Experimental and Theoretical Solid-State Si NMR Studies on Defect Structures in La(SiO)O Apatite Oxide Ion Conductors.

Oxide ion conductors can be used as electrolytes in solid oxide fuel cells, a promising energy-conversion technology. Local structures around the defects in oxide ion conductors are key for understanding the defect stabilization and migration mechanisms. As the defect contents are generally low, it is rather difficult to characterize the defect structure and therefore elucidate how oxide ions migrate. Solid-state nuclear magnetic resonance (NMR) spectroscopy is a powerful technique for probing the local structures. However, the interpretation of NMR signals mainly based on the empirical knowledge could lead to unprecise local structures. There is still controversy regarding the defect structures in the apatite-type interstitial oxide ion conductors containing isolated tetrahedral units. Here, we combine the experimental solid-state Si NMR spectroscopy with theoretical density functional theory calculations to investigate the defect structures in La(SiO)O apatites. The results indicate that the Si resonance signals on the high field side of the main peak corresponding to the Si atoms in the bulk structure are related to La vacancies and there is no steady-state SiO in the defect structures. This finding provides new atomic-level understanding to the stabilization and migration of interstitial oxide ions in silicate apatites, which could guide the design and discovery of new solid oxide fuel cell electrolyte materials.