Role of Fe/Co Ratio in Dual Phase Ce0.8Gd0.2O2-δ-Fe3-xCoxO4 Composites for Oxygen Separation.

Dual-phase membranes are increasingly attracting attention as a solution for developing stable oxygen permeation membranes. Ce0.8Gd0.2O2-δ-Fe3-xCoxO4 (CGO-F(3-x)CxO) composites are one group of promising candidates. This study aims to understand the effect of the Fe/Co-ratio, i.e., x = 0, 1, 2, and 3 in Fe3-xCoxO4, on microstructure evolution and performance of the composite. The samples were prepared using the solid-state reactive sintering method (SSRS) to induce phase interactions, which determines the final composite microstructure. The Fe/Co ratio in the spinel structure was found to be a crucial factor in determining phase evolution, microstructure, and permeation of the material. Microstructure analysis showed that all iron-free composites had a dual-phase structure after sintering. In contrast, iron-containing composites formed additional phases with a spinel or garnet structure which likely contributed to electronic conductivity. The presence of both cations resulted in better performance than that of pure iron or cobalt oxides. This demonstrated that both types of cations were necessary to form a composite structure, which then allowed sufficient percolation of robust electronic and ionic conducting pathways. The maximum oxygen flux is jO2 = 0.16 and 0.11 mL/cm2·s at 1000 °C and 850 °C, respectively, of the 85CGO-FC2O composite, which is comparable oxygen permeation flux reported previously.

Measurement of polarization effects in dual-phase ceria-based oxygen permeation membranes using Kelvin probe force microscopy.

In this study, a dual phase composite (CSO-FC2O) consisting of 60 vol % Ce0.8Sm0.2O1.9 as oxygen-conductive phase and 40 vol % FeCo2O4 as electron-conductive phase was synthesized. TEM measurements showed a relatively pure dual-phase material with only minor amounts of a tertiary (Sm,Ce)(Fe,Co)O3 perovskite phase and isolated residues of a rock salt phase at the grain boundaries. The obtained material was used as a model to demonstrate that a combination of polarization relaxation measurements and Kelvin probe force microscopy (KPFM)-based mapping of the Volta potential before and after the end of polarization can be used to determine the chemical diffusion coefficient of the ceria component of the composite. The KPFM measurements were performed at room temperature and show diffusion coefficients in the range of 3 × 10-13 cm2·s-1, which is comparable to values measured for single-phase Gd-doped ceria thin films using the same method.