Incorporation and Conduction of Protons in Ca Sr Ba-Doped BaLaInO4 with Ruddlesden-Popper Structure

摘要

The new phases BaLa0.9M0.1InO3.95 (M = Ca²⁺, Sr²⁺, Ba²⁺) with a Ruddlesden-Popper structure were obtained. It was established that all investigated samples were capable for the water uptake from the gas phase. The ability of water incorporation was due to not only by the presence of oxygen vacancies, but also due to the presence of La-O blocks in the structure. The degree of hydration of the samples was much higher than the concentration of oxygen vacancies and the composition of the samples appear to be BaLaInO3.42(OH)1.16, BaLa0.9Ca0.1InO3.25(OH)1.4, BaLa0.9Sr0.1InO3.03(OH)1.84, BaLa0.9Ba0.1InO2.9(OH)_2.1. The degree of hydration increased with an increase in the size of the dopant, i.e., with an increase in the size of the salt blocks. It was proven that doping led to the increase in the oxygen ionic conductivity. The conductivities for doped samples BaLa_0.9M_0.1InO_3.95 were higher than for undoped composition BaLaInO₄ at ~1.5 order of magnitude. The increase in the conductivity was mainly attributed to the increase of the carrier concentration as a result of the formation of oxygen vacancies during doping. The proton conductivities of doped samples increased in the order Ca²⁺–Sr²⁺–Ba²⁺ due to an increase in the concentration of protons. It was established that all doped samples demonstrated the dominant proton transport below 450 °C.