Ionic Conductivity of Ce0.91Ca0.09O2 as an Electrolyte for Intermediate Temperature Solid Oxide Fuel Cells

The search for new cost-effective electrolyte materials for IT-SOFC towards its mass scale commercialization has gained momentum in recent years. The Ca- doped ceria having composition Ce0.91Ca0.09O2 was prepared using the facile conventional solid-state method. The structural and electrical properties of low sintered ceramic samples have been characterized by X-ray diffraction (XRD), UV–VIS diffuse reflectance spectroscopy (DRS) and A.C. impedance technique respectively. The oxide ion conductivity was measured between the temperatures 573 K−973 K in air. The obtained results showed that total conductivity is mainly dependent on the grain boundary effect. The nanocrystalline Ce0.91Ca0.09O2 exhibited the high total ionic conductivity of 7.36  103 S cm1 at 973 K with a lower activation energy of 0.96 eV. The obtained results highlight the use of cost-effective dopant in ceria lattice to develop commercially viable electrolyte materials for IT-SOFC.

Facile and reproducible method of stabilizing $$\hbox {Bi}_2\hbox {O}_3$$ phases confined in nanocrystallites embedded in amorphous matrix

Bismuth sesquioxide ($$\hbox {Bi}_2\hbox {O}_3$$ Bi 2 O 3 ) draws much attention due to wide variety of phases in which it exists depending on the temperature. Among them, $$\delta$$ δ phase is specially interesting because of its high oxide ion conductivity and prospects of applications as an electrolyte in fuel cells. Unfortunately, it is stable only in a narrow temperature range ca. 730–830 $$^{\circ }$$ ∘ C. Our group has developed a facile and reproducible two-stage method of stabilizing $$\hbox {Bi}_2\hbox {O}_3$$ Bi 2 O 3 crystalline phases confined in nanocrystallites embedded in amorphous matrix. In the first stage, glassy materials were obtained by a routine melt-quenching method: pure $$\hbox {Bi}_2\hbox {O}_3$$ Bi 2 O 3 powders were melted in porcelain crucibles and fast-cooled down to room temperature. In the second step, the materials were appropriately heat-treated to induce formation of crystallites of $$\beta$$ β , $$\delta$$ δ or $$\gamma$$ γ $$\hbox {Bi}_2\hbox {O}_3$$ Bi 2 O 3 phases confined in a glassy matrix, depending on the process conditions. It was found out that the vitrification of the initial $$\hbox {Bi}_2\hbox {O}_3$$ Bi 2 O 3 and the subsequent nanocrystallization were unexpectedly possible due to the presence of some Al, and Si impurities from the crucibles. Systematic DTA, XRD, optical, Raman and SEM/EDS studies were carried out to investigate the influence of the syntheses processes and allowed us to determine conditions under which the particular phases appear and remain stable down to room temperature.

Influence of Isovalent ‘W’ Substitutions on the Structure and Electrical Properties of La2Mo2O9 Electrolyte for Intermediate-Temperature Solid Oxide Fuel Cells

Lanthanum molybdenum oxide (La2Mo2O9, LAMOX)-based ion conductors have been used as potential electrolytes for solid oxide fuel cells. The parent compound La2Mo2O9 undergoes a structural phase transition from monoclinic (P21) to cubic (P213) at 580 °C, with an enhancement in oxide ion conductivity. The cubic phase is of interest because it is beneficial for oxide ion conduction. In search of alternative candidates with a similar structure that might have a stable cubic phase at lower temperatures, we have studied the variations of the crystal structure and ionic conductivity for 25, 50, 62.5 and 75 mol% W substitutions at the Mo site using high-temperature X-ray diffraction, dilatometry, and impedance spectroscopy. Highly dense ceramic samples have been synthesized by solid-state reaction in a two-step sintering process. Low-angle X-ray diffraction and Rietveld refinement confirm the stabilization of the cubic phase for all compounds in the entire temperature range considered. The substitutions of W at the Mo site produce a decrement in the lattice parameter. The thermal expansion coefficients in the high-temperature range of the W-substituted ceramics, as determined by dilatometry, are much higher than that of the unmodified sample. The impedance spectra have been modeled using a modified genetic algorithm within 300–600 °C. A distribution function of the relaxation times is obtained, and the contributions of ohmic drop, grains and grain boundaries to the conductivity have been identified. Overall, our investigation provides information about cationic substitution and insights into the understanding of oxide ion conductivity in LAMOX-based compounds for developing solid oxide fuel cells.

High oxide-ion conductivity through the interstitial oxygen site in Ba7Nb4MoO20-based hexagonal perovskite related oxides

Oxide-ion conductors are important in various applications such as solid-oxide fuel cells. Although zirconia-based materials are widely utilized, there remains a strong motivation to discover electrolyte materials with higher conductivity that lowers the working temperature of fuel cells, reducing cost. Oxide-ion conductors with hexagonal perovskite related structures are rare. Herein, we report oxide-ion conductors based on a hexagonal perovskite-related oxide Ba7Nb4MoO20. Ba7Nb3.9Mo1.1O20.05 shows a wide stability range and predominantly oxide-ion conduction in an oxygen partial pressure range from 2 × 10−26 to 1 atm at 600 °C. Surprisingly, bulk conductivity of Ba7Nb3.9Mo1.1O20.05, 5.8 × 10−4 S cm−1, is remarkably high at 310 °C, and higher than Bi2O3- and zirconia-based materials. The high conductivity of Ba7Nb3.9Mo1.1O20.05 is attributable to the interstitial-O5 oxygen site, providing two-dimensional oxide-ion O1−O5 interstitialcy diffusion through lattice-O1 and interstitial-O5 sites in the oxygen-deficient layer, and low activation energy for oxide-ion conductivity. Present findings demonstrate the ability of hexagonal perovskite related oxides as superior oxide-ion conductors.

Structural and Electrochemical Properties of Lanthanum Silicate Apatites La10Si6−x−0.2AlxZn0.2O27−δ for Solid Oxide Fuel Cells (SOFCs)

An excellent oxide ion conductivity with high oxygen transportation of lanthanum silicate apatite at the solid oxide fuel cell (SOFC) can be achieved through the solid-state reaction method. The doped La10Si6−x−0.2AlxZn0.2O27−δ (x = 0.2 and 0.4) materials sintered at 1600°C accomplished crystallinity and crystal structure of apatite-type. The structural and electrochemical characterizations of La10Si6−x−0.2AlxZn0.2O27−δ (x = 0.2 and 0.4) were executed using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), and electrochemical impedance spectroscopy (EIS) measurements. The total oxide ion conductivities of La10Si6−x−0.2AlxZn0.2O27−δ (x = 0.2 and 0.4) were measured from low to intermediate operating temperature range (450 to 800°C) using electrochemical impedance spectroscopy. Room temperature XRD patterns of La10Si6−x−0.2AlxZn0.2O27−δ (x = 0.2 and 0.4) exhibited La10Si6O27 apatite phase with space group P63/m as the main phase with the minor appearance of La2SiO5 as an impurity phase. The highest total oxide ion conductivity of 3.24 × 10−3 Scm−1 and corresponding activation energy of 0.30 eV at 800°C were obtained for La10Si5.6Al0.2Zn0.2O26.7 which contains a low concentration of Al3+ dopant.

High Oxide-ion Conductivity in Acceptor-doped Bi-based Perovskites at Modest Doping Levels

A combination of Impedance Spectroscopy, Time-of-Flight Secondary Ion Mass Spectrometry and literature data are used to show that, (i) the bulk oxide ion conductivity of A-site, alkaline earth-doped BiFeO3 (BF)...