Defect Chemistry of the Mixed Conducting Cage Compound Ca12Al14O33 |
J. Janek, D.K. Lee |
Institute of Physical Chemistry, Justus-Liebig-University |
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ABSTRACT |
The electrical transport properties of mayenite ($Ca_{12}Al_{14}O_{33}$ or $12CaO{cdot}7Al_2O_3$; mostly abbreviated as $C_{12}A_7$) can be controlled in a wide range by varying the oxygen deficiency: At high temperatures mayenite becomes either an oxygen solid electrolyte, a mixed ionic/electronic conductor or an inorganic electride with metal-like properties upon chemical reduction (removing oxygen). The underlying defect chemistry can be understood on the basis of a relatively simple model-despite the complex cage structure: A point defect model based on the assumption that the framework $[Ca_{12}Al_{14}O_{32}]^{2+}$ acts as a pseudo-donor describes well the high temperature transport properties. It accounts for the observed conductivity plateau at higher oxygen activities and also describes the experimentally observed oxygen activity dependence of the electronic conductivity with -1/4 slope at temperatures between 800 and $1000^{circ}C$. Doping effects in mayenite are still not well explored, and we review briefly the existing data on doping by different elements. Hydration of mayenite plays a crucial role, as Mayenite is hygroscopic, which may be a major obstacle for technical applications. |
Key words:
Mayenite, $Ca_{12}Al_{14}O_{33}$, Electronic conductivity, Ionic conductivity, Defect structure, $C_{12}A_7$ |
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