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