Structure and bonding in Li/sub 2/MoO/sub 3/ and Li/sub 2-x/MoO/sub 3/ (0 less than or equal to x less than or equal to 1. 7)

Journal Article · Thu Sep 01 00:00:00 EDT 1988 · J. Solid State Chem.; (United States)

DOI:https://doi.org/10.1016/0022-4596(88)90194-6· OSTI ID:6809566

James, A C.W.P.; Goodenough, J B

Li/sub 2/MoO/sub 3/ prepared by hydrogen reduction of Li/sub 2/MoO/sub 4/ was studied by X-ray and neutron diffraction. The results imply that the previous assignment of a ..beta..-Li/sub 2/SnO/sub 3/ structure to this material (C2/c; a = 4.97 A, b = 8.61 A, c = 10.10 A, ..beta.. = 99.5/sup 0/) is inappropriate. Li/sub 2/MoO/sub 3/ has a novel, disordered ..cap alpha..-NaFeO/sub 2/ structure (R anti 3m; a = 2.884 A, c = 14.834 A) with the molybdenum present as Mo/sub 3/O/sub 3/ clusters. This structural model is consistent with the diamagnetism and low electrical conductivity of Li/sub 2/MoO/sub 3/ and accounts for certain features of the Li/sub 2/O-MoO/sub 2/ phase diagram. The presence of Mo/sub 3/O/sub 13/ clusters in Li/sub 2/MoO/sub 3/ was confirmed by comparison of the He-I photoelectron spectra of Li/sub 2/MoO/sub 3/ and Zn/sub 2/Mo/sub 38/; the latter compound is known from single-crystal X-ray diffraction to contain Mo/sub 3/O/sub 13/ clusters. Oxidative extraction of us to 85% of the lithium from Li/sub 2/MoO/sub 3/ was achieved at ambient temperature with mild oxidizing agents and electrochemically. Crystallographic studies of Li/sub 2-x/MoO/sub 3/ by X-ray and neutron powder diffraction show that lithium extraction is accompanied by migration of some molybdenum ions to sites in the lattice previously occupied by lithium ions. Electrochemical delithiation of Li/sub 2/MoO/sub 3/ is kinetically slow and not fully reversible.

• Research Organization: Univ. of Texas, Austin (USA)
• OSTI ID: 6809566
• Journal Information: J. Solid State Chem.; (United States), Journal Name: J. Solid State Chem.; (United States) Vol. 76:1; ISSN JSSCB
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360602 -- Other Materials-- Structure & Phase Studies
360603 -- Materials-- Properties
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKALI METAL COMPOUNDS
COHERENT SCATTERING
CRYSTAL STRUCTURE
DATA
DIAMAGNETISM
DIFFRACTION
ELECTRIC CONDUCTIVITY
ELECTRICAL PROPERTIES
EXPERIMENTAL DATA
INFORMATION
LATTICE PARAMETERS
LITHIUM COMPOUNDS
MAGNETISM
MOLYBDATES
MOLYBDENUM COMPOUNDS
NEUTRON DIFFRACTION
NUMERICAL DATA
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
REFRACTORY METAL COMPOUNDS
SCATTERING
SPACE GROUPS
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION