Publication date: 10th April 2024
In previous studies in our laboratory, we observed that the La-based perovskites have a tendency to increase proton conductivity as the B-site elements vary. This tendency increased as the radius of the B-site elements increased, as the material became more basic to the oxygen sites. As a result, it has undergone a transition from an oxygen-ion conductor to a mixed proton-oxygen conductor, eventually becoming a proton conductor material [1]. In order to understand the trends of conductors with perovskites, Ba-based perovskites were used in this study. By varying the B-site elements BaMO3 (M = Ce, Zr, Sn and Fe) and doping the trivalent elements Y to create oxygen vacancies, changes in both electronic and ionic conductivity were observed.
Firstly, the values of unit cell volume divided by Z (Å3) of BaM0.9Y0.1O3-d (BCY, BZY, BSY, and BFY) were calculated as follows, BCY: 85.1 Å3, BZY: 74 Å3, BSY: 69.3 Å3, and BFY: 64.7 Å3. Comparing these values with previous results of La-based perovskites, the values of unit cell volume divided by Z (Å3) of La0.9Sr0.1InO3-d and La0.9Sr0.1ScO3-d approximately 72.5 Å3 and 58.1 Å3, similar to the values of BSY and BFY. It is thought that BSY and BFY could be considered as mixed conductors. BSY and BFY were also considered as mixed conductors in other studies. In addition, the of La0.9Sr0.1YO3-d shows value around 75.5 Å3, similar to those of BCY and BZY. These materials could be thought of as proton conductors. Thus, similar trends in unit cell volume divided by Z and conduction properties were observed in both La-based and Ba-based perovskites.
Doping with different molar amounts of Y to create more oxygen vacancies was also used to understand the changes in the electronic/ionic conductivity. Ba-based perovskites BaM1-xYxO3-δ (M = Ce, Zr, Sn) (X = 0.1, 0.2, 0.3) were used in this study. As the amount of Y doping increased, the ionic conductivity of each material increased due to the increase in oxygen vacancies. The increase in Y doping also reduced the hole conductivity of P-type conductors in high oxygen atmospheres. It is suggested that an increase in oxygen vacancies suppressed hole conduction. Furthermore, the conductivity of the proton conductors (BCY, BZY) decreased after the dehydration treatment at the same temperature. It is suggested that the dehydration treatment reduced the proton concentration and resulted in a decrease in the ionic conductivity. This study provides a comprehensive understanding of the effect of B-site elements on the conductivity properties and contributes to the development of new materials for proton conductors.
Keyword: Ba perovskite structural material, oxygen vacancy, proton conductor, composite conductor, ionic conductivity
This study was supported by the National Science and Technology Council of Taiwan [Grant No. 112-2221-E-027 -028 – and 112-2622-E-027 -013 -]
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