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Performance of Ca-doped strontium ferrite-molybdate Sr2-xCaxFe1.5Mo0.5O6-δ (x = 0, 0.05, 0.15, 0.3, 0.5) has been studied under reducing conditions. Thermogravimetry (TG) analysis in 5% H2/Ar and DSC measurements in high-purity argon demonstrated that the compositions are highly stable and there are no phase transitions. The best electrochemical and electrical performances of about 0.12 Ω cm2 and 33 S/cm at 800 °C in wet hydrogen, respectively, were obtained for the Sr1.85Ca0.15Fe1.5Mo0.5O6-δ anode. The EIS spectra were analyzed by means of distribution relaxation times and non-linear least squares methods, which made it possible to determine the behavior of the rate-limiting steps of hydrogen oxidation. Solid oxide fuel cells (SOFC) of planar design with the 1.5 mm LaGaO3-based supporting electrolyte, with the Sr1.85Ca0.15Fe1.5Mo0.5O6-δ symmetrical electrodes and with the Sr2-xCaxFe1.5Mo0.5O6-δ (x = 0.15 and 0.3) anode and the 70 wt% Pr0.9Y0.1BaCo2O6–δ + 30 wt% SDC cathode have been studied. The obtained results demonstrated a low anode overvoltage, which was about 0.12 V at 1 A/cm2 and 800 °C in wet hydrogen. The maximum power density of SOFC with the Sr1.85Ca0.15Fe1.5Mo0.5O6-δ anode and cobaltite cathode was about 0.18 W/cm2 at 800 °С under air/wet hydrogen conditions. The obtained results elucidate that Sr1.85Ca0.15Fe1.5Mo0.5O6-δ is a promising anode for solid oxide fuel cells.

The anodic and cathodic polarization dependences for the oxygen electrode based on lanthanum-strontium manganite and the fuel Ni-cermet electrode are studied in the temperature range of 700–900°С in gas media that correspond to working conditions of a reversible fuel cell. The temporal behavior of these electrodes is studied in the course of periodic polarity changes of current with the density of 0.5 A/cm2. The electrode overvoltage is shown to be about 0.1 V in modes of power generation and water electrolysis at 900°С and the current density of 0.5 A/cm2. A single electrolyte supported tubular solid-oxide fuel cell was fabricated and tested in the fuel-cell and hydrogen-generation modes. It is found that at 900°С and overvoltage of 0.7 V, the cell generates the specific electric power of 0.4 W/cm2 when the 50% H2 + 50% H2O gas mixture is used as the fuel and air is used as the oxidizer. At the water electrolysis with the current density of 0.5 A/cm2, which under normal conditions corresponds to generation of about 0.2 and 0.1 L/h of hydrogen and oxygen, respectively, the consumed power is about 0.55 W/cm2. The efficiency of the conversion cycle electric power–hydrogen–electric power is 70–75%.

Oxygen electroreduction kinetics and electrochemical performance of the Pr6O11-impregnated Sr2Fe1.5Mo0.5O6-δ – Ce0.8Sm0.2O1.9 (SFM–SDC) cathode have been first studied. By means of distribution of relaxation times and non-linear least squares analysis of impedance spectra were shown that the addition of Pr6O11 into the cathode leads to the increase in the rate of the low-frequency step. It is suggested that the observed phenomenon is associated with the increase in the rate of surface oxygen exchange. It is shown that the introduction of praseodymium oxide into the cathode results in a decrease in the area specific polarization resistances of the cathode at equilibrium potentials from 0.23 to 0.06 Ω cm2 at 800 °C in air. The maximum power density of symmetrical solid oxide fuel cell (SOFC) with impregnated SFM–SDC electrodes and supporting 760 μm La0.85Sr0.15Ga0.85Mg0.15O3-δ electrolyte without buffer/barrier and collector layers under air/wet hydrogen (dry CH4) condition was about 0.5 (0.26) W cm−2 at 800 °С. The overvoltage of the cathode was higher than that of the anode under air/wet hydrogen and vice versa when methane was supplied to the anode. The obtained results elucidate that the impregnated SFM–SDC is a promising cathode for SOFC application.

Characteristics of fuel cells with supporting Ni-YSZ anode, bilayer YSZ/GDC electrolyte with the thickness of 10 μm, and La2NiO4 + δ cathode are studied. It is shown that when humid (3% water) hydrogen is supplied to the anode and air is supplied to the cathode, the maximum values of cell’s power density are 1.05 and 0.75 W/cm2 at 900 and 800°С, respectively. After the introduction of praseodymium oxide and ceria into the cathode and the anode, respectively, the power density is ca. 1 W/cm2 at 700°С. It is found that the power density of a cell with impregnated electrodes weakly increases with the increase in temperature to ca. 1.4 W/cm2 at 900°С. The analysis of impedance spectra by the distribution of relaxation times shows that such behavior is associated with the gas-diffusion resistance of the SOFC anode. The latter is explained by the low porosity of the anode and the high rate of fuel consumption.

The work contains the results of studies of a promising composite material of Sr2Fe1.5Mo0.5O6 + Ce0.8Sm0.2O1.9 for electrodes of symmetrical solid oxide fuel cells. It is shown that conductivity of the composite at 800°C is about 10 and 15 S/cm, for air and humid hydrogen, respectively, and polarization resistance of the electrodes in contact with the electrolyte based on doped lanthanum gallate under the same conditions is about 0.26 and 0.12 Ohm cm2. Tests of a symmetrical fuel cell with a planar design and the supporting gallate electrolyte with the thickness of 300 μm show that the cell can develop the power of about 0.5 W/cm2 at 800°C when air is supplied to the cathode and humid hydrogen is supplied to the anode. Analysis of polarization losses shows that the polarization of the oxygen electrode considerably exceeds the polarization of the anode.

The possibility of proton ceramic fuel cell (PCFC) fabrication, using a tape calendering method (TCM), is demonstrated for the first time for Ba(Ce,Zr)O 3 -based proton-conducting electrolytes in the present work. The cell consists of the 30 μm BaCe 0.5 Zr 0.3 Y 0.2 O 3−δ (BCZY) electrolyte, the Y 0.8 Ca 0.2 BaCo 4 O 7+δ cathode and the reduced 40%BCZY + 60%NiO and 45%BCZY + 55%NiO support and functional anode layers. Phase structure, thermal and electrical characterization of functional materials are discussed. It is found that the maximal power densities (P max ) of the fabricated PCFC (174 and 308 mW cm −2 at 600 and 725 °C, respectively) are acceptable for an intermediate-temperature range of operation and comparable with those reported in literature. It is also found that the BCZY electrolyte exhibits very high open circuit voltage (OCV) values (1.141 and 1.079 V at 600 and 725 °C) and, correspondingly, predominant ionic transport (average ions transport number ∼0.99 and 0.95 at 600 and 725 °C). The tape calendering method can be considered as effective strategy for PCFCs fabrication, ensuring the formation of gas-tight electrolytes and acceptable electrochemical properties.

The development of solid oxide electrochemical devices with symmetrical electrodes, is a promising direction in the field of resource saving and green energy. A feature of symmetrical electrodes is their stability to reduction–oxidation (redox) cycling, which can be useful in the case of carbon or sulphur deposition on a fuel electrode. The results of studies of a double-layer symmetrical electrode, where the functional layer consist of 50 wt.% Sr2Fe1.5Mo0.5O6-δ + 50 wt.% Ce0.8Sm0.2O1.9-δ and the collector is Sr2Fe1.5Mo0.5O6-δ are presented for the first time. It was shown that the introduction of Ce0.8Sm0.2O1.9-δ into the electrode functional layer, as well as the use of the current layer, does not lead to a change in the mechanism of oxygen reduction and hydrogen oxidation reactions. An analysis of the fuel cell impedance spectra by the distribution of relaxation times (DRT) method and comparison of the DRT functions with the results of the analysis of symmetric cells made it possible to conclude that during redox cycling the resistance of the oxygen exchange stage increases. It has been suggested that the cause of this is the formation of iron under reducing conditions, followed by its oxidation to oxide in an oxidizing atmosphere.

In this work, the effect of the content of CuO, ZnO, Al2O3, NiO, Fe2O3, Co3O4 and MoO3 additives on the sinterability, microstructure, and electrical properties of La0.9Sr0.1ScO3-α proton-conducting oxide in a form of tubes produced by slip casting is studied. It is shown that the relative density of La0.9Sr0.1ScO3-α tubes without sintering aids is ~86%. The introduction of 1.0 wt % ZnO, Al2O3, NiO or 0.5 ÷ 1.0 wt % Co3O4 leads to a relative density of ceramics higher than 95%. Among dense ceramic tubes, LSS +0.5 wt % Co3O4 has the highest electrical conductivity. The introduction of 1 wt % Fe2O3 additive does not affect the sinterability of the LSS, and 1 wt % CuO and MoO3 inhibits LSS sintering. Single protonic ceramic fuel cells based on LSS +0.5 wt % Co3O4 and LSS +1.0 wt % NiO supporting electrolyte tubes with a thickness of 300 μm are studied. The maximum power density of about 30 mW/cm2 at 800 °C was obtained for a cell based on LSS +0.5 wt % Co3O4 using wet hydrogen as fuel and air as an oxidizing gas.

The 61%NiO + 39%Zr 0.84 Y 0.16 O 1.92 (NiO-YSZ) and 56%NiO + 44%Zr 0.83 Sc 0.16 Ce 0.01 O 1.92 (NiO-CeSSZ) composite powders have been prepared using two-steps and one-step combustion synthesis, respectively. The Ni-YSZ anode substrate with a low level of electrical resistance (less than 1 mOhm cm) and porosity of about 53% in the reduced state was fabricated. The functional layer of the anode with the high level of electrochemical activity was made of NiO-CeSSZ. The single anode-supported solid oxide fuel cell with the bi-layer Ni-cermet anode, Zr 0.84 Sc 0.16 O 1.92 film electrolyte and the Pt + 3% Zr 0.84 Y 0.16 O 1.92 cathode was fabricated. The power density and the U–I curves of the fuel cell at initial state and after impregnation of the cathode and anode by praseodymium and cerium oxides, respectively, have been measured at different temperatures. The maximum of power density of the initial fuel cell was 0.35 W cm −2 at conditions of wet hydrogen (air) supply to the anode (cathode) at 900 °C. After the electrodes were impregnated, the value of power density increased by seven times and was approximately 2.4 W cm −2 at 0.6 V. It was suggested that after the electrodes impregnation the polarization resistance of the fuel cell was determined by the gas diffusion in the supported anode.

The supported Ni-YSZ (50 wt.% Ni + 50 wt.% Zr0.84Y0.16O1.92) anodes were produced of powders, obtained by the ceramic method, combustion synthesis, deposition of nickel oxide onto the YSZ ceramics, and deposition of 28 wt.% of nickel oxide onto the 39 wt.% NiO + 61 wt.% YSZ powders. The influence of the NiO-YSZ powder production technique, the amount of pore former and sintering temperature on the porosity, gas permeability, thermal expansion, and anode conductivity were studied. The porosity of anodes made of powders obtained by the ceramic method is always lower than the porosity of the anodes made of powders produced by combustion synthesis under otherwise equal conditions. The anode electrical conductivity greatly depends on the powder production techniques, while the anode thermal expansion is only slightly influenced by them.

Single fuel cells with bilayer supported cathodes are manufactured and tested. The cathodes consist of a high-porous La0.6Sr0.4MnO3 support with the thickness of approximately 1 mm and a functional composite layer with the thickness of 13–15 μm made of La0.75Sr0.2MnO3 and 8YSZ. Voltammetric and power characteristics of single fuel cells with a supported cathode, thin-film YSZ electrolyte, and platinum cathode are determined. The conclusion as to the significant contribution into the polarization overpotential losses on the cathode is made on the basis of the measurements of electric fuel cell characteristics. It decreases significantly as a result of the supported cathode modification by praseodymium oxide. At 850°C and voltage of 0.81 V, electric power density of a fuel cell was 1.65 W/cm2.

Single solid-oxide fuel cells (SOFCs) with a porous (36-41%) supporting Ni-cermet anode are manufactured and tested. The effect of the thickness of the supporting Ni-cermet anode on the electrochemical characteristics of single SOFCs is studied. It is shown that polarization losses on electrodes at the current density of 1.2 A/cm2 increase by about 2 times from 0.13 to 0.25 V at an increase in the thickness of the supporting Ni-cermet anode from 0.40 to 1.27 mm. The impedance spectroscopy method is used to identify relaxation processes responsible for the behavior of the fuel cell anode and cathode. It is found that a significant percentage of polarization losses on the anode is due to transport limitations in fuel supply to the three-phase nickel/electrolyte/gas phase interface and removal of the reaction products away from it.

The electrodes of solid-oxide fuel cells (SOFCs) must be characterized by high conductivity to decrease ohmic losses and sufficient porosity to provide high gas diffusion rate. In the cases, when the SOFC electrodes are substrates, they must be synthesized at the temperature above the temperature of formation of their solid-electrolyte coating. Herewith, manufacturing of supporting electrodes with the required micro-structure is rather complicated. The present paper studies the effect of the method of manufacturing of the initial La0.6Sr0.4MnO3 (LSM) powders, their degree of dispersion, introduction of sintering additives and pore agents on their microstructure, conductivity, and possibility of adjusting the temperature of SOFC cathodic substrate formation at which the required characteristics are reached. It is shown that sintering of cathodic substrates to the relative density of 65–70% can be carried out at the temperatures from 1050 to 1350–1400°C, which would allow obtaining electrolyte films of powders with different sintering ability on such substrates. The average pore size in cathodic substrates can be varied in the range of 0.4 to 2.5 μm by using the initial LSM powder with different dispersion degree and by employing graphite as a pore agent. At 900°C, conductivity of cathodic substrates of LSM grows at an increase in their relative density from 50% to 70% approximately from 50 to 100 S/cm and weakly depends on the dispersion degree of the initial powders.

Characteristics of nickel-cermet anodes obtained from weakly aggregated NiO nanopowders made by wire electric blasting (NiO/WEB) were studied. Electrodes made of NiO/WEB nanopowders have low sheet resistance (

A novel copper-based anode for low-temperature solid oxide fuel cells was prepared through the conventional ceramic technology and using CuO and SDC (Ce 0.8 Sm 0.2 O 1.9 ) powders with controlled particle size. The new Cu–SDC anode also contained highly dispersed CeO 2 and Ni particles to increase its surface area and fuel cell performance. The specific surface area of the Cu–SDC bare anode, CeO 2 and Ni-dispersed phases were estimated to be 1.53, 39.4 and 86.4 m 2 g −1 , respectively. Solid oxide fuel cells having the new anode were tested for both humid hydrogen and methane. Power densities of ca. 250 mW cm −2 were achieved in H 2 at 600 °C and in CH 4 700 °C, even if the SDC–electrolyte supporting membrane was 250-μm thick. Short term stability tests (maximum 64 h) showed an initial impairment, but not dramatic, of the new anode performance and the formation of carbon deposits. The addition of MoO x to the new anode did not prevent the formation of carbon deposits.

The effect of some technological parameters (firing temperature, thickness of an interphase layer made of solid electrolyte Ce0.82Gd0.18O1.91 (GDC), the GDC electrolyte amount in nickel-cermet) on the electrochemical and electric properties of a nickel-cermet (Ni-GDC) anode intended for fuel cells with the La0.88Sr0.12Ga0.82Mg0.18O2.85 (LSGM) electrolyte is studied. The polarization resistance of such an electrode is shown to hardly depend on the thickness of the interphase layer (4.5–23.5 μm) and the GDC electrolyte amount in nickel-cermet and to increase with the anode firing temperature. It is established that the contact resistance is concentrated in cells with the developed nickel-cermet electrode at the GDC/LSGM interface. At a temperature of 700°C the developed anodes may ensure a current density of 1 A cm−2 at an overvoltage of less than 100 mV when using both moist hydrogen and a methane-oxygen mixture as the fuel.

The polarization dependences of a porous gold electrode in contact with a solid electrolyte of the composition La0.88Sr0.12Ga0.82Mg0.18O2.85 are studied at 600–800°C and oxygen pressures of 2 × 10−2-1 atm. It is shown that the rate of cathodic reduction of oxygen out of the gas phase depends on the preliminary treatment of the sample. The activation energy is equal to 110–135 kJ mol−1 at a low polarization. After increasing the polarization, the activation energy for the cathodic reduction of oxygen equals 75–85 kJ mol−1 and depends on the oxygen pressure as a power function with a power index of 1/4. The rate of the anodic evolution of oxygen is dependent neither on the preliminary treatment of the sample nor on the oxygen pressure in the gas phase and the polarization curve has a characteristic segment, which corresponds to a limiting overvoltage.

The air,Au/La0.88Sr0.12Ga0.82Mg0.18O2.85/Au,air cells are studied by an impedancemetry method before and after a week-long exposure at 700°C to atmospheres of hydrogen, humid air, and carbon dioxide. Blank specimens of the same electrolyte are examined by methods of x-ray diffraction, Raman scattering (RS), and x-ray photoelectron spectroscopy. The fact that the shape of the RS spectra and the shape of the electrode impedance dispersion alter unequivocally suggests that, at the very least, the electrode surface interacts with all the gases. The interaction in question is reversible in the case of hydrogen and carbon dioxide. In the case of water vapor, the interaction is irreversible.

The impedance of a porous gold electrode in contact with solid electrolyte La0.88Sr0.12Ga0.82Mg0.18O2.85 and the effect of the manufacture conditions on its polarization resistance are studied at 600–800°C in air. The overall oxygen reaction rate on a gold electrode is described as the sum of two partial constituents, namely, the oxygen exchange at the gas/electrolyte interface at the gold/gas/electrolyte triple-phased boundary.

Electrical conductivity, Raman scattering (RS) spectra, and thermal expansion of the solid solution based on lanthanum gallate having the formula La0.88Sr0.12Ga0.82Mg0.18O2.85 (LSGM12–18) were studied as a function of temperature. X-ray diffraction analysis (XDA) of the samples at room temperature was performed. A dilatometric examination demonstrated that phase transitions of the second order took place at 775±10 and 880±20 K. The transition at 880 K was confirmed both by Raman scattering spectra and by a change in the activation energy of the electrical conductivity. This phase transition is probably due to a change of the oxygen sublattice symmetry.

The overall resistance and resistances of the bulk and grain boundaries of solid electrolyte La0.8Sr0.12Ga0.82Mg0.18O2.85 kept for a long time in air at 773-1073 K are studied by impedance spectroscopy. The increase in the electrolyte resistance with time is shown to be connected with that in the resistance of grain boundaries.

Electric conductivity, Raman spectra, and thermal expansion of La0.88Sr0.12Ga0.82Mg0.18O2.85 solid solution (LSGM12‐18) based on lanthanum gallate were studied at various temperatures, and X‐ray phase analysis was performed at room temperature. Dilatometric measurements showed that second‐order phase transitions occur at 775±10$ and 880± 20 K. The transition around 880 K is confirmed by Raman spectra and by a change in the conductivity activation energy in this temperature range. This transition is associated with a symmetry change in the oxygen sublattice.

The electroconductivity and the nature of conduction of vacuum-dense ceramics BaPr1 – xYxO3 – α(x= 0.05–0.15) is studied at temperatures of 373 to 985°C, \(P_{0_2}\) of 2.1 × 104to 10–11Pa, and \(P_{{\text{H}}_2 0} \) of 40 to 2400 Pa. The coefficient of linear thermal expansion is measured. The ceramics have a perovskite structure and are practically p-type semiconductors with a maximum conductivity of 0.26 S cm–1at x= 0.10 and 800°C, in air. The share of ionic (proton) conductivity of the ceramics does not exceed 0.2–0.4%. The conductivity is weakly dependent on the air humidity. In a hydrogen-containing atmosphere, the ceramics undergoes reduction with destruction. Boundaries of thermodynamic stability of BaPr0.9Y0.1O3 – αat 500–900°C are determined.

In the temperature range 873–1123 K, transport numbers of oxygen ions and protons are determined in the system (H2 + H2O), Me/BaCe0.9Nd0.1O3-α/Me,(H2 + H2O), where Me = Ag, Au, Pt, Ni, by the emf and current methods. The determined transport numbers are independent of the determination method, the electrode material, the current direction (anodic and cathodic polarization of the electrode), polarizability of electrodes, and the partial water (hydrogen) pressure in the gas phase. This unambiguously suggests that the transport numbers refer to the solid electrolyte, and not the electrochemical system as a whole. It also follows that partial currents of the hydrogen ionization and the oxygen ion discharge are determined by the transport numbers of protons and oxygen ions in the electrolyte. At a constant temperature, their ratio is affected by neither the electrode potential nor the gas phase composition, i.e., both electrode reactions have a common limiting step (or steps).