High Ni2+-mobility in the Chevrel phase Ni2Mo6S8: a quasielastic neutron scattering study

Ritter, C.; Nöldeke, C.; Press, W.; Stege, Uwe; Schöllhorn, R.

doi:10.1007/bf01320505

Cited by 11 publications

(9 citation statements)

References 12 publications

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“…In the same way, in site 2, we can have (Ni )> pairs from a geometric point of view. These assumptions are reinforced by the high mobility of the nickel atoms in nickel molybdenum sul"de (19).…”

Section: Iii2 Ni Y Mo 6 Se 8!x S X (Yand2) Single Crystalsmentioning

confidence: 95%

Single Crystal Structural Investigations on NiyMo6Se8−xSx Solid Solution: A New Location of Nickel Counterions

Belin

Chevrel

Sergent

2000

Journal of Solid State Chemistry

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Section: Iii2 Ni Y Mo 6 Se 8!x S X (Yand2) Single Crystalsmentioning

confidence: 95%

Single Crystal Structural Investigations on NiyMo6Se8−xSx Solid Solution: A New Location of Nickel Counterions

Belin

Chevrel

Sergent

2000

Journal of Solid State Chemistry

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“…It is clear that the reason of the slow kinetics of Mg ions insertion into inorganic hosts is their divalent character; however the aspects of transport phenomena related to Mg ions insertion are not covered at all by the literature in electrochemistry, physical chemistry or solid state ionics. Some researchers speak in general about possible strong interactions between the inserted divalent cations with the anions and the cations of the hosts [10] or about high activation energies for site changes in cases where the inserted ions have high charge/radius ratio (e 2 /r) [11].…”

Section: Introductionmentioning

confidence: 99%

A review on the problems of the solid state ions diffusion in cathodes for rechargeable Mg batteries

et al. 2007

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This work summarizes the results of our studies devoted to Mg ions mobility in Chevrel phases (CPs), M x Mo 6 T 8 (M -metal, T = S, Se) and presents our vision of the problem of multivalent ions' diffusion in intercalation compounds. A simplified analysis of the main factors, which affect the activation energy barriers, as well as experimental data of Mg ions insertion into different hosts, show that low Mg ions mobility in common transition metal oxides or sulfides cannot be explained only by strong ionic interactions, but it is rather caused by a hard redistribution of the bivalent cations charge in inorganic materials. In contrast to these hosts, CPs allow for a high mobility of multivalent cations, because their unusual crystal structure with octahedral Mo 6 -clusters enables a fast and efficient attainment of local electro-neutrality upon insertion of cations of high charge density. Analysis of diffusion pathways based on the detailed structural determinations sheds light on important aspects of the electrochemical behavior of CPs, such as partial Mg ions trapping in the course of reversible Mg insertion and the ways to avoid it.

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“…Similar models are conceivable for the cadmium homologue. Models based on partial charge transfer are also invoked for explaining the unexpectedly high mobility of divalent cations as recently detected in Ni 2 Mo 6 S 8 by neutron diffraction and in Cu 2+ -doped HgMo 6 S 8 by EPR spectroscopy . Confirmation of such high mobility for other divalent cations (such as Cd 2+ ) and by independent experimental methods would be highly desirable.…”

Section: Introductionmentioning

confidence: 93%

Solid-State NMR Structural Studies of the Ternary Molybdenum Cluster Chalcogenides Cd_xMo₆Se₈ (x = 1, 2)

Janssen¹,

Eckert²,

Müller‐Warmuth³

et al. 1998

Chem. Mater.

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The structures of the ternary Chevrel phases CdMo 6 Se 8 and Cd 2 Mo 6 Se 8 have been studied by several complementary 111 Cd NMR spectroscopic techniques. Specifically, cadmium mobility and bonding properties are probed by temperature and frequency dependent measurements of static line shapes, magic angle spinning (MAS) NMR spectra, and spinlattice relaxation rates. Furthermore, models for the spatial cadmium distribution are tested on the basis of 111 Cd-111 Cd dipole-dipole interactions, measured by spin-echo decay spectroscopy on isotopically labeled materials (97% 111 Cd). CdMo 6 Se 8 undergoes a phase transition near 130 K; the cadmium ions are static on the NMR time scale over the whole temperature range in both phases. The spatial cation distribution is close to homogeneous, and it specifically excludes the presence of Cd-Cd dimers. For the high-temperature phase, the 111 Cd spectra indicate a large degree of static disorder. In addition, the large 111 Cd chemical shift temperature coefficient and fast spin-lattice relaxation reveal strong interactions between the intercalated cadmium atoms and the conduction band wave functions of the Mo 6 Se 8 matrix. This behavior is typical for charge-transfer intercalation compounds in which the conduction band is only partially filled. Cd 2 Mo 6 Se 8 , which crystallizes in the rhombohedral R3 h structure, shows the typical NMR signature of a rigid, semiconducting compound. The intercalated metal species show no apparent interaction with conduction electron wave functions. 111 Cd MAS and spin-echo decay data suggest a disordered atomic distribution of Cd 2+ ions with a minimum Cd-Cd internuclear distance of 258 pm.

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High Ni2+-mobility in the Chevrel phase Ni2Mo6S8: a quasielastic neutron scattering study

Cited by 11 publications

References 12 publications

Single Crystal Structural Investigations on NiyMo6Se8−xSx Solid Solution: A New Location of Nickel Counterions

Single Crystal Structural Investigations on NiyMo6Se8−xSx Solid Solution: A New Location of Nickel Counterions

A review on the problems of the solid state ions diffusion in cathodes for rechargeable Mg batteries

Solid-State NMR Structural Studies of the Ternary Molybdenum Cluster Chalcogenides Cd_xMo₆Se₈ (x = 1, 2)

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High Ni2+-mobility in the Chevrel phase Ni2Mo6S8: a quasielastic neutron scattering study

Cited by 11 publications

References 12 publications

Single Crystal Structural Investigations on NiyMo6Se8−xSx Solid Solution: A New Location of Nickel Counterions

Single Crystal Structural Investigations on NiyMo6Se8−xSx Solid Solution: A New Location of Nickel Counterions

A review on the problems of the solid state ions diffusion in cathodes for rechargeable Mg batteries

Solid-State NMR Structural Studies of the Ternary Molybdenum Cluster Chalcogenides CdxMo6Se8 (x = 1, 2)

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Solid-State NMR Structural Studies of the Ternary Molybdenum Cluster Chalcogenides Cd_xMo₆Se₈ (x = 1, 2)