Molybdenum cluster chalcogenides Mo6X8: intercalation of lithium via electron/ion transfer

Journal Article · Wed Jun 03 04:00:00 EDT 1987 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00258a034· OSTI ID:6428391

Gocke, E; Schoellhorn, R; Aselmann, G; Mueller-Warmuth, W

The electrochemical intercalation of lithium at 300 K into the rhombohedral molybdenum cluster chalcogenides Mo6X8 (X = S, Se) under formation of ternary phases Li/sub x/Mo6X8 has been investigated with respect to the changes of composition, structure, and bonding. Complete XLi NMR phase diagrams have been established, and thermodynamic data are given. Diffusion coefficients and NMR dipolar lie width demonstrate a rather high lithium ionic mobility; the reactions are fully reversible. Results are closely similar for the sulfide and selenide system. Four distinct rhombohedral phases with x = 1, 3, 3.8, and 4 could be identified. The transition from x = 1 to x = 3 is correlated with a significant increase in unit cell volume and an unusually strong decrease in NMR line shift. The latter has been interpreted in terms of a partial charge transfer with formation of triangular (Li3)S clusters, i.e. (Li3)S (Mo6S8)S . For Li4Mo6S8 the NMR shift changes again abruptly in the inverse sense to values indicating normal Li ions. This is attributed to the loss in symmetry of the lithium clusters as well as the tendency for quantitative saturation of the Mo6 clusters with 24 electrons (metal/semiconductor transition).

• Research Organization: Technische Universitaet Berlin, West Germany
• OSTI ID: 6428391
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:11; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360102* -- Metals & Alloys-- Structure & Phase Studies
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500 -- Photochemistry
ALKALI METAL ISOTOPES
ALKALI METALS
CHALCOGENIDES
CHEMICAL BONDS
CHEMISTRY
CLATHRATES
COMPLEXES
DATA
DIAGRAMS
ELECTROCHEMISTRY
ELECTRON TRANSFER
ELEMENTS
EXPERIMENTAL DATA
INFORMATION
ISOTOPES
LIGHT NUCLEI
LITHIUM
LITHIUM 7
LITHIUM ISOTOPES
MAGNETIC RESONANCE
MEDIUM TEMPERATURE
METALS
MOLYBDENUM COMPLEXES
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
PHASE DIAGRAMS
PHASE STUDIES
PHYSICAL PROPERTIES
RESONANCE
SELENIDES
SELENIUM COMPOUNDS
SPECTRA
STABLE ISOTOPES
SULFIDES
SULFUR COMPOUNDS
SUPERCONDUCTORS
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPLEXES