Cation size effects in oxygen ion dynamics of highly disordered pyrochlore-type ionic conductors
In this work we evaluate the effect of cation size on the dc activation energy needed for oxygen ion migration, E_(dc), in highly disordered pyrochlore-type ionic conductors A_(2)B_(2)O_(7). Twenty six compositions with the general formula, Ln_(2)Zr_(2−y)Ti_(y)O_(7), Ln_(1.7)Mg_(0.3)Zr_(2)O_(7) (Ln=...
| Autores: | , , , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2008 |
| País: | España |
| Institución: | Universidad Complutense de Madrid (UCM) |
| Repositorio: | Docta Complutense |
| Idioma: | inglés |
| OAI Identifier: | oai:docta.ucm.es:20.500.14352/51401 |
| Acceso en línea: | https://hdl.handle.net/20.500.14352/51401 |
| Access Level: | acceso abierto |
| Palabra clave: | 537 Electrical relaxation Constituent oxides Coupling model Spin ice Conductivity Migration Diffusion Gd_(2)Ti_(2)O_(7) Glasses Melts. Electricidad Electrónica (Física) 2202.03 Electricidad |
| Sumario: | In this work we evaluate the effect of cation size on the dc activation energy needed for oxygen ion migration, E_(dc), in highly disordered pyrochlore-type ionic conductors A_(2)B_(2)O_(7). Twenty six compositions with the general formula, Ln_(2)Zr_(2−y)Ti_(y)O_(7), Ln_(1.7)Mg_(0.3)Zr_(2)O_(7) (Ln=Y, Dy, and Gd), and Gd_(2−y)La_(y)Zr_(2)O_(7), were prepared by mechanical milling, and their electrical properties were measured by using impedance spectroscopy as a function of frequency and temperature. By using the coupling model we also examine the effect of cation radii R_(A) and R_(B) on the microscopic potential-energy barrier, E_(a), which oxygen ions encounter when hopping into neighboring vacant sites. We find that, for a fixed B-site-cation radius R_(B), both activation energies decrease with increasing A-site-cation size, R_(A), as a consequence of the increase in the unit-cell volume. In contrast, for a given R_(A) size, the E_(dc) of the Ln_(2)Zr_(2−y)Ti_(y)O_(7) series increases when the average R_(B) size increases. This behavior is associated with enhanced interactions among mobile oxygen ions as the structural disorder increases with R_(B). |
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