Local structure and oxide-ion conduction mechanism in apatite-type lanthanum silicates

Abstract

The local structure of apatite-type lanthanum silicates of general formula La_9.33+x(SiO₄)₆O_2+3x/2 has been investigated by combining the atomic pair distribution function (PDF) method, conventional X-ray and neutron powder diffraction (NPD) data and density functional theory (DFT) calculations. DFT was used to build structure models with stable positions of excess oxide ions within the conduction channel. Two stable interstitial positions were obtained in accordance with literature, the first one located at the very periphery of the conduction channel, neighbouring the SiO₄ tetrahedral units, and the second one closer to the channel axis. The corresponding PDFs and average structures were then calculated and tested against experimental PDFs obtained by X-ray total scattering and NPD Rietveld refinements results gathered from literature. It was shown that of the two stable interstitial positions obtained with DFT only the second one located within the channel is consistent with experimental data. This result consolidates one of the two main conduction mechanisms along the c-axis reported in the literature, namely the one involving cooperative movement of O4 and Oi ions.

Keywords:

• Lanthanum silicate
• local structure
• conduction mechanism
• pair distribution function (PDF)
• density functional theory (DFT)

Classification:

• 50 Energy Materials
• 107 Glass and ceramic materials
• 207 Fuel cells / Batteries / Super capacitors
• 401 1st principle calculations
• 504 X-ray / Neutron diffraction and scattering

Acknowledgments

This work was supported by a CNRS International Scientific Collaborative Project (PICS) between SPCTS laboratory and Nagoya Institute of Technology.