Structure transformations and proton conductivity of hydrogen zirconium phosphates with the NASICON structure, H1 +/- XZr2-XMX(PO4)(3)center dot H2O (X = 0, 0.02, and 0.1, M = Nb, Y), were studied by X-ray powder diffraction, calorimetry, IR- and impedance spectroscopy. Substitution of zirconium by niobium leads to decrease of the lattice parameters, while yttrium doping leads to their increase. H0.9Zr1.9Nb0.1(PO4)(3) structure was determined at 493 and 733 K. This phase crystallizes in rhombohedral space group R (3) over barc with lattice parameters a = 8.8564(5) angstrom, c = 22.700(1) angstrom at 493 K and a = 8.8470(2) angstrom, c = 22.7141(9) angstrom at 733 K. The a parameter and lattice volume were found to decrease with temperature increasing. Structure transformations upon heating are caused mainly by the decrease of the M1 site and C cavities. Ion conductivity of obtained materials was found to increase in humid atmosphere. Activation energies of conductivity were calculated. Rhombohedral-triclinic phase transition found by X-ray powder diffraction was proved by calorimetry data. According to XRD and IR spectroscopy data hydrogen bond in HZr2(PO4)(3) was found to be weaker than in hydrated material. (C) 2009 Elsevier Ltd. All rights reserved.
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CNRS, Chim Coordinat Lab, F-31077 Toulouse, France
Univ Toulouse, UPS, INPT, LCC, F-31077 Toulouse, FranceIndian Inst Sci, Solid State & Struct Chem Unit, Bangalore 560012, Karnataka, India
Dhers, Sebastien
Sahoo, Shaon
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Indian Inst Sci, Solid State & Struct Chem Unit, Bangalore 560012, Karnataka, India
Indian Inst Sci, Dept Phys, Bangalore 560012, Karnataka, IndiaIndian Inst Sci, Solid State & Struct Chem Unit, Bangalore 560012, Karnataka, India
Sahoo, Shaon
Costes, Jean-Pierre
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CNRS, Chim Coordinat Lab, F-31077 Toulouse, France
Univ Toulouse, UPS, INPT, LCC, F-31077 Toulouse, FranceIndian Inst Sci, Solid State & Struct Chem Unit, Bangalore 560012, Karnataka, India
Costes, Jean-Pierre
Duhayon, Carine
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CNRS, Chim Coordinat Lab, F-31077 Toulouse, France
Univ Toulouse, UPS, INPT, LCC, F-31077 Toulouse, FranceIndian Inst Sci, Solid State & Struct Chem Unit, Bangalore 560012, Karnataka, India
机构:
Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China
Chinese Acad Sci, Grad Sch, Beijing 100049, Peoples R ChinaChinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China
Zhuge, Fuyu
Wu, Biao
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Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China
Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R ChinaChinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China
Wu, Biao
Dong, Lihuan
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Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R ChinaChinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China
Dong, Lihuan
Yang, Jin
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Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R ChinaChinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China
Yang, Jin
Janiak, Christoph
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Univ Freiburg, Inst Anorgan & Analyt Chem, D-79104 Freiburg, GermanyChinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China
Janiak, Christoph
Tang, Ning
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Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R ChinaChinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China
Tang, Ning
Yang, Xiao-Juan
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Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China
Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R ChinaChinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China