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Title: Effect of sintering on the ionic conductivity of garnet-related structure Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12} and In- and K-doped Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12}

Abstract

Garnet-structure related metal oxides with the nominal chemical composition of Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12}, In-substituted Li{sub 5.5}La{sub 3}Nb{sub 1.75}In{sub 0.25}O{sub 12} and K-substituted Li{sub 5.5}La{sub 2.75}K{sub 0.25}Nb{sub 2}O{sub 12} were prepared by solid-state reactions at 900, 950, and 1000 deg. 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 Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12}. The variation in the cubic lattice parameter was found to change with the size of the dopant ions, for example, substitution of larger In{sup 3+}(r {sub CN6}: 0.79 A) for smaller Nb{sup 5+} (r {sub CN6}: 0.64 A) shows an increase in the lattice parameter from 12.8005(9) to 12.826(1) A at 1000 deg. C. Samples prepared at higher temperatures (950, 1000 deg. C) show mainly bulk lithium ion conductivity in contrast to those synthesized at lower temperatures (900 deg. C). The activation energies for the ionic conductivities are comparable for all samples. Partial substitution of K{sup +} for La{sup 3+} and In{sup 3+} for Nb{sup 5+} in Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12} exhibits slightly higher ionic conductivity than that of the parent compound over the investigatedmore » temperature regime 25-300 deg. C. Among the compounds investigated, the In-substituted Li{sub 5.5}La{sub 3}Nb{sub 1.75}In{sub 0.25}O{sub 12} exhibits the highest bulk lithium ion conductivity of 1.8x10{sup -4} S/cm at 50 deg. 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{sup -1}-10{sup -7} cm{sup 2}/s over the temperature regime 50-200 deg. C, which is extraordinarily high and comparable with liquids. Substitution of Al, Co, and Ni for Nb in Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12} was found to be unsuccessful under the investigated conditions.« less

Authors:
 [1];  [2]
  1. Chair for Sensors and Solid State Ionics, Faculty of Engineering, University of Kiel, Kaiserstr. 2, D 24143-Kiel (Germany). E-mail: vt@tf.uni-kiel.de
  2. Chair for Sensors and Solid State Ionics, Faculty of Engineering, University of Kiel, Kaiserstr. 2, D 24143-Kiel (Germany)
Publication Date:
OSTI Identifier:
20784946
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 179; Journal Issue: 4; Other Information: DOI: 10.1016/j.jssc.2005.12.025; PII: S0022-4596(05)00613-4; Copyright (c) 2005 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACTIVATION ENERGY; CHEMICAL COMPOSITION; CUBIC LATTICES; DOPED MATERIALS; GRAIN BOUNDARIES; INDIUM IONS; IONIC CONDUCTIVITY; LANTHANUM COMPOUNDS; LANTHANUM IONS; LATTICE PARAMETERS; LITHIUM COMPOUNDS; LITHIUM IONS; NIOBIUM COMPOUNDS; NIOBIUM IONS; OXIDES; SINTERING; TEMPERATURE RANGE 0273-0400 K; TEMPERATURE RANGE 0400-1000 K; TEMPERATURE RANGE 1000-4000 K; X-RAY DIFFRACTION

Citation Formats

Thangadurai, Venkataraman, and Weppner, Werner. Effect of sintering on the ionic conductivity of garnet-related structure Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12} and In- and K-doped Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12}. United States: N. p., 2006. Web. doi:10.1016/j.jssc.2005.12.025.
Thangadurai, Venkataraman, & Weppner, Werner. Effect of sintering on the ionic conductivity of garnet-related structure Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12} and In- and K-doped Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12}. United States. doi:10.1016/j.jssc.2005.12.025.
Thangadurai, Venkataraman, and Weppner, Werner. Sat . "Effect of sintering on the ionic conductivity of garnet-related structure Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12} and In- and K-doped Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12}". United States. doi:10.1016/j.jssc.2005.12.025.
@article{osti_20784946,
title = {Effect of sintering on the ionic conductivity of garnet-related structure Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12} and In- and K-doped Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12}},
author = {Thangadurai, Venkataraman and Weppner, Werner},
abstractNote = {Garnet-structure related metal oxides with the nominal chemical composition of Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12}, In-substituted Li{sub 5.5}La{sub 3}Nb{sub 1.75}In{sub 0.25}O{sub 12} and K-substituted Li{sub 5.5}La{sub 2.75}K{sub 0.25}Nb{sub 2}O{sub 12} were prepared by solid-state reactions at 900, 950, and 1000 deg. 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 Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12}. The variation in the cubic lattice parameter was found to change with the size of the dopant ions, for example, substitution of larger In{sup 3+}(r {sub CN6}: 0.79 A) for smaller Nb{sup 5+} (r {sub CN6}: 0.64 A) shows an increase in the lattice parameter from 12.8005(9) to 12.826(1) A at 1000 deg. C. Samples prepared at higher temperatures (950, 1000 deg. C) show mainly bulk lithium ion conductivity in contrast to those synthesized at lower temperatures (900 deg. C). The activation energies for the ionic conductivities are comparable for all samples. Partial substitution of K{sup +} for La{sup 3+} and In{sup 3+} for Nb{sup 5+} in Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12} exhibits slightly higher ionic conductivity than that of the parent compound over the investigated temperature regime 25-300 deg. C. Among the compounds investigated, the In-substituted Li{sub 5.5}La{sub 3}Nb{sub 1.75}In{sub 0.25}O{sub 12} exhibits the highest bulk lithium ion conductivity of 1.8x10{sup -4} S/cm at 50 deg. 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{sup -1}-10{sup -7} cm{sup 2}/s over the temperature regime 50-200 deg. C, which is extraordinarily high and comparable with liquids. Substitution of Al, Co, and Ni for Nb in Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12} was found to be unsuccessful under the investigated conditions.},
doi = {10.1016/j.jssc.2005.12.025},
journal = {Journal of Solid State Chemistry},
number = 4,
volume = 179,
place = {United States},
year = {Sat Apr 15 00:00:00 EDT 2006},
month = {Sat Apr 15 00:00:00 EDT 2006}
}