Modification of Ruddlesden-Popper-type Nd2-xNi0.75Cu0.2M0.05O4±δ by the Nd-site cationic deficiency and doping with Sc, Ga or In: Crystal structure, oxygen content, transport properties and oxygen permeability

Abstract

Abstract Nd2-xNi0.75Cu0.2M0.05O4±δ (x\xa0\u200b=\xa0\u200b0 and 0.1; M\xa0\u200b=\xa0\u200bSc, Ga, and In) Ruddlesden-Popper-type oxides are obtained by a sol-gel route and characterized concerning phase composition and crystal structure. It is found that the largest In3+ cannot be effectively introduced into the structure, while Nd stoichiometric and cation-deficient Nd2-xNi0.75Cu0.2Sc0.05O4±δ and Nd2-xNi0.75Cu0.2Ga0.05O4±δ (x\xa0\u200b=\xa0\u200b0; 0.1) can be obtained as single-phase materials. Systematic characterization of the crystal structure at high temperatures, oxygen content, as well as transport properties reveals that while the Nd-site deficiency has rather negligible influence on the structure, it causes a substantial decrease of the oxygen content, which at high temperatures leads to a change of the dominant type of defects from the oxygen interstitials to the vacancies for Nd1.9Ni0.75Cu0.2Sc0.05O4±δ and Nd1.9Ni0.75Cu0.2Ga0.05O4±δ. The Nd-site deficiency also causes a decrease of the total conductivity. Importantly, all the examined materials exhibit full chemical stability in CO2 atmosphere, which together with moderate thermal expansion makes them good candidates for the oxygen transport membranes, which can be used e.g. in the air separation technologies. The selected Sc- and Ga-doped compounds evaluated as ceramic membranes show relatively high oxygen fluxes, with the highest value of 0.78\xa0\u200bmL\xa0\u200bcm-2 min-1 at ca. 880\xa0\u200b°C registered for 0.9\xa0\u200bmm thick, dense Nd1.9Ni0.75Cu0.2Ga0.05O4±δ membrane.