High Proton Conduction in the Octahedral Layers of Fully Hydrated Hexagonal Perovskite-Related Oxides.
Kohei MatsuzakiKei SaitoYoichi IkedaYusuke NambuMasatomo YashimaPublished in: Journal of the American Chemical Society (2024)
Proton conductors have potential applications such as fuel cells, electrolysis cells, and sensors. These applications require new materials with high proton conductivity and high chemical stability at intermediate temperatures. Herein we report a series of new hexagonal perovskite-related oxides, Ba 5 R 2 Al 2 SnO 13 ( R = Gd, Dy, Ho, Y, Er, Tm, and Yb). Ba 5 Er 2 Al 2 SnO 13 exhibited a high proton conductivity without chemical doping (e.g., 0.01 S cm -1 at 303 °C), which is attributed to its high proton concentration and diffusion coefficient. The high diffusion coefficient of Ba 5 Er 2 Al 2 SnO 13 can be attributed to the fast proton migration in the octahedral layers. The high proton concentration is attributed to full hydration in hydrated Ba 5 Er 2 Al 2 SnO 13 and the large amount of intrinsic oxygen vacancies in the dry sample, as evidenced by both neutron diffraction and thermogravimetric analysis. Ba 5 Er 2 Al 2 SnO 13 was found to exhibit high chemical stability under wet atmospheres of O 2 , air, H 2 , and CO 2 . High proton conductivity and high chemical stability indicate that Ba 5 Er 2 Al 2 SnO 13 is a superior proton conductor. Ba 5 R 2 Al 2 SnO 13 ( R = Gd, Dy, Ho, Y, Tm, and Yb) exhibited high electrical conductivity in wet N 2 , suggesting that these materials also exhibit high proton conductivity. These findings will open new avenues for proton conductors. The high proton conductivity via full hydration and fast proton migration in octahedral layers in highly oxygen-deficient hexagonal perovskite-related materials would be an effective strategy for developing next-generation proton conductors.