Proton and oxygen ion conductivity in the pyrochlore/fluorite family of Ln(2-x)Ca(x)ScMO(7-delta) (Ln = La, Sm, Ho, Yb; M = Nb, Ta; x=0, 0.05, 0.1) niobates and tantalatesстатья
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Дата последнего поиска статьи во внешних источниках: 7 марта 2018 г.
Аннотация:The tolerance factor is a good criterion to understand the structural transitions in Ln(2-x)Ca(x)ScMO(7-delta) (Ln = La, Sm, Ho, Yb; M = Nb, Ta; x = 0, 0.05, 0.1). Decreasing the Ln ionic radius in Ln(2)ScNb(Ta)O-7 leads to a morphotropic transition from a pyrochlore to a fluorite-like structure. Ca2+-doping leads to a pyrochlore-to-fluorite transition in Ln(2-x)Ca(x)ScMO(7-delta) (Ln = La, Sm) and a fluorite-to-pyrochlore transition in Ho2-xCaxScNbO7-delta. Proton contribution to the total conductivity was observed for Ln(2-x)CaxScNb(Ta)O7-delta (Ln = La, Sm; x = 0, 0.05, 0.1) 3+/5+ pyrochlores and the maximum proton contribution was shown by Sm1.9Ca0.1ScMO6.95 (M = Nb, Ta), which are located at the boundary between pyrochlores and fluorites (comparative study of electrical conduction and oxygen diffusion). Proton conduction of Sm1.9Ca0.1ScNbO6.95 and Sm1.9Ca0.1ScTaO6.95 pyrochlores persists up to 800 and 850 degrees C, respectively. The conductivity of fluorite-like Ho2-xCaxScNbO7-delta (x = 0, 0.05) and Yb2ScNbO7 is dominated by the oxygen ion transport, in accordance with their energy activation values 1.09-1.19 eV. The dielectric permittivity and TG studies were used for the investigation of oxygen vacancy dynamics and water incorporation into the Ln(2-x)Ca(x)ScNb(Ta)O7-delta (Ln = La, Sm, Ho, Yb; x = 0, 0.05, 0.1) lattice. It is shown that oxygen vacancy-related dielectric relaxation in the range of 550-650 degrees C (ambient air), typical of pyrochlores and fluorites with pure oxygen ion conductivity, decreases and disappears for proton-conducting oxides.