Crystal structure, thermal expansion and high-temperature electrical conductivity of A-site deficient La{sub 2−z}Co{sub 1+y}(Mg{sub x}Nb{sub 1−x}){sub 1−y}O{sub 6} double perovskites
- Department of Materials and Manufacturing Technology, Chalmers University of Technology, SE-412 96 Gothenburg (Sweden)
- Department of Physics, Albanova University Center, Stockholm University, S-106 91 Stockholm (Sweden)
- Department of Materials and Environmental Chemistry, Stockholm University, S-106 91 Stockholm (Sweden)
- Department of Chemistry, M.V. Lomonosov Moscow State University, 119991 Moscow (Russian Federation)
New La-deficient double perovskites with P2{sub 1}/n symmetry, La{sub ∼1.90}(Co{sup 2+}{sub 1−x}Mg{sup 2+}{sub x})(Co{sup 3+}{sub 1/3}Nb{sup 5+}{sub 2/3})O{sub 6} with x=0, 0.13 and 0.33, and La{sub 2}(Co{sup 2+}{sub 1/2}Mg{sup 2+}{sub 1/2}) (Co{sup 3+}{sub 1/2}Nb{sup 5+}{sub 1/2})O{sub 6} were prepared by solid state reaction at 1450 °C. Their crystal structures were refined using time-of-flight neutron powder diffraction data. Our results show that certain cations such as Nb{sup 5+}, with very strong B–O bonds in the perovskite structure, can induce A-site vacancies in double perovskites. Upon heating in N{sub 2} gas atmosphere at 1200 °C ∼1% O atom vacancies are formed together with a partial reduction of the Co{sup 3+} content. The average thermal expansion coefficient between 25 and 900 °C of La{sub 1.90}(Co{sup 2+}{sub 2/3}Mg{sup 2+}{sub 1/3})(Co{sup 3+}{sub 1/3}Nb{sup 5+}{sub 2/3})O{sub 6} was determined to be 17.4 ppm K{sup −1}. Four-point electronic conductivity measurements showed that the compounds are semiconductors, with conductivities varying between 3.7·10{sup −2} and 7.7·10{sup −2} S cm{sup −1} at 600 °C and activation energies between 0.77 and 0.81 eV. Partial replacement of La{sup 3+} with Sr{sup 2+} does not lead to any increase of conductivity, while replacement of Mg{sup 2+} with Cu{sup 2+} in La{sub 1.9}CoCu{sub 1/3}Nb{sub 2/3}O{sub 6} and La{sub 1.8}CoCu{sub 1/2}Nb{sub 1/2}O{sub 6} leads to ∼100 times larger conductivities at 600 °C, 0.35 and 1.0 S cm{sup −1}, respectively, and lower activation energies, 0.57 and 0.73 eV, respectively. - Highlights: • Double perovskites, P2{sub 1}/n, La{sub 2−z}(Co{sup 2+}{sub 1−x}Mg{sup 2+}{sub x})(Co{sup 3+}{sub 1/3}Nb{sup 5+}{sub 2/3})O{sub 6} have been synthesized. • Crystal structures have been refined using neutron powder diffraction data. • Strong Nb–O bond and size ordering of Mg{sup 2+}/Co{sup 2+} and Nb{sup 5+}/Co{sup ~3+} leads to La-deficiency. • The compounds are semi conductors (~10{sup −2} S cm{sup −1}) at 600 °C. • Replacement of Mg{sup 2+} with Cu{sup 2+} leads to higher conductivity (~1.0 S cm{sup −1}) at 600 °C.
- OSTI ID:
- 22486771
- Journal Information:
- Journal of Solid State Chemistry, Vol. 229; Other Information: Copyright (c) 2015 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
SUPERCONDUCTIVITY AND SUPERFLUIDITY
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACTIVATION ENERGY
COBALT COMPOUNDS
COBALT IONS
COPPER IONS
ELECTRIC CONDUCTIVITY
LANTHANUM COMPOUNDS
LANTHANUM IONS
MAGNESIUM COMPOUNDS
MONOCLINIC LATTICES
NEUTRON DIFFRACTION
NIOBATES
NIOBIUM IONS
PEROVSKITE
REDUCTION
SEMICONDUCTOR MATERIALS
STRONTIUM IONS
THERMAL EXPANSION
TIME-OF-FLIGHT METHOD
VACANCIES