Volume 54, Nº 6 (2018)

The crystals of (ZrO₂)_1–x(Sc₂O₃)_x(СeO₂)_0.01 solid solutions (x = 0.08–0.10) were obtained by directional crystallization. The crystals of the grown composites were semitransparent, opalescent, and without cracks and had varying microstructure in the bulk. In the range of compositions under study, it was impossible to obtain optically homogeneous, fully transparent crystals. The crystals grown at a growth rate of 10 mm/h had a nonuniform distribution of ceria along the length of the ingot. The introduction of ceria in an amount of 1 mol % increased the conductivity of the crystals, but the increase in the specific electric conductivity depended on the Sc₂O₃ content and the phase composition of the crystals. The highest conductivity was inherent in the (ZrO₂)_0.89(Sc₂O₃)_0.10(CeO₂)_0.01 crystals.

To study the effect of chromium oxide on the electric properties of Ce_0.9Gd_0.1O₂, a solid-oxide fuel cell electrolyte, two approaches were used: (a) the studying of electrochemical properties of the Ce_0.9Gd_0.1O₂- electrolyte after the spontaneous adsorption of chromium-containing molecules from a gas phase and (b) the analyzing of transport properties of the Ce_0.9Gd_0.1O₂-based chromium-containing compositions obtained by the mixing of solid-oxide electrolyte with chromium(III) oxide. It was found that the chromium reduction at the electrolyte surface dominates when chromium is adsorbed from gas phase. Both approaches allow concluding that the chromium presence in Ce_0.9Gd_0.1O₂ deteriorates the electrolyte transport properties at temperatures above 735°С. This is caused by the chromium incorporation into the electrolyte’s fluorite structure, as well as surface microheterogeneity induced by the chromium presence at the Ce_0.9Gd_0.1O₂ surface and the cerium and gadolinium cation redistribution between the grains’ bulk and surface. At intermediate temperatures (below 735°С) the electric conductivity of the Ce_0.9Gd_0.1O₂-based chromium-containing composition exceeds that of the initial solid-oxide electrolyte, which can be due to changes in transport properties of the chromium-containing phases formed at the Ce_0.9Gd_0.1O₂ surface and grain boundaries.

The oxygen nonstoichiometry and electrical conductivity of fluorite-type solid solutions Ce_0.6‒xLa_0.4Pr_xO_2–δ (x = 0.1–0.2) were studied in the oxygen partial pressure range 10^–19–0.35 atm at 1023–1223 K. It was confirmed that the Pr^4+/3+ and Ce^4+/3+ redox pairs, which determine the concentration of p- and n-type electron charge carriers, play the dominant roles under oxidizing and reducing conditions, respectively. The conductivity vs. charge carrier concentration dependencies in these conditions are almost linear. Increasing praseodymium content leads to a substantially higher hole conductivity and an expanded range of the oxygen nonstoichiometry variations at high oxygen partial pressures. Under reducing conditions when praseodymium cations become trivalent opposite trends are observed on doping.

The effect of the type (semolina, starch, and ashless filter paper) and amount (5 and 10 wt %) of pore-forming agents on the structure of supporting Ni-cermet anodes and characteristics of solid-oxide fuel cells on their basis has been studied. It has been found that the use of paper fibers as the pore-forming agent doubles the open porosity of the anode as compared with equal amounts of semolina or starch. It has been shown that the long cylindrical pores formed by fibers allow fast transport of gases through the anode bulk, which has a positive effect on the fuel cell characteristics.

In this work, effects of molybdenum doping on the crystal structure, stability, electrical conductivity, oxygen permeability and thermomechanical properties of Sr(Fe,Al)O_3–δ-based perovskites, were studied. The electrochemical performance of model anodes of solid oxide fuel cells (SOFCs), made of SrFe_0.7Mo_0.3O_3–δ, was assessed. Whilst the introduction of Mo cations improves structural stability with respect to the oxygen vacancy ordering processes, excessive molybdenum content leads to a worse phase and mechanical stability under oxidizing conditions. Mo-doping was shown to decrease the thermal and chemical expansivity, to reduce p-type electronic conductivity and to increase n-type electronic conduction. The oxygen permeation fluxes through gas-tight Sr_0.97Fe_0.75Al_0.2Mo_0.05O_3–δ membranes are determined by both the bulk oxygen diffusion and surface exchange kinetics. The role of the latter factor increases on decreasing temperature and reducing oxygen partial pressure. Due to a relatively high electrical conductivity and moderate thermal expansion coefficients in reducing conditions, SrFe_0.7Mo_0.3O_3–δ-based anodes show a substantially high electrochemical activity.

In order to evaluate applicability of mixed-conducting PrBaFe_2–xNi_xО_{5 + δ} perovskites for cathodes of solid oxide fuel cells (SOFCs), their crystal structure, thermal and chemical expansion, electrical conductivity and electrochemical behavior were studied. The solubility limit of nickel in PrBaFe₂O_{5 + δ} corresponds to x = 0.8. At x > 0.2, the disordered cubic phase transformed into the tetragonal phase. The maximum level of conductivity (50–120 S/cm) at the operating temperatures of SOFC was found for the composition with the maximum nickel content, PrBaFe_1.2Ni_0.8О_{5 + δ}. This material is also characterized by moderate thermal and chemical expansion relative to other ferrite-nickelates. The polarization resistance of a porous PrBaFe_1.2Ni_0.8О_{5 + δ} cathode in a cell with a protective Ce_0.6La_0.4O_2–δ layer and a solid electrolyte (La_0.9Sr_0.1)_0.98Ga_0.8Mg_0.2O_3–δ was ~0.9 Ohm cm² at a temperature of 1073 K, atmospheric oxygen pressure, and current density of–120 mA cm^–2.

The microtubular design of solid oxide fuel cells (SOFCs), which are promising electrochemical power sources, has a number of significant advantages over traditional planar and tubular designs: increased resistance to the cell (stack) heating rate and packing density of cells in a stack. The paper presents results on the development of a microtubular SOFC (MT-SOFC) fabrication method based on compaction and co-sintering a set of films. The formation of an anode-supported MT-SOFC having a Ni-cermet collector (support) and functional layers of about 300 and 50 μm thick, respectively; a Zr_0.84Y_0.16O_2–δ solid electrolyte layer (40 μm); and a cathode based on La_0.7Sr_0.3MnO_3–δ has been developed. The outer diameter and length of the MT-SOFC were 3.9 and 12 mm, respectively. The maximum specific power generated by the MT-SOFC at 850°C was 0.21 W/cm².

PtIr/C electrocatalyst with the metal phase uniformly distributed over the carbon support surface and the average size of PtIr nanoparticles of 5.9 nm is synthesized by electrochemical dispersion of Pt₉₀Ir₁₀ alloy under the action of alternating pulse current. It is shown that the presence of iridium within the composition of a Pt/C catalyst lowers down the overpotential of CO oxidation and increases catalyst’s specific activity with respect to electrochemical oxidation of ethanol.