Electrochemical evaluation of La2NiO4+δ -based composite electrodes screen-printed on Ce0.8Sm0.2O1.9 electrolyte

La₂NiO_4+δ , 60 wt.% La₂NiO_4+δ –40 wt.% La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ , and 60 wt.% La₂NiO_4+δ –40 wt.% Ce_0.8Sm_0.2O_1.9 electrodes were prepared from fine powders on dense Ce_0.8Sm_0.2O_1.9 electrolyte substrates by screen-printing technique. Electrochemical impedance spectroscopy and chronopotentiometry techniques were employed to evaluate the electrochemical properties of the composite electrodes in comparison with the La₂NiO_4+δ electrode. For the three electrodes, main electrode processes were resolved to be charge-transfer at the electrode/electrolyte interface and oxygen exchange on the electrode surface. The contribution of the surface oxygen exchange process was detected to be dominant for the overall electrode polarization. The addition of Ce_0.8Sm_0.2O_1.9 into La₂NiO_4+δ was favorable for the charge transfer process whereas it was undesired for the surface oxygen exchange process. On comparison, adding La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ into La₂NiO_4+δ was found to benefit both the two electrode processes. The La₂NiO_4+δ -La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ composite electrode showed optimum electrochemical properties among the three electrodes. At 800 °C, the composite electrode achieved a polarization resistance of 0.20 Ω cm², an overpotential of 45 mV at a current density of 200 mA cm^?2, together with an exchange current density of ～200 mA cm^?2.     

Preparation and characterization of Ce1−xSmxO2−δ (x = 0.1–0.3) as electrolyte material for intermediate temperature SOFC

The effect of Sm doping on CeO₂ for its use as a solid electrolyte material for intermediate temperature solid oxide fuel cells (IT-SOFCs) has been explored here. Ce_1−xSm_xO_2−δ (x = 0.1–0.3) samples are successfully synthesized by carbonate co-precipitation method. TG–DTA, XRD, Raman, UV–Vis, FT-IR, SEM and ac-impedance are used for structural and electrical characterization. From the XRD patterns, well-crystalline cubic fluorite structured solid solution is confirmed. Lattice parameters increased with increase in Sm³⁺ while the crystallite size decreased. The optical absorption spectra exhibits a red shift for Sm³⁺ doped CeO₂. Raman spectra show an intense peak at 463 cm⁻¹, a characteristic peak for doped ceria. SEM shows cluster like particles. Based on ac-impedance data, the total oxygen ionic conductivity is highest for Ce_0.8Sm_0.2O_2−δ in the temperature range of 473–623 K.     

On the sol–gel synthesis and catalytic activity of Ce1−xAxO2−δ (A = Pr, Sm, Gd) SOFCs anode materials for reforming of methane

A sol–gel route to synthesize nanocrystalline praseodymium-, samarium- and gadolinium-doped ceria powders for solid oxides fuel Cells SOFCs is presented. The method involves metal nitrates with propionic acid (both as chelating ligand and solvent), gel formation, liquid nitrogen quenching, drying at 150 °C/24 h, and finally decomposition at 450 °C in nitrogen followed by calcination at 650 °C in air. TG–DTA, BET, XRD, FTIR, UV–vis and catalytic tests were used to characterize the samples. Ce_0.8Pr_0.2O_2?δ sample exhibited the best catalytic performance in methane steam reforming under water deficient conditions, closely followed by Ce_0.9Gd_0.1O_2?δ, Ce_0.8Sm_0.2O_2?δ and Ce_0.8Gd_0.2O_2?δ catalysts. The superior catalytic performance of Ce_0.8Pr_0.2O_2?δ sample was attributed to the existence of praseodymium species (Pr⁴⁺/Pr³⁺) strongly interacting with ceria. The two systems act synergistically in the catalytic steam reforming of methane.     

A novel cathode material BaCe0.4Sm0.2Co0.4O3−δ for proton conducting solid oxide fuel cell

A novel cathode material BaCe_0.4Sm_0.2Co_0.4O_3−δ composed of two phases BaCe_1−x(Sm/Co)_xO_3−δ and BaCo_1-x(Sm/Ce)_xO_3−δ was prepared in situ via the citric–nitrate route and its performance as cathode material for proton conducting solid oxide fuel cell (SOFC-H) was characterized. BaCe_0.4Sm_0.2Co_0.4O_3−δ exhibited simultaneous protonic, electronic, and oxygen ionic conduction in air, leading to a good electrode performance. The polarization resistance of the novel cathode material in symmetrical cell was 0.36 Ω cm² with Pt as the current collector at 700 °C in wet air. The electrode performance can be further improved through microstructure optimization. It also showed good thermal expansion compatibility with BaCe_0.8Sm_0.2O_3−δ electrolyte over a 100 h duration test. BaCe_0.4Sm_0.2Co_0.4O_3−δ is a promising cathode material for SOFC-H.     

Co3−δO4 paracrystal: 3D assembly of nanosize defect clusters in spinel lattice

Paracrystalline array of defect clusters ca. five times the lattice spacing of the average Co_3−δO₄ spinel structure occurred more or less in a relaxed manner when the sintered Co_1−xO polycrystals were air-quenched below the Co_1−xO/Co_3−δO₄ transition temperature to activate oxy-precipitation of cube-like Co_3−δO₄ at dislocations. The same paracrystalline spacing was obtained for Co_3−δO₄ when formed via oxidizing/sintering the Co_1−xO powders at 800°C in air, suggesting a nearly constant δ value for Co_3−δO₄ in the T-P_O2 conditions encountered. The extra cobalt vacancies and Co³⁺ interstitials, as a result of δ value, may form additional 4:1-derived defect clusters for further paracrystalline distribution in the spinel lattice. The nanosize defect clusters self-assembled by columbic interactions and lattice relaxation in ionic crystal may have potential applications as step-wise sensor of oxygen partial pressure at high temperatures.     

Structural characterisation of the Ce1−xLaxNbO4+δ solid solution series: In-situ high-temperature powder diffraction studies

High-resolution neutron powder diffraction has been utilised to investigate the effect of lanthanum substitution on the structure of cerium niobate, CeNbO_4+δ, as a function of temperature. Two members of the Ce_1−xLa_xNbO_4+δ solid solution series, Ce_0.8La_0.2NbO_4+δ and Ce_0.2La_0.8NbO_4+δ, were examined over a temperature range of 293-923 K under a positive pressure of O₂ (500 mbar). From this data it was found that on increasing lanthanum substitution there was an associated reduction in the temperature of the monoclinic-to-tetragonal phase transition. The data also suggested that increasing lanthanum substitution caused an associated decrease in the excess oxygen content. In addition, high-temperature X-ray powder diffraction data recorded in static air were also examined for four compositions of the Ce_1−xLa_xNbO_4+δ series (x=0.2, 0.4, 0.6 and 0.8). These data corroborated the results of the neutron diffraction experiments and also suggested that there was formation of an intermediate phase, analogous to the CeNbO_4.08 phase of the parent material, during the phase transitions of the x=0.8 and 0.6 compositions.     

Mixed-conducting perovskite-type SrxBi1-xFeO3-δ oxygen-permeating membranes

Sr_xBi_1-xFeO_3-δ (SBF) series mixed conductors were synthesized using standard ceramic method. The properties of such materials were characterized by XRD, O₂-TPD techniques. Abnormal crystal phenomena were found and explained and correlated with the oxygen permeation results. By analysis of the critical radius (r_c), the degree of openness of the lattice (F_v) and the average metal-oxygen bonding energy of the perovskite lattice (ABE), it was proposed that the oxygen permeation flux is determined mainly by the oxygen diffusion rate in bulk when 1-x?0.5, and by the concentration of oxygen vacancy when 1-x ? 0.5. The stability of Sr_0.5Bi_0.5FeO_3-δ was also investigated, and the high stability of it was attributed to the stable BO₆ octahedra.     

Preparation, characterization and gas-sensitive properties of nano-crystalline Cr2O3Fe2O3 mixed oxides

A series of Fe₂-_xCr_xO₃(x = 0, 0.4, 0.8, 1.2, 1.6, 2.0) mixed oxides have been prepared with the chemical coprecipitation method and characterized by specific surface area, transmission electron microscopy (TEM), powder X-ray diffraction (XRD), IR and Mössbauer spectroscopy. Single-phase Fe-Cr mixed oxide nano-crystalline powders with corundum structure are obtained, and the results of the five characterization methods are well accordant with each other. Furthermore, gas-sensitive properties of the sensors made of the oxide powders have been studied.     

Phase equilibria and crystal structure of the complex oxides in the Ln-Ba-Co-O (Ln=Nd, Sm) systems

The phase equilibria in the Ln-Ba-Co-O (Ln=Nd, Sm) systems were systematically studied at 1100 °C in air. The homogeneity ranges and crystal structure of the solid solutions: Ln_2−xBa_xO_3−δ (0<x≤0.1 for Ln=Nd and 0<x≤0.3 for Ln=Sm), Nd_3−yBa_yCo₂O₇ (0.70≤y≤0.80), BaCo_1−zSm_zO_3−δ (0.1≤z≤0.2) were determined by X-ray diffraction of quenched samples. The values of oxygen content (5+δ) for slowly cooled LnBaCo₂O_5+δ (Ln=Nd, Sm) samples were estimated as 5.73 for Ln=Nd, and 5.60 for Ln=Sm. The unit cell parameters were refined using Rietveld full-profile analysis. It was shown that NdBaCo₂O_5.73 possesses tetragonal structure and SmBaCo₂O_5.60 - orthorhombic structure. The projections of isothermal-isobaric phase diagrams for the Ln-Ba-Co-O (Ln=Nd, Sm) systems to the compositional triangle of metallic components were presented.     

Crystallization of Mg(Fe0.8Ga0.2)2O4-δ films on silicon with SiO2 and TiO2 buffer layers

The results of analysis of conceivable interactions between film and substrate materials during crystallization of Mg(Fe_0.8Ga_0.2)₂O_4-δ films with SiO₂ and TiO₂ buffer layers on silicon are reported. The calculated data are compared with the physicochemical parameters of Mg(Fe_0.8Ga_0.2)₂O_4-δ/Si, Mg(Fe_0.8Ga_0.2)₂O_4-δ/TiO₂/Si, and Mg(Fe_0.8Ga_0.2)₂O_4-δ/SiO₂/Si film heterostructures.     

Oxygen permeability, thermal expansion and mixed conductivity of GdxCe0.8−xPr0.2O2−δ, x=0, 0.15, 0.2

The non-linear thermal expansion behaviour observed in Ce_1−yPr_yO_2−δ materials can be substantially controlled by Gd substitution. Coulometric titration shows that the charge compensation mechanism changes with increasing x, in the system Gd_xCe_0.8−xPr_0.2O_2−δ. For x=0.15, charge compensation is by vacancy formation and destabilises the presence of Pr⁴⁺. At x=0.2, further Gd substitution is charge compensated by additionally raising the oxidation state of Pr rather than solely the creation of further oxygen ion vacancies. Oxygen concentration cell e.m.f. measurements in an oxygen/air potential gradient show that increasing Gd content decreases ionic and electronic conductivities. Ion transference numbers measured under these conditions show a positive temperature dependence, with typical values t_o=0.90,0.98 and 0.80 for x=0,0.15 and 0.2, respectively, at 950 °C. These observations are discussed in terms of defect association. Oxygen permeation fluxes are limited by both bulk ambipolar conductivity and surface exchange. However, the composition dependent trends in permeability are shown to be dominated by ambipolar conductivities, and limited by the level of electronic conductivity. At the highest temperatures, oxygen permeability of composition x=0.2 approaches that of composition x=0, Ce_0.8Pr_0.2O_2−δ, with specific oxygen permeability values approximately 2×10⁻⁹ mol s⁻¹ cm⁻¹ at 950 °C, but offering much better thermal expansion properties.     

Relationship between powder structure and electrochemical performance of Ba0.5Sr0.5Co0.8Fe0.2O3 − δ cathode material

Highly pure Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3???δ (BSCF) perovskite nanocompound was synthesized via glycine-nitrate process (GNP) and coprecipitation-azeotropic distillation method (ADM), respectively. Compared to ADM, GNP was proved to facilitate the synthesis of BSCF powder with small crystal and particle sizes as well as large surface area. BSCF material was employed as the cathode of solid oxide fuel cell (SOFC) incorporating with Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte. Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) tests indicated that the GNP powder-based cathode not only exhibited high electrocatalytic activity but also possessed low oxygen diffusion resistance due to the high porosity. As a result, the cell with GNP powder-based cathode showed a power density of 0.35 W cm^?2 when the voltage was 0.7 V at 650 °C. Furthermore, the cathode performance was significantly improved at the high current density condition.     

Phase equilibria,crystal structure at 1373 K and properties of complex oxides in the Nd–Co–Fe–O system

Phase equilibria in the Nd–Co–Fe–O system were systematically studied at 1373 K in air. The homogeneity range and crystal structure of solid solution NdCo_1–xFe_xO₃ (0.0 ≤ x ≤ 1.0) have been studied by the X-ray powder diffraction method. The structural parameters of complex oxides have been refined by the full-profile Rietveld method. It was shown that all oxides reveal practically stoichiometric oxygen composition within the entire temperature range under investigation. The values of thermal expansion coefficients for the cobaltites NdCo_1–xFe_xO₃ (x = 0.3, 0.7) have been calculated within the wide temperature range in air. Chemical stability of NdCo_1–xFe_xO₃ (x = 0.3, 0.7) in respect to the solid electrolyte materials (Ce_0.8Sm_0.2O_2–δ and La_0.88Sr_0.12Ga_0.82Mg_0.18O3-δ) was examined. Electrical conductivity of NdCo_1–xFe_xO₃ (x = 0.3, 0.7) was measured as a function of temperature within the range 300–1373 K in air. It was shown that substitution of cobalt for iron leads to the decrease of conductivity. The isothermal-isobaric cross-section of the phase diagram for the Nd–Co–Fe–O system at 1373 K in air has been presented.     

Preparation of an asymmetric perovskite-type membrane and its oxygen permeability

A crack-free asymmetric membrane of perovskite-type oxide (La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ) was successfully prepared by coating a slurry containing La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ powders directly on the surface of a green support of the same composition, followed by sintering. It was found that crack-free asymmetric membranes could be obtained by controlling the powder concentration of the slurry in the range of 15–25 wt.%. After sintering, the crystal phase of the top layer of asymmetric membranes prepared was the same as that of powders, which were of the cubic perovskite phase. The nitrogen permeability and SEM photograph of the support showed that the support was porous, and the gas-tight test and SEM demonstrated that the top layer of asymmetric membrane was dense and crack-free. The asymmetric membrane prepared, whose dense top layer was 200 μm thick, exhibited about three to four times as high an oxygen flux as a 2 mm dense sintered disc.     

Preparation of aqueous sols of Ce1 − x Gd x O2-δ, Y0.9Eu0.1VO4 and nanocomposites Ce1 − x Gd x O2-δ/Y0.9Eu0.1VO4 stabilized by polyacrylic acid

A method for the synthesis of stable aqueous sols of nanocrystalline solid solutions Ce_1?x Gd _x O_2-δ (x = 0.10, 0.15, 0.20) and Y_0.9Eu_0.1VO₄ and nanocomposites Ce_{1 ? x} Gd _x O_2-δ/Y_0.9Eu_0.1VO₄ stabilized by biocompatible low-molecular-weight polyacrylic acid was proposed. Polyacrylic acid was shown to be a promising matrix for the preparation of polyfunctional composite materials.     

Using <Emphasis Type="Italic">ex situ</Emphasis> X-ray powder diffraction at synchrotron radiation to follow changes in the phase composition of perovskite-like strontium cobaltites

Precision X-ray diffraction at synchrotron radiation was used to reveal the separation of perovskite-like oxides SrCo_0.8-x Fe_0.2Nb _x O_3-z (x = 0.2 and 0.3) into two phases of a similar structure identical to initial perovskite structure, but having different unit cell parameters and supposedly different oxygen deficiency. The structural transformation is accompanied by oxygen outlet from the structure. The study of oxygen atoms intercalation from air into the oxygen-deficient structure showed that the structural changes are reversible: heating to 400°C in air restores the initial state of samples.     

Structural and electric properties of the Ce0.8(Sm1 ? xCax)0.2O2 ? δ system (x = 0.0–1.0)

CeO₂-based solid solutions with a fluorite structure are promising materials as electrolytes of medium-temperature electrochemical devices. This work presents the results of systematic studies of structural and electric properties and oxygen nonstoichiometry of the Ce_0.8(Sm_{1 − x} Ca _x )_0.2O_{2 − δ} system in a wide range of concentrations of 0 < x < 1 performed in order to establish the causes affecting the system conductivity and its behavior in a reducing medium. It is found that a single-phase solid solution of the fluorite type is formed in the whole concentration range. Parameters of its lattice cells decrease linearly at an increase in the concentration of Ca²⁺. Conductivity in air grows when calcium is added due to a decrease in the grain boundary resistance. The maximum conductivity in air was obtained for the composition of Ce_0.8(Sm_0.8Ca_0.2)_0.2O_{2 − δ} and is 13.71 × 10⁻³ S/cm at 873 K. Studies of the dependence of conductivity of the partial pressure of oxygen showed that electron conductivity is observed at a higher oxygen partial pressure at an increase in the temperature and calcium concentration. The critical partial pressure of oxygen ( p_O2 ^* )\left( {p_{O_2 }^* } \right) for the compositions of Ce_0.8(Sm_{1 − x} Ca _x )_0.2O_{2 − δ} with x = 0; 0.2, and 0.5 is 1.83 × 10⁻¹⁶, 1.73 × 10⁻¹³, and 3.63 × 10⁻¹³ atm at 1173 K, respectively, and 2.76 × 10⁻²¹, 5.05 × 10⁻¹⁸, and 1.31 × 10⁻¹⁸ atm at 1023 K.     

Manganites de fer de structure spinelle déformée à très fort champ coercitif. Exemple de l'oxyde lacunaire à valence mixte Mn1,7Fe1,3O4+δ

Mn_xFe_3-xO_4+δ (x = 1.00, 1.21, 1.50, 1.70) spinels with acicular shape have been prepared from oxalic precursors. Due to their state of division, these ferrites can be oxidized at moderate temperatures into mixed-valence defect spinels Mn_xFe_3-xO_4+δ. These phases can exhibit a high content of Mn³⁺ ions which are responsible for changes in crystalline structure, the lattice becoming tetragonal. The coercive force of tetragonal spinels increases with the c/a ratio of the unit cell parameters. Coercivities of about 4 000 Oe were reached.     

Single-step fabrication of asymmetric dual-phase composite membranes for oxygen separation

Asymmetric dual-phase composite membranes for oxygen separation were conveniently fabricated by an acid leaching technique. A thin dense layer of Ce_0.85Sm_0.15O_1.925/Sm_0.6Sr_0.4FeO_3−δ was left by controlling the degree of acid leaching, and a porous substrate of Ce_0.85Sm_0.15O_1.925 with a fluorite structure was formed after dissolution of Sm_0.6Sr_0.4FeO_3−δ with a perovskite structure in HCl. Thus, a thin dense layer and a porous substrate can be fabricated in a single step in which traditional shrinkage mismatch and chemical reaction between thin dense layers and porous substrates can be avoided. The thickness of the dense layer can be controlled by varying the acid leaching time. Hence, dual-phase composite membranes with high oxygen flux can be obtained.     

Composite cathode materials Ag-Ba0.5Sr0.5Co0.8Fe0.2O3 for solid oxide fuel cells

Silver-Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF) cathodes were prepared in two ways. In the first method, Ag-BSCF composite powder was prepared in ethanol solution, where Ag nanoparticles serving as a component in the preparation of Ag-BSCF composite cathodes had been previously obtained via one-step synthesis in absolute ethanol using a neutral polymer (polyvinylpyrrolidone). To the best of our knowledge, this is the first study to use a Ag sol obtained by the above method for preparation of Ag-BSCF composite powder. Then, a paste containing this powder was screen-printed on a Sm_0.2Ce_0.8O_1.9 electrolyte and sintered at 1,000 °C. In the second technique, an aqueous solution of AgNO₃ was added to a previously sintered BSCF cathode, which was then sintered again at 800 °C. The oxygen reduction reaction at the quasi-point BSCF cathode on the Sm_0.2Ce_0.8O_1.9 electrolyte was tested by electrochemical impedance spectroscopy at different oxygen concentrations in three electrode setup. The continuous decrease of polarization resistance was observed under polarization ?0.5 V at 600 °C. The comparative studies of both obtained composite Ag-BSCF materials were performed in hydrogen-oxygen IT-SOFC involving samaria-doped ceria as an electrolyte and Ni-Gd_0.2Ce_0.8O_1.9 anode. In both cases, the addition of silver to the cathode caused an increase in current and power density compared with an IT-SOFC built with the same components but involving a monophase BSFC cathode material.