Structure and high-temperature properties of the (Sr,Ca,Y)(Co, Mn)O{sub 3-y} perovskites - perspective cathode materials for IT-SOFC

Journal Article · Wed Aug 15 00:00:00 EDT 2012 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/J.JSSC.2012.03.056· OSTI ID:22131121

Napolsky, Ph. S.; Drozhzhin, O. A. ^[1]; Kazakov, S. M.; Antipov, E. V. ^[1]; Galeeva, A. V.; Gippius, A. A. ^[2]; Svensson, G. ^[3]; Abakumov, A. M.; Van Tendeloo, G. ^[4]

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1. Department of Chemistry, Moscow State University, Leninskie Gory, Moscow 119991 (Russian Federation)
2. Department of Physics, Moscow State University, Leninskie Gory, Moscow 119991 (Russian Federation)
3. Department of Materials and Environmental Chemistry, Stockholm University, Stockholm S-10691 (Sweden)
4. EMAT, University of Antwerp, Groenenborgerlaan, Antwerp 171, B-2020 (Belgium)

Oxygen deficient perovskites Sr{sub 0.75}Y{sub 0.25}Co{sub 1-x}Mn{sub x}O{sub 3-y}, x=0.5 and 0.75, were prepared by using the citrate route at 1373-1573 K for 48 h. The cubic Pm-3m perovskite structure for x=0.5 was confirmed by electron diffraction study and refined using neutron powder diffraction (NPD) data. For x=0.75, the superstructure corresponding to a={radical}(2) Multiplication-Sign a{sub per}, b=2 Multiplication-Sign a{sub per}, c={radical}(2) Multiplication-Sign a{sub per} (a{sup 0}b{sup -}b{sup -} tilt system, space group Imma) was revealed by electron diffraction. The solid solution Sr{sub 0.75-x}Ca{sub x}Y{sub 0.25}Co{sub 0.25}Mn{sub 0.75}O{sub 3-y}, 0.1{<=}x{<=}0.6 and compound Ca{sub 0.75}Y{sub 0.25}Mn{sub 0.85}Co{sub 0.15}O{sub 2.92} were prepared in air at 1573 K for 48 h. The crystal structure of Ca{sub 0.75}Y{sub 0.25}Mn{sub 0.85}Co{sub 0.15}O{sub 2.92} was refined using NPD data (S.G. Pnma, a=5.36595(4), b=7.5091(6), c=5.2992(4) A, R{sub p}=0.057, R{sub wp}=0.056, {chi}{sup 2}=4.26). High-temperature thermal expansion properties of the prepared compounds were studied in air using both dilatometry and high-temperature X-ray powder diffraction data (HTXRPD). They expanding non-linearly at 298-1073 K due to the loss of oxygen at high temperatures. Calculated average thermal expansion coefficients (TECs) for Sr{sub 0.75}Y{sub 0.25}Co{sub 1-x}Mn{sub x}O{sub 3-y}, x=0.5, 0.75 and Ca{sub 0.75}Y{sub 0.25}Mn{sub 0.85}Co{sub 0.15}O{sub 2.92(1)} are 15.5, 15.1, and 13.8 ppm K{sup -1}, respectively. Anisotropy of the thermal expansion along different unit cell axes was observed for Sr{sub 0.15}Ca{sub 0.6}Y{sub 0.25}Co{sub 0.25}Mn{sub 0.75}O{sub 3-y} and Ca{sub 0.75}Y{sub 0.25}Mn{sub 0.85}Co{sub 0.15}O{sub 2.92}. Conductivity of Sr{sub 0.75}Y{sub 0.25}Co{sub 1-x}Mn{sub x}O{sub 3-y}, x=0.5 and 0.75 increases with the temperature reaching 110 S/cm for x=0.5 and 44 S/cm for x=0.75 at 1173 K. Samples of Sr{sub 0.75-x}Ca{sub x}Y{sub 0.25}Co{sub 0.25}Mn{sub 0.75}O{sub 3-y}, 0.1{<=}y{<=}0.6 were found to be n-type conductors at room temperature with the similar temperature dependence of the conductivity and demonstrated the increase of the {sigma} value from {approx}1 to {approx}50 S/cm as the temperature increases from 300 to 1173 K. Their conductivity is described in terms of the small polaron charge transport with the activation energy (E{sub p}) increasing from 340 to 430 meV with an increase of the calcium content from x=0 to x=0.6. - Graphical abstract: The substitution of cobalt in the 314-phase Sr{sub 0.75}Y{sub 0.25}CoO{sub 2.62} by manganese leads to the formation of oxygen deficient compounds Sr{sub 0.75}Y{sub 0.25}Co{sub 1-x}Mn{sub x}O{sub 3-y}, x=0.5 and 0.75, with the cubic and orthorhombic perovskite structures. The conductivity of the x=0.5 sample (110 S/cm) at 1173 K is substantially higher in comparison with x=0.75 (44 S/cm). Together with comparable TEC values for x=0.5 (15.5 ppm K{sup -1}) and 0.75 (15.1 ppm K{sup -1}) samples this makes the former one a promising cathode material for IT-SOFC. Partial replacement of Sr by Ca in Sr{sub 0.75}Y{sub 0.25}Co{sub 0.25}Mn{sub 0.75}O{sub 3-y} leads to the formation of the solid solution with the orthorhombic perovskite structure, Sr{sub 0.75-x}Ca{sub x}Y{sub 0.25}Co{sub 0.25}Mn{sub 0.75}O{sub 3-y}, 0.1{<=}y{<=}0.6. Along with Sr{sub 0.75}Y{sub 0.25}Co{sub 0.5}Mn{sub 0.5}O{sub 3-y}, novel perovskite Ca{sub 0.75}Y{sub 0.25}Mn{sub 0.85}Co{sub 0.15}O{sub 3-y} represent promising cathode material for IT-SOFC due to low TEC value (13.8 ppm K{sup -1}) and high conductivity of 135 S/cm at 1173 K. Highlights: Black-Right-Pointing-Pointer Mn-doped 314-phases Sr{sub 0.75}Y{sub 0.25}Co{sub 1-x}Mn{sub x}O{sub 3-y}, x=0.5, 0.75 were synthesized. Black-Right-Pointing-Pointer Sr{sub 0.75-x}Ca{sub x}Y{sub 0.25}Co{sub 0.25}Mn{sub 0.75}O{sub 3-y}, x=0.1--0.6, Ca{sub 0.75}Y{sub 0.25}Mn{sub 0.85}Co{sub 0.15}O{sub 3-y} were made. Black-Right-Pointing-Pointer High-temperature conductivity properties and crystal structure were studied. Black-Right-Pointing-Pointer High-temperature thermal expansion behavior was investigated.

• OSTI ID: 22131121
• Journal Information: Journal of Solid State Chemistry, Vol. 192; Other Information: Copyright (c) 2012 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

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACTIVATION ENERGY
ANISOTROPY
CATHODES
DOPED MATERIALS
NEUTRON DIFFRACTION
N-TYPE CONDUCTORS
ORTHORHOMBIC LATTICES
OXYGEN
PEROVSKITE
SOLID OXIDE FUEL CELLS
SOLID SOLUTIONS
SPACE GROUPS
TEMPERATURE DEPENDENCE
TEMPERATURE RANGE 0400-1000 K
TETRAGONAL LATTICES
THERMAL EXPANSION
X-RAY DIFFRACTION