Synthesis, structural characterization and Li+ ion conductivity of a new vanado-molybdate phase, LiMg3VMo2O12

Lisa J. Gillie, Sharon A. De Souza, Denis Sheptyakov, Nik Reeves-Mclaren, Denis Pasero, Anthony R. West

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

A new vanado-molybdate LiMg3VMo2O12 has been synthesized, the crystal structure determined an ionic conductivity measured. The solid solution Li2-zMg2zVzMo 3-zO12 was investigated and the structures of the z=0.5 and 1.0 compositions were refined by Rietveld analysis of powder X-ray (XRD) and powder neutron diffraction (ND) data. The structures were refined in the orthorhombic space group Pnma with a∼5.10, b∼10.4 and c∼17.6 , and are isostructural with the previously reported double molybdates Li 2M2(MoO4)3 (M=M2, z=0). The structures comprise of two unique (Li/Mg)O6 octahedra, (Li/Mg)O6 trigonal prisms and two unique (Mo/V)O4 tetrahedra. A well-defined 1:3 ratio of Li+:Mg2 is observed in octahedral chains for LiMg3VMo2O12. Li+ preferentially occupies trigonal prisms and Mg2 favours octahedral sheets. Excess V5 adjacent to the octahedral sheets may indicate short-range order. Ionic conductivity measured by impedance spectroscopy (IS) and differential scanning calorimetry (DSC) measurements show the presence of a phase transition, at 500600 °C, depending on x. A decrease in activation energy for Li+ ion conductivity occurs at the phase transition and the high temperature structure is a good Li+ ion conductor, with σ=1×10-34×10-2S cm -1 and Ea=0.6 to 0.8 eV.

Original languageEnglish
Pages (from-to)2589-2597
Number of pages9
JournalJournal of Solid State Chemistry
Volume183
Issue number11
DOIs
Publication statusPublished - Nov 2010

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molybdates
Ionic conductivity
Prisms
ion currents
prisms
Phase transitions
Ions
Rietveld analysis
conductivity
Neutron powder diffraction
synthesis
tetrahedrons
Powders
neutron diffraction
Differential scanning calorimetry
Solid solutions
ions
solid solutions
heat measurement
conductors

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Gillie, Lisa J. ; De Souza, Sharon A. ; Sheptyakov, Denis ; Reeves-Mclaren, Nik ; Pasero, Denis ; West, Anthony R. / Synthesis, structural characterization and Li+ ion conductivity of a new vanado-molybdate phase, LiMg3VMo2O12. In: Journal of Solid State Chemistry. 2010 ; Vol. 183, No. 11. pp. 2589-2597.
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title = "Synthesis, structural characterization and Li+ ion conductivity of a new vanado-molybdate phase, LiMg3VMo2O12",
abstract = "A new vanado-molybdate LiMg3VMo2O12 has been synthesized, the crystal structure determined an ionic conductivity measured. The solid solution Li2-zMg2zVzMo 3-zO12 was investigated and the structures of the z=0.5 and 1.0 compositions were refined by Rietveld analysis of powder X-ray (XRD) and powder neutron diffraction (ND) data. The structures were refined in the orthorhombic space group Pnma with a∼5.10, b∼10.4 and c∼17.6 , and are isostructural with the previously reported double molybdates Li 2M2(MoO4)3 (M=M2, z=0). The structures comprise of two unique (Li/Mg)O6 octahedra, (Li/Mg)O6 trigonal prisms and two unique (Mo/V)O4 tetrahedra. A well-defined 1:3 ratio of Li+:Mg2 is observed in octahedral chains for LiMg3VMo2O12. Li+ preferentially occupies trigonal prisms and Mg2 favours octahedral sheets. Excess V5 adjacent to the octahedral sheets may indicate short-range order. Ionic conductivity measured by impedance spectroscopy (IS) and differential scanning calorimetry (DSC) measurements show the presence of a phase transition, at 500600 °C, depending on x. A decrease in activation energy for Li+ ion conductivity occurs at the phase transition and the high temperature structure is a good Li+ ion conductor, with σ=1×10-34×10-2S cm -1 and Ea=0.6 to 0.8 eV.",
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Synthesis, structural characterization and Li+ ion conductivity of a new vanado-molybdate phase, LiMg3VMo2O12. / Gillie, Lisa J.; De Souza, Sharon A.; Sheptyakov, Denis; Reeves-Mclaren, Nik; Pasero, Denis; West, Anthony R.

In: Journal of Solid State Chemistry, Vol. 183, No. 11, 11.2010, p. 2589-2597.

Research output: Contribution to journalArticle

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T1 - Synthesis, structural characterization and Li+ ion conductivity of a new vanado-molybdate phase, LiMg3VMo2O12

AU - Gillie, Lisa J.

AU - De Souza, Sharon A.

AU - Sheptyakov, Denis

AU - Reeves-Mclaren, Nik

AU - Pasero, Denis

AU - West, Anthony R.

PY - 2010/11

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N2 - A new vanado-molybdate LiMg3VMo2O12 has been synthesized, the crystal structure determined an ionic conductivity measured. The solid solution Li2-zMg2zVzMo 3-zO12 was investigated and the structures of the z=0.5 and 1.0 compositions were refined by Rietveld analysis of powder X-ray (XRD) and powder neutron diffraction (ND) data. The structures were refined in the orthorhombic space group Pnma with a∼5.10, b∼10.4 and c∼17.6 , and are isostructural with the previously reported double molybdates Li 2M2(MoO4)3 (M=M2, z=0). The structures comprise of two unique (Li/Mg)O6 octahedra, (Li/Mg)O6 trigonal prisms and two unique (Mo/V)O4 tetrahedra. A well-defined 1:3 ratio of Li+:Mg2 is observed in octahedral chains for LiMg3VMo2O12. Li+ preferentially occupies trigonal prisms and Mg2 favours octahedral sheets. Excess V5 adjacent to the octahedral sheets may indicate short-range order. Ionic conductivity measured by impedance spectroscopy (IS) and differential scanning calorimetry (DSC) measurements show the presence of a phase transition, at 500600 °C, depending on x. A decrease in activation energy for Li+ ion conductivity occurs at the phase transition and the high temperature structure is a good Li+ ion conductor, with σ=1×10-34×10-2S cm -1 and Ea=0.6 to 0.8 eV.

AB - A new vanado-molybdate LiMg3VMo2O12 has been synthesized, the crystal structure determined an ionic conductivity measured. The solid solution Li2-zMg2zVzMo 3-zO12 was investigated and the structures of the z=0.5 and 1.0 compositions were refined by Rietveld analysis of powder X-ray (XRD) and powder neutron diffraction (ND) data. The structures were refined in the orthorhombic space group Pnma with a∼5.10, b∼10.4 and c∼17.6 , and are isostructural with the previously reported double molybdates Li 2M2(MoO4)3 (M=M2, z=0). The structures comprise of two unique (Li/Mg)O6 octahedra, (Li/Mg)O6 trigonal prisms and two unique (Mo/V)O4 tetrahedra. A well-defined 1:3 ratio of Li+:Mg2 is observed in octahedral chains for LiMg3VMo2O12. Li+ preferentially occupies trigonal prisms and Mg2 favours octahedral sheets. Excess V5 adjacent to the octahedral sheets may indicate short-range order. Ionic conductivity measured by impedance spectroscopy (IS) and differential scanning calorimetry (DSC) measurements show the presence of a phase transition, at 500600 °C, depending on x. A decrease in activation energy for Li+ ion conductivity occurs at the phase transition and the high temperature structure is a good Li+ ion conductor, with σ=1×10-34×10-2S cm -1 and Ea=0.6 to 0.8 eV.

KW - 3D framework compounds

KW - Cation ordering

KW - Impedance spectroscopy

KW - Ionic conductivity

KW - Lithium molybdate

KW - Neutron diffraction

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