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1.
In this paper, we report the electrical properties of Fe-doped perovskite-like compounds with a nominal chemical formula of BaNb0.75-xNa0.25FexO3-δ (0.05 < x < 0.5) (BNF). Various solid-state structural and electrical characterization techniques, including powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), alternating current (AC) impedance spectroscopy and direct current (DC) methods were used for characterization. PXRD patterns for BNF members show the formation of perovskite-like structure. The total electrical conductivity values were determined under ambient air and wet air in the temperature up to 700 °C. The Fe concentration was strongly correlated to the conductivity response, with the x = 0.5 member exhibiting the highest conductivity in air. A relationship between the humidity content and conductivity in air was also observed in low Fe concentration BNF members (x = 0.5, 0.15), suggesting the presence of potential proton conduction; while the conductivity of high Fe content samples (x ≥ 0.3) showed little dependence on the humidity. The chemical stability of BNF samples was investigated in boiling H2O and in flowing 100% CO2 at elevated temperatures and the results demonstrated that all members were structurally stable under both conditions, except the x = 0.5 member which decomposed into BaCO3 in the presence of CO2 at 800 °C.  相似文献   

2.
Apatite-type oxides of formula (La/Sr)10−xSi6O26+y have been attracting significant interest recently, because of their high oxide ion conductivity. In this paper we report the synthesis and conductivities of phases based on doping La9.33Si6O26 with Co, Fe, Mn on the Si site, according to the formula La9.33+x/3Si6−xMxO26 (M=Co, Fe, Mn). Substitution limits observed were x≤1.5 (Co), x≤1.25 (Fe), x≤0.5 (Mn). Higher Mn levels could be achieved by substituting onto the La site, with it being possible to prepare the phase La8Mn2Si6O26. The highest conductivities were observed for the Co doped samples, although investigations into the dependence of conductivity on p(O2) (0.2–10−5 atm.) indicated that the conductivity was dominated by the electronic component in these cases. In contrast, the conductivities for the Fe and Mn doped samples were mainly ionic in the same p(O2) range. Experiments into varying the oxygen content of these doped phases indicated that increasing the oxygen content above the nominally stoichiometric O26 appears to increase the oxide ion conductivity. Preliminary studies of the reactivity of the electrolyte La9.33Si6O26 with potential SOFC cathode materials (La1−xSrxMO3; M=Co, Fe, Mn) suggests that reaction can occur at high temperatures leading to the incorporation of the transition metal into the apatite electrolyte. However, the fact that these doped phases exhibit high conductivities suggests that this may limit any problems caused by such a reaction at the electrolyte-electrode interface. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.  相似文献   

3.
La0.6Sr0.4CoxFe1−xO3−δ (LSCF), La0.6Sr0.4Cu0.2Fe0.8O3−δ, Ba0.5Sr0.4Co0.8Fe0.2O3−δ and LaFeO3−δ nanoparticles were synthesized by a reverse micelle procedure. Controlling the size of the micelles through the water:oil phase ratio enabled synthesis of phase pure perovskite particles with average sizes from 14 nm to 50 nm. Small amounts of an impurity phase, likely cobalt oxide, were detected in the XRD spectrum of high cobalt content samples of LSCF (x = 0.8). La0.6Sr0.4Co0.2Fe0.8O3−δ nanoparticles were utilized to coat the surface of a dense thin-film La0.6Sr0.4Co0.2Fe0.8O3−δ solid oxide fuel cell cathode. The polarization resistance of the nanoparticle coated electrode, measured at open circuit in air at 973 K, was 20% lower than an equivalent un-coated electrode.  相似文献   

4.
Electronic as well as ionic conducting properties for oxyapatite-type solid electrolytes based on lanthanum silicate, La9.333 + xSi6O26 + 1.5x (LSO) were investigated in the oxygen-excess region (x > ca. 0.3). We have found that the oxygen excess-type LSO (OE-LSO), namely La10Si6O27 on weighted basis, exhibited high conductivity, and substitution of the Si-site of LSO with some dopants (Mn+) had a positive effect toward the conducting property. Furthermore, it was also found that addition of a very small amount of iron ions into the M-doped OE-LSO, La10(Si6-yMn+y)O27-(2-0.5n)y, improved its conductivity. On the other hand, replacement of the La-site with various ions for La10(Si6-yMn+y)O27-(2-0.5n)y did little to improve conductivity. The electronic transport numbers for Al-doped OE-LSO with Fe-addition, (1-α){La10(Si5.8Al0.2)O26.9}-α(FeOγ), evaluated with the Hebb-Wagner polarization method were very low: i.e., 1.1 × 10− 3 and 2.9 × 10− 3 under P(O2) = 1.1 × 104 Pa at 1073 K for α = 0.00 and 0.005, respectively. Conductivity for each sample was unchanged under humidified atmosphere at 1073 K sustained for over 50 h, revealing that both compositions were chemically stable. It was concluded that 0.995{La10(Si5.8Al0.2)O26.9}-0.005(FeOγ) is suitable for the fuel cell electrolytes because of its high and almost pure ionic conductivity, and its good chemical stability under humidified as well as reducing conditions.  相似文献   

5.
We present results on the Hall coefficient RH in the normal state for a GdBa2Cu3O7−δ/La0.75Sr0.25MnO3 bilayer and a La0.75Sr0.25MnO3 film grown by dc magnetron sputtering on (1 0 0) SrTiO3. We find that the electric transport on the bilayer can be qualitatively described using a simple parallel layers model. The GdBa2Cu3O7−δ layer presents a carrier density approximately equal to that reported for 7 − δ = 6.85 oxygen doping. Also we observe an unexpected presence of two Hall resistivity regimes, effects that may be associated with the internal magnetic field induced on the superconducting layer by the ferromagnetic layer.  相似文献   

6.
The effect of nickel substitution on defect chemistry, electrical properties, and dimensional stability of calcium-doped yttrium chromite was studied for use as an interconnect material in high temperature solid oxide fuel cells (SOFCs). The compositions of Y0.8Ca0.2Cr1 − xNixO3 ± δ (x = 0-0.15), prepared using the glycine nitrate process, showed single phase orthorhombic perovskite structures over a wide range of oxygen partial pressures (4.6 × 10− 20 atm ≤ pO2 ≤ 0.21 atm at 900 °C). X-ray diffraction (XRD) analysis indicated that most of the nickel ions replacing chromium ions are divalent and act as acceptor dopants, leading to a substantial increase in conductivity. In particular, the conductivity at 900 °C in air increased from 10 S/cm to 34 S/cm with 15% nickel substitution, and an increase in charge carrier density was confirmed by Seebeck measurements, which validated the predominant Ni2+ oxidation state. A point defect model was derived, and the relationship between electrical conductivity and oxygen partial pressure was successfully fitted into the proposed model. The defect modeling results indicated that nickel substitution improves the stability of calcium-doped yttrium chromite toward reduction and suppresses the oxygen vacancy formation, which results in significantly increased electrical conductivity in reducing environment. The electrical conductivity of Y0.8Ca0.2Cr0.85Ni0.15O3 ± δ at 900 °C in reducing atmosphere (pO2 = 10− 17 atm) was 5.8 S/cm, which was more than an order of magnitude higher than that of Y0.8Ca0.2CrO3 ± δ (0.2 S/cm). Improved stability in reducing atmosphere was further confirmed by dilatometry measurements showing reduced isothermal “chemical” expansion, and the isothermal expansion in reducing atmosphere (pO2 = 10− 17 atm) at 900 °C decreased from 0.07% for Y0.8Ca0.2CrO3 ± δ to 0.03% for Y0.8Ca0.2Cr0.85Ni0.15O3 ± δ. Based on these results, enhanced electrical performance and mechanical integrity is expected with nickel substitution on calcium-doped yttrium chromite in SOFC operating conditions.  相似文献   

7.
Apatite silicates have recently been reported as promising electrolyte materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). In this work, a series of apatite-type compounds La9.67Si6-xAlxO26.5-x/2 (LSAO) with x = 0-2 are synthesized by the sol-gel process at calcining temperature of 800-900 °C. Thermal expansion coefficient, relative density and electrical conductivity of these samples with different Al doped contents are investigated. A symmetrical cell, which is composed of La9.67Si5AlO26 electrolyte and (La0.74Bi0.10Sr0.16)MnO3+δ (LBSM) cathode, is fabricated and electrochemically characterized. LBSM cathode shows a good electrochemical performance, which proves LBSM to be a promising candidate cathode for LSAO-based electrolyte.  相似文献   

8.
Raman spectra of eight polycrystalline apatites of the general formula La10−xSi6−yM′yO26 ± δ with M′ = Al or Fe were obtained at 300 K. Raman spectra of La10Si4Fe2O26 and La9.83Si4.5Al1.5O26 were investigated in the range 80–1000 K and 80–623 K, respectively. Tentative assignments of bands to stretching and bending modes of SiO4 tetrahedra and to M'O vibrations are proposed. Except for the two new bands, which appear around 700 cm−1 when Al is replaced by Fe, only some band broadenings and relative intensity changes are observed as a function of the rate of O5 or La vacancies. Most of the bands soften and broaden continuously when raising the temperature. This is an indication that the Al‐ and Fe‐substituted apatites do not undergo any structural change up to 1000 K. Above 1000 K, the broad and weak shoulder observed at 850 cm−1 for La10Si4Fe2O26 is replaced by a strong band at 868 cm−1, suggesting that SiO4 tetrahedra undergo a structural modification. All compounds show the same residual band broadening at 80 K. This suggests that there is a small rate of static disorder preferentially related to the solubility of Al and Fe in the Si sublattice rather than to other defects. Moreover, the observation of FeO modes indicates that the dynamics of the solid solution obeys the so‐called two‐mode behavior. The occurrence of FeO stretching vibrations 150 cm−1 lower than for those of SiO suggests that the coordination number of iron could be larger than 4, particularly for the Fe4+ species. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

9.
Electrochemical synthesis of ammonia was investigated using a cobalt-free La0.6Sr0.4Fe0.8Cu0.2O3-δ-Ce0.8Sm0.2O2-δ (LSFCu-SDC) composite cathode and SDC-ternary carbonate composite electrolyte. La0.6Sr0.4Fe0.8Cu0.2O3-δ and Ce0.8Sm0.2O2-δ were prepared via combined EDTA-citrate complexing sol-gel and glycine nitrate processes, respectively, and characterised by X-ray diffraction (XRD). Ammonia was successfully synthesised from wet hydrogen and dry nitrogen under atmospheric pressure using Ni-SDC, SDC-carbonate and LSFCu-SDC composites as anode, electrolyte and cathode respectively. Ammonia formation was observed at 400, 425, 450 and 475 °C and the maximum rate of ammonia production was found to be 5.39 × 10−9 mol s−1 cm−2 at 450 °C and 0.8 V. The AC impedance measurements were recorded before and after the ammonia synthesis in the range of temperature 400-475 °C. The formation of ammonia at the N2 side together with stable current at 450 °C under constant voltage demonstrates that SDC-(Li/Na/K)2CO3 composite electrolyte exhibits significant proton conduction at a temperature around 450 °C.  相似文献   

10.
Baoan Fan  Xiangli Liu 《Solid State Ionics》2009,180(14-16):973-977
A-deficit La0.54Sr0.44Co0.2Fe0.8O3 ? δ cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs) was synthesized by a citrate complexation (Pechini) route. Using La0.54Sr0.44Co0.2Fe0.8O3 ? δ as cathode material, a superior cell performance with the maximum power density of 309, 470 and 855 mW cm? 2 at 600, 650 and 700 °C was achieved, in contrast with the maximum power density of 266, 354 and 589 mW cm? 2 using conventional La0.6Sr0.4Co0.2Fe0.8O3 ? δ as cathode material at the same temperatures. The reason of this improvement was analyzed on the basis of defect chemistry. Thermal shrinkage experiment testified that the oxygen vacancies in La0.54Sr0.44Co0.2Fe0.8O3 ? δ are more mobile than in La0.6Sr0.4Co0.2Fe0.8O3 ? δ. Furthermore, theoretical calculation in terms of their composition and the shift of peak position in XRD pattern showed that the concentration of oxygen vacancies of La0.54Sr0.44Co0.2Fe0.8O3 ? δ is higher than that of La0.6Sr0.4Co0.2Fe0.8O3 ? δ. Therefore, the oxygen ion conductivity via vacancies transfer mechanism is enhanced, which induces the polarization resistance of La0.54Sr0.44Co0.2Fe0.8O3 ? δ being decreased with a result of cell performance improved.  相似文献   

11.
Preparation of LaNi1 − xFexO3, which is one of the candidate materials of solid oxide fuel cell cathode, current collecting layer and interconnect coating was examined with Pechini method and solid state reaction method. Single phase LaNi1 − xFexO3 with large Ni content has successfully been prepared by low temperature sintering as 750 °C with Pechini method, whereas large amount of raw materials has remained with solid state reaction method by sintering at the same temperature. It can be ascribed to more homogenous cation distribution in raw powder material prior to sintering with Pechini method. It has also been revealed that LaNi1 − xFexO3 with x lower than 0.3 is thermodynamically unstable in air above 1000 °C. LaNi0.6Fe0.4O3 showed superior property as cathode material with high electrical conductivity, thermodynamic stability and appropriate sintering property.  相似文献   

12.
Using (Bi2O3)0.75(Dy2O3)0.25 nano-powder synthesized by reverse titration co-precipitation method as raw material, dense ceramics were sintered by both Spark Plasma Sintering (SPS) and pressureless sintering. According to the predominance area diagram of Bi-O binary system, the sintering conditions under SPS were optimized. (Bi2O3)0.75(Dy2O3)0.25 ceramics with relative density higher than 95% and an average grain size of 20 nm were sintered in only 10 min up to 500 °C. During the pressureless sintering process, the grain growth behavior of (Bi2O3)0.75(Dy2O3)0.25 followed a parabolic trend, expressed as D2 − D02 = Kt, and the apparent activation energy of grain growth was found to be 284 kJ mol− 1. Dense (Bi2O3)0.75(Dy2O3)0.25 ceramics with different grain sizes were obtained, and the effect of grain size on ion conductivity was investigated by impedance spectroscopy. It was shown that the total ion conductivity was not affected by the grain size down to 100 nm, however lower conductivity was measured for the sample with the smallest grain size (20 nm). But, although only the δ phase was evidenced by X-ray diffraction for this sample, a closer inspection by Raman spectroscopy revealed traces of α-Bi2O3.  相似文献   

13.
To characterize the local relaxation in the structure of lanthanum silicate oxyapatite materials, six compositions with different cation and oxygen stoichiometries (La8Ba2Si6O26, La9BaSi6O26.5, La10Si5.5Mg0.5O26.5, La9.33SiO26, La9.67SiO26.5 and La9.83Si5.5Al0.5O26.5) were investigated by combining Raman scattering and 29Si and 27Al magic‐angle spinning nuclear magnetic resonance (MAS‐NMR) spectroscopies. Only [SiO4]4− species were evidenced and the hypotheses of [Si2O7]6− and [Si2O9]8− entities were ruled out. Both oxygen excess and cation vacancies induce local distortions in the structure, which leads to nonequivalent [SiO4]4− species, characterized by different 29Si MAS‐NMR signals and by splitting of Raman signals. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

14.
The oxygen nonstoichiometry of La0.6Sr0.4FeO3 − δ was measured at intermediate temperatures (773 to 1173 K) between 1 bar and the decomposition oxygen partial pressure by thermogravimetry and coulometric titration. The decomposition of the ABO3 perovskite phase was found to occur at low oxygen partial pressures (below 10− 20 bar). Using an atmosphere-controlled high-temperature XRD setup, the rhombohedral lattice parameters were obtained between 10− 4 and 1 bar at 773 to 1173 K. A phase transition from rhombohedral to cubic might be expected to occur at high temperatures and for δ near the plateau at δ = [Sr] / 2. The lattice expansion was separated into “pure” thermal and chemically induced expansion by combining the lattice parameters with the oxygen nonstoichiometry data. The linear thermal expansion was formulated with a “pure” thermal expansion coefficient of αth = 11.052 · 10− 6 K− 1 and a chemical expansion coefficient of αchem = 1.994 · 10− 2.The results were compared with previous data obtained for La0.6Sr0.4Co1 − yFeyO3 − δ with y = 0.2-0.8. La0.6Sr0.4FeO3 − δ was confirmed to show the highest thermo-chemical stability. While the chemical expansion of La0.6Sr0.4Co1 − yFeyO3 − δ seems little affected by the iron content, the thermal expansion coefficient was the lowest for La0.6Sr0.4FeO3 − δ.  相似文献   

15.
Melilite type ceramics ABC3O7 such as La1.54Sr0.46Ga3O7.27 are a new class of oxide conductors where the conductivity is carried out through interstitial oxygen ions. This work presents the attempt to replace the A-site element La with the other lanthanide elements and Y, resulting in various Ln1 + xSr1 − xGa3O7 + x/2 ceramics, in which Ln = La, Pr, Nd, Sm, Eu, Gd, Dy, Yb, Y, and 0.1 < x < 0.54. X-ray diffraction analysis shows that the melilite structure could be formed when the replacement is conducted with most lanthanides but not Yb and Y. Impedance spectroscopy demonstrates that the conductivity decreases dramatically with the decreasing of Ln3+ size and the charge-carrier concentration. These results suggest that, as an interstitial oxide ion electrolyte, La1.54Sr0.46Ga3O7.27 is the most promising ceramic in the Ln1 + xSr1 − xGa3O7+x/2 melilite family since La3+ has the largest ionic radius of the lanthanide elements.  相似文献   

16.
Magnetic measurements have been performed on 40-nm sphere-like Fe3 − δO4 (δ=0.043) nanoparticles using a Quantum Design vibrating sample magnetometer. Coating Fe3 − δO4 nanoparticles with SiO2 effectively eliminates magnetic interparticle interactions so that the coercive field HC in the high-temperature range between 300 K and the Curie temperature (855 K) can be well fitted by an expression for noninteracting randomly oriented single-domain particles. From the fitting parameters, the effective anisotropy constant K is found to be (1.38±0.11)×105 erg/cm3, which is very close to the bulk magnetocrystalline anisotropy constant of 1.35×105 erg/cm3. Moreover, the inferred mean particle diameter from the fitting parameters is in quantitative agreement with that determined from transmission electron microscope. Such a quantitative agreement between data and theory suggests that the ensemble of our SiO2-coated sphere-like Fe3 − δO4 nanoparticles represents a good system of noninteracting randomly-oriented single-domain particles.  相似文献   

17.
Crystal structure, thermogravimetry (TG), thermal expansion coefficient (TEC), electrical conductivity and AC impedance of (Ba0.5Sr0.5)1-xLaxCo0.8Fe0.2O3-δ (BSLCF; 0.05?x?0.20) were studied in relation to their potential use as intermediate temperature solid oxide fuel cell (IT-SOFC) cathode. A single cubic pervoskite was observed by X-ray diffraction (XRD). The TEC of BSLCF was increasing slightly with the increasing content of La, and all the compounds showed abnormal expansion at high temperature. Proved by the TG result, it was associated with the loss of lattice oxygen. The electrical conductivity, which is the main defect of Ba0.5Sr0.5 Co0.8Fe0.2O3-δ (BSCF), was improved by La doping, e.g., the compound of x=0.20 demonstrated a conductivity of σ=376 S cm−1 at 392 °C. The increase of electrical conductivity resulted from the increased concentration of charge carrier induced by La doping. In addition, the AC impedance revealed the better electrochemical performance of BSLCF. For example, at 500 °C, the sample with composition x=0.15 yielded the resistance values of 2.12 Ω cm2, which was only 46% of BSCF.  相似文献   

18.
Magnetoelectric (ME) nanocomposites containing Ni0.75Co0.25Fe2O4-BiFeO3 phases were prepared by citrate sol-gel process. X-ray diffraction (XRD) analysis showed phase formation of xNi0.75Co0.25Fe2O4-(1−x)BiFeO3 (x=0.1, 0.2, 0.3 and 0.4) composites on heating at 700 °C. Transmission electron microscopy revealed the formation of powders of nano order size and the crystal size was found to vary from 30 to 85 nm. Dispersion in dielectric constant (ε) and dielectric loss (tan δ) in the low-frequency range have been observed. It is seen that nanocomposites exhibit strong magnetic properties and a large ME effect. On increasing Ni0.75Co0.25Fe2O4 contents in the nanocomposites, the saturation magnetization (MS) and coercivity (HC) increased after annealing at 700 °C. The large ME output in the nanocomposites exhibits strong dependence on magnetic bias and magnetic field frequency. The large value of ME output can be attributed to small grain size of ferrite phase of nanocomposite being prepared by citrate precursor process.  相似文献   

19.
The oxygen transport properties of the Bi0.775La0.225O1.5 electrolyte material have been investigated. Isotopic exchange depth profiling (IEDP) technique with secondary ion mass spectrometry (SIMS) was used in order to measure the oxygen tracer diffusion coefficient D. The activation energy for oxygen tracer diffusion was found to be 115 ± 2 kJ/mol (1.19 ± 0.02 eV). The measured D values were converted using the Nernst-Einstein relationship to conductivity and compared with data from AC Impedance. The agreement of the two sets of data implies that the material is an oxygen ion conductor.  相似文献   

20.
《Solid State Ionics》2006,177(19-25):1753-1756
La1−xSrxMeO3 (Me = Mn, Co, Fe) perovskites are used as cathodes and are also attractive materials for application as the contact layer between cathode and interconnect in solid oxide fuel cells. In this contribution, three perovskite series, La0.8Sr0.2Mn1−xCoxO3-δ (series 1), La0.8Sr0.2Fe1−xCoxO3-δ (series 2) and La0.8Sr0.2Mn1−x/2Fe(1−x)/2CoxO3-δ (series 3) with x = 0, 0.25, 0.5, 0.75 and 1 were re-investigated under identical synthesis and measurement conditions with the aim of obtaining a full overview of the quasi-ternary system La0.8Sr0.2MnO3-δ–La0.8Sr0.2FeO3-δ–La0.8Sr0.2CoO3-δ. The distribution of the different crystallographic phases in the selected series, the DC electrical conductivity and the thermal expansion coefficients are presented.  相似文献   

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