Synthesis and properties of fuel cell anodes based on (La0.5 + x Sr0.5 − x )1 − y Mn0.5Ti0.5O3 − δ (x = 0–0.25, y = 0–0.03)

Results are presented of studying electrochemical properties of perovskite-like solid solutions (La_{0.5 + x} Sr_{0.5 ? x} )_{1 ? y} Mn_0.5Ti_0.5O_{3 ? δ} (x = 0–0.25, y = 0–0.03) synthesized using the citrate technique and studied as oxide anodic materials for solid oxide fuel cells (SOFC). X-ray diffraction (XRD) analysis is used to establish that the materials are stable in a wide range of oxygen chemical potential, stable in the presence of 5 ppm H₂S in the range of intermediate temperatures, and also chemically compatible with the solid electrolyte of La_0.8Sr_0.2Ga_0.8Mg_0.15Co_0.05O_{3 ? δ} (LSGMC). It is shown that transition to a reducing atmosphere results in a decrease in electron conductivity that produced a significant effect on the electrochemical activity of porous electrodes. Model cells of planar SOFC on a supporting solid-electrolyte membrane (LSGMC) with anodes based on (La_0.6Sr_0.4)_0.97Mn_0.5Ti_0.5O_{3 ? δ} and (La_0.75Sr_0.25)_0.97Mn_0.5Ti_0.5O_{3 ? δ} and a cathode of Sm_0.5Sr_0.5CoO_{3 ? δ} are manufactured and tested using the voltammetry technique.     

Mechanical properties of mixed conducting La0.5Sr0.5Fe1−x Co x O3−δ (0≤x≤1) materials

Young’s modulus, strain–stress behavior, fracture strength, and fracture toughness of (0≤×≤1) materials have been investigated in the temperature range 20–1,000°C. Young’s moduli of and , measured by resonant ultrasound spectroscopy, were 130±1 and 133±3 GPa, respectively. The nonlinear stress–strain relationship observed by four-point bending at room temperature was inferred as a signature of ferroelastic behavior of the materials. Above the ferroelastic to paraelastic transition temperature, the materials showed elastic behavior, but due to high-temperature creep, a nonelastic respond reappeared above ∼800°C. The room temperature fracture strength measured by four-point bending was in the range 107–128 MPa. The corresponding fracture toughness of , measured by single edge V-notch beam method, was 1.16±0.12 MPa·m^1/2. The measured fracture strength and fracture toughness were observed to increase with increasing temperature. The fracture mode changed from intragranular at low temperature to intergranular at high temperature. Tensile stress gradient at the surface of the materials caused by a frozen-in gradient in the oxygen content during cooling was proposed to explain the low ambient temperature fracture strength and toughness.     

Oxygen transport in La0.5Sr0.5Fe1−yTiyO3−δ (y=0.0, 0.2) membranes

The influence of partial substitution of Fe with Ti on the oxygen transport properties of La_1−x Sr _x FeO₃ membranes was investigated in view of their application for oxygen separation. Samples of composition (y=0, 0.2) were prepared and their oxygen transport properties characterised by potential step relaxation and by oxygen permeation measurement in an air/argon gradient. With the first technique, chemical diffusion and surface exchange (k _S) coefficients were obtained by fitting of the current relaxation data to a single expression valid over the complete time range. The Ti-substituted composition gave slightly larger values of and k _S. The trend was opposite for the measured oxygen permeation flux. In the latter experience, ordering of oxygen vacancies was observed at lower temperature, reducing significantly the performance of the material.     

In situ study of electrochemical activation and surface segregation of the SOFC electrode material La0.75Sr0.25Cr0.5Mn0.5O(3±δ)

Mixed-conducting perovskite-type electrodes which are used as cathodes in solid oxide fuel cells (SOFCs) exhibit pronounced performance improvement after cathodic polarization. The current in situ study addresses the mechanism of this activation process which is still unknown. We chose the new perovskite-type material La(0.75)Sr(0.25)Cr(0.5)Mn(0.5)O(3±δ) which is a potential candidate for use in symmetrical solid oxide fuel cells (SFCs). We prepared La(0.75)Sr(0.25)Cr(0.5)Mn(0.5)O(3±δ) thin film model electrodes on YSZ (111) single crystals by pulsed laser deposition (PLD). Impedance spectroscopy (EIS) measurements show that the kinetics of these electrodes can be drastically improved by applying a cathodic potential. To understand the origin of the enhanced electrocatalytic activity the surfaces of operating LSCrM electrodes were studied in situ (at low pressure) with spatially resolving X-ray photoelectron spectroscopy (μ-ESCA, SPEM) and quasi static secondary ion mass spectrometry (ToF-SIMS) after applying different electrical potentials in the SIMS chamber. We observed that the electrode surfaces which were annealed at 600 °C are enriched significantly in strontium. Subsequent cathodic polarization decreases the strontium surface concentration while anodic polarization increases the strontium accumulation at the electrode surface. We propose a mechanism based on the reversible incorporation of a passivating SrO surface phase into the LSCrM lattice to explain the observed activation/deactivation process.     

Phase Transitions in the BaCe1–x Nd x O3–δ System (x = 0–0.15)

Phase transitions in BaCe_{1 – x} Nd _x O_3– (x = 0–0.15) are studied on ceramic samples by dilatometry (at 370–1100 K) and by measuring electroconductivity (at 750–1220 K). Ion transport numbers are measured by an EMF method at 850–1240 K. All measurements are done in dry air (₂ 40 Pa). By treating the obtained temperature dependences of linear expansion with a difference method (difference between first-degree polynomial approximating the dependence and experimental points), the position and the sort of the phase transitions are determined. High-temperature phase transitions are confirmed by measuring the electroconductivity and ion transport numbers. Second-order phase transitions in pure BaCeO₃ are discovered at 480 ± 10, 530 ± 10, 900 ± 10, 1030 ± 20, and 1170 ± 10 K and a first-order transition, at 665 ±10 K. Phase transitions at 900 and 1030 K are discovered for the first time ever.     

Nature of conductivity of Perovskites La1 ? x Sr x ScO3 ? α (x = 0.01–0.15) under oxidative and reducing conditions

Transport numbers of ions and protons are measured on ceramic samples of La_{1 ? x} Sr _x ScO_{3 ? ??} (x = 0.01?C0.15); partial conductivities (hole, proton, and oxygen-ion) are determined in the temperature range of 500?C900°C at pH₂O = 0.04?C2.35 kPa and pO₂ from air to 10^?15 Pa.     

Magnetic and Transport Properties of Bi_(0.5)Ca_(0.5–x)La_xFe_(0.3)Mn_(0.7)O_3(x=0, 0.05, 0.10, 0.15, 0.20, 0.25) Prepared by Molten Salt Method

Polycrystallines Bi0.5Ca0.5–xLaxFe0.3Mn0.7O3(x=0, 0.05, 0.10, 0.15, 0.20, 0.25) were prepared by molten salt method and showed perovskite orthorhombic structure with space group Pnma. The magnetic measurements indicate that the compounds exhibit antiferromagnetic behavior in a temperature range of 4―300 K. The measurements of transport properties suggest that the substitution of La for Ca enhanced the conductivity, and a kink appeared on the curve of temperature dependence of resistivity at 275 K, which is ...     

La0.67Sr0.33Mn1-yFeyO3(y=0, 0.01, 0.02, 0.03)磁谱特性分析

采用固相反应法制备了La0．67Sr0．33Mn1-yFeyO3（y=0,0．01,0．02,0．03）氧化物多晶样品,XRD测试表明形成了钙钛矿单相结构,铁掺人后材料的晶体结构没有明显变化。SEM测试表明样品晶粒大小为1～3μm,随着铁含量增加饱和磁化强度下降。样品室温磁导率（10kHz～1．8GHz）测试表明,复磁导率频谱曲线是典型的弛豫型谱线,且随铁离子含量增加其起始磁导率下降。同时通过最小二乘曲线拟合的方法分析了频谱曲线,分别给出了畴壁位移和磁畴转动对磁导率的贡献,结果表明,y=0,0．01的样品畴壁位移对磁导率的贡献大于畴转对磁导率的贡献,y=0．02,0．03的样品,畴转对磁导率的贡献大于畴壁位移的贡献。     

Crystal structural, magnetic, and transport properties of layered cobalt oxyfluorides, Sr2CoO(3+x)F(1-x) (0 ≤ x ≤ 0.15)

The crystal structure of the layered cobalt oxyfluoride Sr(2)CoO(3)F synthesized under high-pressure and high-temperature conditions has been determined from neutron powder diffraction and synchrotron powder diffraction data collected at temperatures ranging from 320 to 3 K. This material adopts the tetragonal space group I4/mmm over the measured temperature range and the crystal structure is analogous to n = 1 Ruddlesden-Popper type layered perovskite. In contrast to related oxyhalide compounds, the present material exhibits the unique coordination environment around the Co metal center: coexistence of square pyramidal coordination around Co and anion disorder between O and F at the apical sites. Magnetic susceptibility and electrical resistivity measurements reveal that Sr(2)CoO(3)F is an antiferromagnetic insulator with the Néel temperature T(N) = 323(2) K. The magnetic structure that has been determined by neutron diffraction adopts a G-type antiferromagnetic order with the propagation vector k = (1/2 1/2 0) with an ordered cobalt moment μ = 3.18(5) μ(B) at 3 K, consistent with the high spin electron configuration for the Co(3+) ions. The antiferromagnetic and electrically insulating states remain robust even against 15%-O substation for F at the apical sites. However, applying pressure exhibits the onset of the metallic state, probably coming from change in the electronic state of square-pyramidal coordinated cobalt.     

Electrode performance and X-ray absorption spectroscopy of La0.8Sr0.2Mn1−x Cu x O3 (0 ≤ x ≤ 0.2)–GDC composite cathodes for SOFCs

Electrochemical properties of composite cathodes consisting of La_0.8Sr_0.2Mn_1?x Cu _x O₃ (LSMCu, 0?≤?x?≤?0.2) and Ce_0.8Gd_0.2O_2?x (GDC) were determined by impedance spectroscopy, and conduction mechanism for the composite cathodes was investigated by a near-edge X-ray absorption fine-structure analysis (NEXAFS). LSMCu–GDC cathodes showed lower polarization resistance (R _p) than LSM–GDC up to 750 °C, whereas they exhibited better performance at higher temperature (≥800 °C). The best performance was achieved with the LSMCu10–GDC cathode: 0.27 and 0.08?Ω cm² at 800 °C and 850 °C, respectively. NEXAFS and refinement results confirmed that Cu doping caused the oxidation of Mn³⁺ to Mn⁴⁺ and lattice contraction. This additional Mn⁴⁺ can lead to the formation of oxygen vacancies when Mn⁴⁺ is converted to Mn³⁺ at relatively high temperatures (above 600 °C). This in turn contributes to improved oxygen ion transport in LSM. The LSMCu–GDC composite cathode can thus be considered a suitable potential cathode for SOFC applications.     

Structural and electrical properties of sol–gel grown (1 − x) (ZnO) + (x) (SnO2) (x = 0, 0.25, 0.5) nanocomposites

Journal of Sol-Gel Science and Technology - Semiconducting oxide nanocomposites of ZnO/SnO2 with different weight ratio, i.e. (i) ZnO:SnO2?=?100:0 (ZnO0), (ii)...     

Electrical properties of Ba2(In1 − x Al x )2O5 solid solutions

The electric conductivity of perovskite-like Ba₂(In_{1 ? x} Al _x )₂O₅ solid solutions (0 < x ≤ 0.20) characterized by structural disordering in the oxygen sublattice was studied as a function of temperature and partial pressure of oxygen in an atmosphere with a low content of water vapors ( $p_{H_2 O}$ = 3 × 10^?5 atm). When In³⁺ was partially replaced by Al³⁺, the oxygen ion conductivity increased because of the disordering of oxygen structural vacancies, leading to a significant increase in the total electric conductivity of the samples.     

Electrochemical properties and first-principle analysisof Na x [M y Mn1−y ]O2 (M = Fe,Ni) cathode

Journal of Solid State Electrochemistry - Sodium-ion batteries are the commercially and environmentally viable next-generation candidates for automobiles. Structural and electrochemical aspects are...     

Characterization of non-stoichiometric co-sputtered Ba0.6Sr0.4(Ti1???x Fe x )1?+?x O3???δ thin films for tunable passive microwave applications

The fabrication of novel iron-doped barium strontium titanate thin films by means of radio frequency (RF) magnetron co-sputtering is shown. Investigations of the elemental composition and the dopant distribution in the thin films obtained by X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, and time-of-flight secondary ion mass spectroscopy reveal a homogeneous dopant concentration throughout the thin film. The incorporation of the iron dopant and the temperature-dependent evolution of the crystal structure and morphology are analyzed by electron paramagnetic resonance spectroscopy, X-ray diffraction, Raman spectroscopy, atomic force microscopy, and scanning electron microscopy. In summary, these results emphasize the RF magnetron co-sputter process as a versatile way to fabricate doped thin films.     

Thermal characterization and compatibility studies of perovskite-type Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) oxide with Cr2O3 at high temperature

The chemical compatibility of perovskite-type Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCF) oxides with Cr₂O₃ has been examined between room temperature and 1,100 °C. Differential thermal analysis and thermogravimetric analysis were used to analyze the thermal behavior of BSCF–Cr₂O₃ binary mixtures in all composition ranges (0–100 mass% BSCF). The reaction products were identified by X-ray analysis after heating at 700–1,100 °C. As we expected, it was found that perovskite-type BSCF oxide had a poor chemical compatibility with the Cr₂O₃ oxide. In particular, the decomposition process of the BSCF–Cr₂O₃ binary mixture is quite complex and it starts at about 700–750 °C. The mixtures of BSCF and Cr₂O₃ oxides reacted forming mixed complex oxides based on (Ba/Sr)FeO₃, (Co/Fe)CrO₄, and (Ba/Sr)CrO₄ mixtures.     

Phosphates M 0.5(1 + x) 2+ Cr x Ti2 − x (PO4)3: Synthesis, structure, and catalytic properties

Complex phosphates of titanium, chromium, and metals(2+) of the general formula M_{0.5(1 + x} )Cr _x Ti_{2 ? x} (PO₄)₃ (M = Mg, Ca, Mn, Ni, Sr, Ba, and Pb) were synthesized. Their phase formation was studied by means of X-ray powder diffraction, electron probe microanalysis, differential thermal analysis, and IR spectroscopy. Individual phases and solid solutions crystallizing in kosnarite and langbeinite structure types were identified; their crystallographic parameters were calculated. The catalytic properties of phosphates Ca_{0.5(1 + x} )Cr _x Ti_{2 ? x} (PO₄)₃ in methanol conversion were studied.     

Synthesis and magnetic properties of Cu0.5Fe0.5 ? x In x Cr2S4 (x = 0?0.4) solid solutions

Multistep synthesis with X-ray diffraction monitoring of the phase composition has been carried out, optimal synthesis parameters have been determined, and the magnetic properties of solid solutions between thiospinels with ordered tetrahedral A lattices (ferrimagnet Cu_0.5Fe_0.5Cr₂S₄ (T _C = 347 K) and anti-ferromagnet Cu_0.5In_0.5Cr₂S₄ (T _N = 35 K) have been studied. Both compounds crystallize in F $\bar 4$ 3m (T _d ² ) structure. Measurements over wide ranges of fields (0.05?C40 kOe) and temperatures (5?C300 K) highlighted the nature of magnetism in the samples; new magnetic species have been discovered.