Effect of sintering on the ionic conductivity of garnet-related structure Li5La3Nb2O12 and In- and K-doped Li5La3Nb2O12

被引:139
作者
Thangadurai, V [1 ]
Weppner, W [1 ]
机构
[1] Univ Kiel, Fac Engn, Chair Sensors & Solid State Ion, D-24143 Kiel, Germany
关键词
synthesis; structure; AC impedance; ionic conductivity; Li5La3Nb2O12; In- and K-doped Li5La3Nb2O12; garnets; lithium; solid electrolytes;
D O I
10.1016/j.jssc.2005.12.025
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Garnet-structure related metal oxides with the nominal chemical composition of Li5La3Nb2O12, In-substituted Li5.5La3Nb1.75In0.25O12 and K-substituted Li5.5La2.75K0.25Nb2O12 were prepared by solid-state reactions at 900, 950, and 1000 degrees C using appropriate amounts of corresponding metal oxides, nitrates and carbonates. The powder XRD data reveal that the In- and K-doped compounds are isostructural with the parent compound Li5La3Nb2O12. The variation in the cubic lattice parameter was found to change with the size of the dopant ions, for example, substitution of larger In3+(r(CN6): 0.79 angstrom) for smaller Nb5+ (r(CN6): 0.64 angstrom) shows an increase in the lattice parameter from 12.8005(9) to 12.826(1) angstrom at 1000 degrees C. Samples prepared at higher temperatures (950, 1000 degrees C) show mainly bulk lithium ion conductivity in contrast to those synthesized at lower temperatures (900 degrees C). The activation energies for the ionic conductivities are comparable for all samples. Partial substitution of K+ for La3+ and In3+ for Nb5+ in Li5La3Nb2O12 exhibits slightly higher ionic conductivity than that of the parent compound over the investigated temperature regime 25-300 degrees C. Among the compounds investigated, the In-substituted Li5.5La3Nb1.75In0.25O12 exhibits the highest bulk lithium ion conductivity of 1.8 x 10(-4)S/cm at 50 degrees C with an activation energy of 0.51 eV. The diffusivity ("component diffusion coefficient") obtained from the AC conductivity and powder XRD data falls in the range 10(-10)-10(-7) cm(2)/s over the temperature regime 50-200 degrees C, which is extraordinarily high and comparable with liquids. Substitution of Al, Co, and Ni for Nb in Li5La3Nb2O12 was found to be unsuccessful under the investigated conditions. (c) 2005 Elsevier Inc. All rights reserved.
引用
收藏
页码:974 / 984
页数:11
相关论文
共 39 条
  • [1] Fast Li-circle plus conducting ceramic electrolytes
    Adachi, GY
    Imanaka, N
    Aono, H
    [J]. ADVANCED MATERIALS, 1996, 8 (02) : 127 - +
  • [2] [Anonymous], 2002, PEROVSKITES MODERN A
  • [3] HIGH LI+ CONDUCTING CERAMICS
    AONO, H
    IMANAKA, N
    ADACHI, G
    [J]. ACCOUNTS OF CHEMICAL RESEARCH, 1994, 27 (09) : 265 - 270
  • [4] Thin-film lithium and lithium-ion batteries
    Bates, JB
    Dudney, NJ
    Neudecker, B
    Ueda, A
    Evans, CD
    [J]. SOLID STATE IONICS, 2000, 135 (1-4) : 33 - 45
  • [5] STUDY OF SOLID ELECTROLYTE POLARIZATION BY A COMPLEX ADMITTANCE METHOD
    BAUERLE, JE
    [J]. JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS, 1969, 30 (12) : 2657 - &
  • [6] PREPARATION, STRUCTURAL CHARACTERIZATION AND CONDUCTIVITY OF LIZR2(PO4)3
    CASCIOLA, M
    COSTANTINO, U
    MERLINI, L
    ANDERSEN, IGK
    ANDERSEN, EK
    [J]. SOLID STATE IONICS, 1988, 26 (03) : 229 - 235
  • [7] Stable lithium-ion conducting perovskite lithium-strontium-tantalum-zirconium-oxide system
    Chen, CH
    Xie, S
    Sperling, E
    Yang, AS
    Henriksen, G
    Amine, K
    [J]. SOLID STATE IONICS, 2004, 167 (3-4) : 263 - 272
  • [8] Temperature dependence of oxygen ion transport in Sr plus Mg-substituted LaGaO3 (LSGM) with varying grain sizes
    Haavik, C
    Ottesen, EM
    Nomura, K
    Kilner, JA
    Norby, T
    [J]. SOLID STATE IONICS, 2004, 174 (1-4) : 233 - 243
  • [9] Lithium ion conductivity of A-site deficient perovskite solid solutions
    Harada, Y
    Watanabe, H
    Kuwano, J
    Saito, Y
    [J]. JOURNAL OF POWER SOURCES, 1999, 81 : 777 - 781
  • [10] CRYSTAL-STRUCTURES OF LA3LI5NB2O12, LA3LI5TA2O12
    HYOOMA, H
    HAYASHI, K
    [J]. MATERIALS RESEARCH BULLETIN, 1988, 23 (10) : 1399 - 1407