New phases in the system LiMnVO{sub 4}-Mn{sub 3}(VO{sub 4}){sub 2}

Journal Article · Sat Oct 15 00:00:00 EDT 2011 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2011.07.042· OSTI ID:21580016

Clemens, Oliver ^[1]; Haberkorn, Robert ^[2]

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1. Universitaet des Saarlandes, Institut fuer Anorganische und Analytische Chemie und Radiochemie, Am Markt, Zeile 5, 66125 Saarbruecken (Germany)
2. Universitaet des Saarlandes, Anorganische Festkoerperchemie, Am Markt, Zeile 3, 66125 Saarbruecken (Germany)

The synthesis of orthorhombic Mn{sub 3}(VO{sub 4}){sub 2} via a simple solid state route as well as the description of a new tetragonal high temperature phase are reported in this paper. Additionally, the system LiMnVO{sub 4}-Mn{sub 3}(VO{sub 4}){sub 2} (=Mn{sub 1.5}VO{sub 4}), described by the formula Li{sub x}Mn{sub 1.5-x/2}VO{sub 4}, is investigated in detail, showing that substitution of one Mn{sup 2+} in Mn{sub 1.5}VO{sub 4} by two Li{sup +} ions favors the formation of the tetragonal high temperature phase for x{<=}0.22. This substitution is facilitated by the statistical half occupancy of the 4b site by Mn{sup 2+} in tetragonal Mn{sub 1.5}VO{sub 4}, whereas additional crystallographic sites would have to be occupied in the orthorhombic phase. The inverse substitution of Li by Mn in orthorhombic LiMnVO{sub 4} is also shown to be possible in the range 0.72{<=}x{<=}1. For 0.22{<=}x{<=}0.72, there is a large miscibility gap with a two phase mixture of the tetragonal Mn{sub 1.5}VO{sub 4} type and orthorhombic LiMnVO{sub 4} type phases. - Graphical Abstract: The unusual coordination of Mn in the form of a stella quadrangula with the surrounding vanadate groups. Highlights: > First synthesis of orthorhombic Mn{sub 3}(VO{sub 4}){sub 2} via a simple solid state route. > The crystal chemistry of the phases involved is rather complicated and it depends on the amount of Li that is incorporated. > System LiMnVO{sub 4}-Mn{sub 3}(VO{sub 4}){sub 2} (=Mn{sub 1.5}VO{sub 4}), described by the formula Li{sub x}Mn{sub 1.5-x/2}VO{sub 4}, is investigated in detail.

• OSTI ID: 21580016
• Journal Information: Journal of Solid State Chemistry, Vol. 184, Issue 10; Other Information: DOI: 10.1016/j.jssc.2011.07.042; PII: S0022-4596(11)00421-X; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CRYSTALLOGRAPHY
CRYSTALS
LITHIUM
LITHIUM IONS
MANGANESE
MANGANESE IONS
MIXTURES
ORTHORHOMBIC LATTICES
PHASE TRANSFORMATIONS
SOLIDS
SYNTHESIS
TEMPERATURE RANGE 0400-1000 K
VANADATES
ALKALI METALS
CHARGED PARTICLES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DISPERSIONS
ELEMENTS
IONS
METALS
OXYGEN COMPOUNDS
TEMPERATURE RANGE
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS
VANADIUM COMPOUNDS