Disorder and Diffusion in Mayenite

H. Boysena, I. Kaiser-Bischoffa, M. Lerchb, S. Berendtsb, M. Hoelzelc and A. Senyshync a Department für Geo- und Umweltwissenschaften, Sektion Kristallographie, LMU München, Am Coulombwall 1, 85748 Garching, Germany b Institut für Chemie, TU Berlin, Str. des 17. Juni 135, 10623 Berlin, Germany c TU Darmstadt, Institute of Materials Science, Petersenstr. 23, 64287 Darmstadt, Germany

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Mayenite, Ca12Al14O33, has attracted enormous attention for novel technological applications after the discovery of its high oxygen ionic conductivity. The crystal structure consists of a calcium-aluminate framework, comprising 32 of the 33 oxygen anions. The remaining oxygen is distributed over 1/6 of large cages within the framework. The true structure is heavily disordered and usually non-stoichiometric due to the presence of extra anions and is presented for four samples: pure oxygen mayenite (O-mayenite), partly (O/N-mayenite) and fully (N-mayenite) exchanged by nitrogen and doped with iron (Fe-mayenite). All samples were investigated by neutron powder diffraction up to 1050°C. Data were analysed by the Rietveld method and by difference Fourier methods. As prepared O-mayenite contains O2- and OH-, N- and O/N-mayenite also NH2-, NH2- and N3-, while Fe-mayenite was free of extra radicals. In O- and N-mayenite the extra species are lost under vacuum conditions above ca. 700°C, whereas O/N-mayenite retained NH2- up to high temperatures. Diffusion of oxygen proceeds via a jump-like interstitialcy process involving exchange of the "free" oxygen with framework oxygen, coupled to relaxations of Ca ions. In O/N-mayenite NH2- diffuses via interstitial process. In Fe-mayenite encaged oxygen is "invisible" due to extreme delocalisation or loss.

DOI: 10.12693/APhysPolA.117.38 PACS numbers: 61.43.-j, 61.66.-f, 61.05.fm