Phase transition and mixed oxide-proton conductivity in germanium oxy-apatites

La9.75□0.25(Ge6O24)O2.62 oxy-apatite shows a phase transition from triclinic to hexagonal symmetry at approximately 1020 K that has been characterised by high-temperature synchrotron X-ray and neutron powder diffraction, and ionic conductivity measurements. The crystal structure at 1073 K has been determined from joint Rietveld refinements of synchrotron X-ray and neutron powder diffraction data. The study shows that hexagonal-La9.75□0.25(Ge6O24)O2.62 contains interstitial oxygen at the position previously reported for other oxy-germanates. Changes in the oxide conductivity associated with this structural transition are discussed. The thermal analyses showed a weight loss on heating close to 600 K very likely due to water release. The synchrotron thermodiffractometric study shows an anomaly in the cell parameters evolution at that temperature, which indicates that this residual water is located into the apatite channels. The electrical characterisation under different atmospheres (dry and wet synthetic air) indicates that there is a significant proton contribution to the overall conductivity below 600 K, mainly under wet atmosphere.

La9.75□0.25(Ge6O24)O2.62 oxide-conductor shows triclinic–hexagonal phase transition (see inset) at ∼1020 K, meanwhile La9.55□0.45(Ge6O24)O2.32 is hexagonal at all temperatures. Both compounds have mixed proton and oxide conductivities below 600 K.Figure optionsDownload as PowerPoint slide