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Isovalent and aliovalent substitution effects on redox chemistry of Sr2MgMoO6 - δ SOFC-anode material
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Isovalent and aliovalent substitution effects on redox chemistry of Sr2MgMoO6 - δ SOFC-anode material

S. Vasala, M. Lehtimäki, S.C. Haw, J.M. Chen, R.S. Liu, H. Yamauchi and M. Karppinen
Solid State Ionics, Vol.181(15-16), pp.754-759
03/06/2010

Abstract

Cation substitution Degree of B-site cation order Double-perovskite oxide Oxygen non-stoichiometry Redox chemistry Solid oxide fuel cell XANES spectroscopy
An SOFC-anode material, Sr 2 MgMoO 6 - δ , is investigated for both isovalent and aliovalent substitution effects at its redox-active cation site. Isovalent W VI -for-Mo VI substitution has little effect on crystal and redox chemistry of the phase, whereas aliovalent Nb V -for-Mo VI substitution lowers the degree of cation order and, rather importantly, creates oxygen vacancies in the lattice. The increased oxygen-vacancy concentration should be a positive factor regarding the SOFC-anode performance, but a disadvantage is that electrical conductivity is slightly depressed in Sr 2 Mg(Mo,Nb)O 6 - δ with increasing Nb content. The two systems, Sr 2 Mg(Mo,W)O 6 - δ and Sr 2 Mg(Mo,Nb)O 6 - δ , are found stable (up to 1000 °C or higher) in both reductive (5% H 2 /Ar) and oxidative (air) atmospheres, the range of oxygen-content variation upon such redox-cycling getting narrower with increasing substitution level. XANES data at the L edges of Mo, W and Nb reveal that in Sr 2 Mg(Mo,W)O 6 - δ both Mo and W show variable oxidation states whereas in Sr 2 Mg(Mo,Nb)O 6 - δ Nb is more redox-active than Mo. © 2010 Elsevier B.V. All rights reserved.

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