Phase transitions, structure and ion conductivity of zirconium hydrogen phosphates, H1±XZr2-XMX(PO4)3•H2O (M = Nb, Y)

被引:15
|
作者
Stenina, I. A. [1 ]
Zhizhin, M. G. [2 ]
Lazoryak, B. I. [2 ]
Yaroslavtsev, A. B. [1 ]
机构
[1] Russian Acad Sci, NS Kurnakov Gen & Inorgan Chem Inst, Moscow 119991, Russia
[2] Moscow MV Lomonosov State Univ, Moscow 119992, Russia
关键词
Inorganic compounds; Phase transactions; Ionic conductivity; Thermal expansion; THERMAL-EXPANSION; CRYSTAL-STRUCTURES;
D O I
10.1016/j.materresbull.2009.01.011
中图分类号
T [工业技术];
学科分类号
08 ;
摘要
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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收藏
页码:1608 / 1612
页数:5
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