Solid-state metathesis as a quick route to transition-metal mixed dichalcogenides

Bonneau, Philippe; Jarvis, Robert F.; Kaner, Richard B.

doi:10.1021/ic00037a027

Cited by 71 publications

(40 citation statements)

References 6 publications

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“…Experimental lattice parameters and atomic positions have been reported for the Na-S crystals. [40][41][42][43][44][45] Table II shows lattice constants and Wycoff atomic positions fully-optimized by PBE calculations and experimental values for orthorhombic Na 2 S 5 (space group Pnma), tetragonal Na 2 S 4 (I " 42d), hexagonal ¡-Na 2 S 2 (P " 62m), hexagonal ¢-Na 2 S 2 (P6 3 =mmc), and cubic Na 2 S (Fm " 3m), respectively. All the lattice constants calculated by PBE agree well with the experiments, overestimating within the range from +0.2 to +1.9%.…”

Section: ¡-Smentioning

confidence: 99%

First-Principles Study on Structural and Electronic Properties of α-S and Na–S Crystals

2014

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Several Na-S solid phases have been considered to be produced in low-temperature Na/S batteries during chargedischarge reactions. We study structural and electronic properties of ¡-S and Na 2 S x (x = 1, 2, 4, and 5) crystals using first-principles calculations. Calculated structural properties are in good agreement with experiments, and the van der Waals interactions have an essential role on the cohesive properties in ¡-S. The results of energetics and electronic structures show that all the calculated Na-S crystal phases are insulating and are stable relative to the elemental Na and S phases. We estimate voltage curves as a function of the Na concentration in the S-cathode of all-solid Na/S batteries, showing mainly three voltage regions at 2.

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Section: ¡-Smentioning

confidence: 99%

First-Principles Study on Structural and Electronic Properties of α-S and Na–S Crystals

2014

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“…While this metathesis reaction reaches stoichiometric completion in the end, high-resolution synchrotron powder X-ray diffraction (HRSXRD) data suggest a far more complex mechanism than crystal chemistry would suggest, perhaps through reductive recombination to the elements or ionic exchange as previously hypothesized. 2,7,21,22 ■ RESULTS From differential scanning calorimetry (DSC), significant exothermic events occur on heating the reaction, even after the formation of NaCl (Figure 2a). Both thermodynamic and kinetic effects are required to reconcile the DSC and powder Xray diffraction (PXRD) data.…”

Section: ■ Introductionmentioning

confidence: 99%

Pyrite Formation via Kinetic Intermediates through Low-Temperature Solid-State Metathesis

Martinolich

Neilson

2014

J. Am. Chem. Soc.

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The preparation of materials with limited phase stabilities yet high kinetic activation barriers is challenging. Knowledge of their possible formation pathways aids in addressing these challenges. Metathesis reactions present an approach to circumvent these barriers; however, solid-state metathesis reactions are often too rapid from extensive self-heating to understand the reaction. The stoichiometric reaction of MCl2 salts (M = Mn, Fe, Co, Ni, Cu, Zn) with Na2S2 enables the formation of pyrite (FeS2), CoS2, and NiS2 at low temperatures (250-350 °C). Na2S2 has the same polyanionic dimer as found in the pyrite structure, which would suggest the possibility of a facile ion-exchange reaction. However, from high-resolution synchrotron X-ray diffraction and differential scanning calorimetry, the energetic driving force does not appear to result solely from NaCl formation but also from formation of intermediate and pyrite phases. It is apparent that the reaction proceeds through polyanionic disproportionation and formation of a low-density alkali-rich intermediate, followed by anionic comproportionation and atomic rearrangement into the pyrite phase. These results have profound implications for the use of low-temperature metathesis in achieving materials by design.

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“…Recently, solid-state metathesis routes have been developed to synthesize metal nitrides [11,12], which also need high temperature or critical reaction conditions. As for TaN, its bulk material has been prepared by heating tantalum in nitrogen at high temperatures [13].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of nanocrystalline TaN

Shi

Yang

Chen

et al. 2005

Solid State Communications

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Solid-state metathesis as a quick route to transition-metal mixed dichalcogenides

Cited by 71 publications

References 6 publications

First-Principles Study on Structural and Electronic Properties of α-S and Na–S Crystals

First-Principles Study on Structural and Electronic Properties of α-S and Na–S Crystals

Pyrite Formation via Kinetic Intermediates through Low-Temperature Solid-State Metathesis

Synthesis and characterization of nanocrystalline TaN

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