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1.
《Solid State Ionics》2006,177(26-32):2333-2337
Pulsed laser deposition has been used to fabricate nanostructured BaCe0.85Y0.15O3−δ films. Protonic conduction of the fabricated BaCe0.85Y0.15O3−δ films was compared to the sintered BaCe0.85Y0.15O3−δ. Sintered samples and laser targets were prepared by sintering BaCe0.85Y0.15O3−δ powders derived by solid state synthesis. Films 1 to 8 μm thick were deposited by KrF excimer laser on porous Al2O3 substrates. Thin films were fabricated at deposition temperatures of 700 to 950 °C at O2 pressures up to 200 mTorr using laser pulse energy densities of 1.4–3 J/cm2. Fabricated films were characterized by X-ray diffraction, electron microscopy and electrical impedance spectroscopy. Single phase BaCe0.85Y0.15O3−δ films with a columnar growth morphology are observed with preferred crystal growth along the [100] or [001] direction. Results indicate [100] growth dependence upon laser pulse energy. Electrical conductivity of bulk samples produced by solid state sintering and thin film samples were measured over a temperature range of 100 to 900 °C. Electrical conduction behavior was dependent upon film deposition temperature. Maximum conductivity occurs at deposition temperature of 900 °C; the electrical conductivity exceeds the sintered specimen. All other deposited films exhibit a lower electrical conductivity than the sintered specimen. Activation energy for electrical conduction showed dependence upon deposition temperature, it varied from 115 to 54 kJ. Film microstructure was attributed to the difference in electrical conductivity of the BaCe0.85Y0.15O3−δ films.  相似文献   

2.
BaZr0.8 − xPrxY0.2O3 − δ (BZPYx, 0.1 ≤ x ≤ 0.4) perovskite oxides were investigated for application as cathode materials for intermediate temperature solid oxide fuel cells based on proton conducting electrolytes (protonic-SOFCs). The BZPYx reactivity with CO2 and water vapor was evaluated by thermogravimetric and X-ray diffraction analyses, and good chemical stability was observed for each BZPYx composition. Conductivity measurements of BZPYx sintered pellets were performed as a function of temperature and pO2 in humidified atmospheres, corresponding to cathode operating condition in protonic-SOFCs. Different conductivity values and activation energies were measured depending on the Pr content, suggesting the presence of different charge carriers. For all the compositions, the partial electronic conductivity, calculated from conductivity measurements at different pO2, increased with increasing the temperature from 500 to 700 °C. Furthermore, the larger the Pr content, the larger the electronic conductivity. BaZr0.7Pr0.1Y0.2O3 − δ and BaZr0.4Pr0.4Y0.2O3 − δ showed mostly pure proton and electron conductivity, respectively, whereas the intermediate compositions showed mixed proton/electronic conductivity. Among the two mixed proton/electronic conductors, BaZr0.6Pr0.3Y0.2O3 − δ presented the larger conductivity, which coupled with its good chemical stability, makes this perovskite oxide a candidate cathode materials for protonic-SOFCs.  相似文献   

3.
Oxygen nonstoichiometry (δ), total conductivity (σ) and thermoelectric power (S) of the LaFe0.7Ni0.3O3 − δ sample have been studied as functions of temperature and oxygen partial pressure. Based on the results of the direct reduction of the sample in hydrogen flow at 1100 °C the absolute oxygen content (3 − δ) has been found to vary from 2.999 to 2.974 in the range of 1273-1373 K and 10− 3-0.21 atm. The point defect equilibrium models have been proposed and fitted to the set of experimental data in the form of log p(O2) = f(δ)T dependences. The values of standard thermodynamic quantities of defect formation reactions have been assessed. The joint analysis of oxygen nonstoichiometry, total conductivity and thermoelectric power has been performed using a small-polaron approach. The values of partial conductivity, partial thermopower and mobilities of electronic charge carriers have been calculated. The p-type semiconducting behavior of LaFe0.7Ni0.3O3 − δ has been explained by the higher mobility values of electron holes than those of electrons in the whole range of thermodynamic parameters studied.  相似文献   

4.
The total conductivity of BaCe0.9Y0.1O3 − δ material was measured under air, in a large p(H2O) range up to 0.30 bar. The defect concentrations (OHO·, VO· · and h·) and electrical conductivities were calculated on the basis of chemical constants (diffusion coefficients and equilibrium constants reported in the past literature) and compared to the experimental data. Protonic transport number as high as 0.8 was found at 700 °C, under air containing 0.30 bar of water, which allows a possible extension of the protonic temperature range of this material using water rich atmosphere. In-situ Raman spectroscopy under wet and dry air was performed from room temperature up to 700 °C in two wavenumber ranges. At low wavenumber, characteristic of lattice vibrations, this study clearly shows that no significant changes occur upon water insertion while at high wavenumbers, characteristic of OH vibrations, two contributions to the OH vibrations were found. This is discussed in terms of proton environment and transient hydrogen bonds. Moreover, this in situ study confirms that, at moderate p(H2O), water insertion becomes significant at temperature below 650 °C.  相似文献   

5.
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   

6.
The electrical conductivities of SrZr0.9Y0.1O3-δ (SZY10) and BaCe0.95Y0.05O3-δ(BCY5) were measured as a function of hydrogen partial pressure P(H2), oxygen partial pressure P(O2), steam partial pressure P(H2O) and temperature. Their relaxation processes were analyzed using the solution of Fick's diffusion equation to determine the chemical diffusion coefficients and surface reaction rate constants. There were the differences in chemical relaxation kinetics and the conductivity dependence on P(H2O) between the both oxides. The chemical diffusion coefficients depend on temperature but are essentially independent of P(H2), P(O2) and P(H2O). The ambipolar diffusion treatment can explain the temperature dependence of chemical diffusion coefficients quantitatively. The chemical diffusion coefficients of SZY10 is one or two order of magnitude smaller than those of BCY5 at low temperature. The sluggish conductivity relaxation in SZY10 was due to considerably small oxygen vacancy diffusion coefficients at low temperatures. The total conductivity depends on P(H2O) in the case of SZY10, but not for BCY5. This different dependence on P(H2O) is caused by the difference in the ratio between proton mobility and oxide-ion mobility.  相似文献   

7.
Agnieszka Lacz 《Ionics》2016,22(8):1405-1414
Y-doped barium cerate BaCe0.9Y0.1O3???δ was synthesised by a solid-state reaction method. Materials with different average grain sizes and grain boundary surface areas were obtained. The effect of microstructure on the chemical stability in the CO2 and H2O-containing atmosphere and electrical properties was analysed and discussed. To evaluate the chemical stability of BaCe0.9Y0.1O3???δ , the exposure test was performed. Samples were exposed to the carbon dioxide and water vapour-rich atmosphere at 25 °C for 700 h. Thermogravimetry supplied by mass spectrometry was applied to analyse the samples before and after this comprehensive test. The mass loss for samples before and after the test and the amount of BaCO3 formed during the test were directly treated as the measure of chemical instability of BaCe0.9Y0.1O3???δ in the atmosphere rich in carbon dioxide and water vapour. As it was observed, the BaCe0.9Y0.1O3???δ chemical stability towards CO2 and H2O is not affected by the materials’ microstructure. Electrical properties of BaCe0.9Y0.1O3???δ which differs with microstructure were determined using electrochemical impedance spectroscopy (EIS). It was found that the grain interior resistivity and activation energy of grain interior conductivity is microstructure independent. However, the effect on microstructure was seen on the EIS spectra in the range of grain boundary contribution. Therefore, the lowest activation energy and the highest conductivity were observed for a material with the lowest grain boundary surface area.  相似文献   

8.
(Y0.95Er0.05)2O3 single-crystalline nanorods with intense red emission via up-conversion are synthesized by a hydrothermal method under modest reaction conditions. Green and red emissions are observed for both as-synthesized sample and post-treated sample after excitation at 488 nm and with upconversion pumping (810 nm). The experimental results indicate that the stokes and up-conversion luminescence of the post-treated (500 °C for 2 h) Y2O3:Er nanorods is more efficient than those of as-prepared materials. The increase of the Stokes luminescence may result from the improved crystallization, smooth surface and uniform diameter distribution. The enhanced red emission via upconversion is due to removal of part of surface contaminants, such as CO32− and OH. It is believed that a new mechanism is responsible for populating the 4S3/2 and 4F9/2 levels.  相似文献   

9.
Perovskite-type SrFe0.7Al0.3O3 − δ and SrCo0.8Fe0.2O3 − δ, and two related dual-phase composites with nominal compositions (SrFeO3 − δ)0.7(SrAl2O4)0.3 and (SrCo0.8Fe0.2O3 − δ)0.7(SrAl2O4)0.3, were comparatively studied employing controlled-atmosphere dilatometry, thermogravimetry, Mössbauer spectroscopy, and measurements of steady-state oxygen permeation fluxes through dense ceramic membranes. The composite materials display lower thermal and chemical expansion compared to the parent single-phase perovskites. The thermal expansion coefficients at 1023-1223 K are however still high, (20-23) × 10− 6 K− 1 at atmospheric oxygen pressure and (17-18) × 10− 6 K− 1 at p(O2) = 10 Pa, thus limiting the range of possible membrane reactor configurations. Sr(Co,Fe)O3 − δ-based materials exhibit extensive vacancy-ordering processes in inert atmospheres, resulting in a slow relaxation of the oxygen nonstoichiometry, chemical expansion and oxygen permeation fluxes. In comparison to Sr(Fe,Al)O3 − δ, the stability of cobalt-containing ceramics in CO2 is also poor, which leads to a partial blocking of the membrane surface by decomposition products and degradation of the oxygen transport. Thermogravimetric analysis showed that the interaction with carbon dioxide occurs even at elevated temperatures, up to 1223 K. Under high oxygen chemical potential gradients such as air/(H2-H2O), the composite membranes showed kinetically stable operation without bulk decomposition at 1073 K. The kinetic stabilization associated with surface-limited oxygen permeation was confirmed by the conversion-electron Mössbauer spectroscopy analysis of one (SrFeO3 − δ)0.7(SrAl2O4)0.3 membrane exposed to dry CH4 at 1173 K, where no traces of Fe2+ and metallic iron were detected in the reduced surface layer.  相似文献   

10.
Multiferroic Bi0.95Sm0.05Fe1−xCoxO3 (x=0−0.1) ceramics were prepared by the rapid liquid phase sintering method. For all the samples studied, the dielectric constant and dielectric loss decrease with increasing frequency in the range from 1 kHz to 1 MHz. It shows that the dielectric constant of Bi0.95Sm0.05FeO3 at 10 kHz is about forty times larger than that of pure BiFeO3. This dramatic change in the dielectric properties of Bi0.95Sm0.05Fe1−xCoxO3 (x=0−0.1) samples can be understood in terms of the space charge limited conduction associated with crystal defects, which was indicated by the increase of magnetoelectric effect with doping Co3+ under applied magnetic field from 1 to 8 kOe. It was believed that the ferroelectric polarization enhancement comes from the exchange interaction between the Sm3+ and Fe3+ or Co3+ ions for Bi0.95Sm0.05Fe0.95Co0.05O3 at room temperature.  相似文献   

11.
The chemomechanical properties and microstructural stability of nanocrystalline PrxCe1 − xO2 − δ solid solutions are studied as a function of temperature by in situ X-ray diffraction measurements under oxidizing conditions at P(O2) ~ 200 mbar. The chemical expansion coefficient of nanocrystalline powder specimens, operative at intermediate temperatures during which Pr4+ is reduced to Pr3+, is found to be similar to that obtained for coarse-grained PrxCe1 − xO2 − δ. This is contrary to reports regarding variation of physical and chemical properties with crystallite size. The thermal expansion coefficient, measured under conditions for which PrxCe1 − xO2 − δ is highly oxygen deficient, was found to be greater than that measured for fully oxidized PrxCe1 − xO2 − δ, with potential sources of these changes discussed. Moreover, the microstructure of nanocrystalline PrxCe1 − xO2 − δ is observed to have excellent stability at working temperatures below 800 °C, enabled by the inherent microstrain in the structure, highlighting the potential application of this material for solid state electrochemical devices.  相似文献   

12.
We carefully studied the nonsuperconducting sample of the magneto-superconducting RuSr2(Eu1−xCex)Cu2O10−δ series with composition RuSr2EuCeCu2O10−δ. This compound seems to exhibit a complex magnetic state as revealed by host of techniques like resistivity, thermopower, magnetic susceptibility, and MR measurements. The studied compound exhibited ferromagnetic like M(H) loops at 5, 20, and 50 K, and semiconductor like electrical conduction down to 5 K, with −MR7 T of up to 4% at low temperatures. The −MR7 T decreases fast above 150 K and monotonically becomes close to zero above say 230 K. Below, 150 K −MR7 T decreases to around 3% monotonically down to 75 K, with further increase to 4% at around 30 K and lastly having a slight decrease below this temperature. The thermopower S(T) behavior closely followed the −MR7 T steps in terms of d(S/T)/dT slopes. Further, both MR7 T steps and d(S/T)/dT slopes are found in close vicinity to various magnetic ordering temperatures (Tmag) of this compound.  相似文献   

13.
Sr-doped and Sr-free La1 − xSrxMn1 − yCryO3 ± δ (LSMC, x(Sr) = 0-0.2, y(Cr) = 0.4-0.6) perovskite-type oxides were synthesized and evaluated as single phase anodes for use in intermediate temperature solid oxide fuel cell applications. Their thermo-chemical and chemical stabilities were investigated in hydrogen at high temperatures and correlated with their oxygen non-stoichiometry (3 ± δ), determined by permanganate titration. The catalytic activity towards hydrogen oxidation was examined as a function of oxide sintering time, operating temperature, and the Sr and Cr contents, using a Pt mesh current collector. While all of the perovskite oxides studied here showed some irreversible performance degradation with time under both open circuit and anodically polarized conditions, La0.9Sr0.1Mn0.6Cr0.4O3.03 (LSMC9164), sintered at 1200 °C for 10 h, was found to be the most catalytically active and also the most stable.  相似文献   

14.
Bismuth- and yttrium-co-doped barium cerates were successfully synthesised by solid-state reactions followed by sintering between 1,400 and 1,500 °C for 1 to 6 h allowing densification above 98 % to be obtained. All samples were found to retain their original orthorhombic structure after treatment in either oxidising or reducing atmospheres (dry and wet). Mechanical strength was affected by structure upon reduction due in part to strains and stresses induced by bismuth ionic size variations. Conductivity values as high as 0.055 S/cm were obtained for sample BaCe0.6Zr0.1Y0.1Bi0.2O3?δ and of 0.0094 S/cm for the Zr-free compound BaCe0.7Y0.2Bi0.1O3?δ at 700 °C in air. In all the investigated materials, sample BaCe0.6Zr0.1Y0.1Bi0.2O3?δ exhibits the highest conductivity in both air and wet 5 % H2/Ar with good mechanical strength. BaCe0.6Zr0.1Y0.1Bi0.2O3?δ is a promising mixed H+/e? conductor, a potential component of composite anode for solid oxide fuel cells.  相似文献   

15.
Y1.9−xLi0.1EuxO3 (x=0.02, 0.05, 0.08, and 0.12) films were fabricated by spin-coating method. A colloidal silica suspension with Y1.9−xLi0.1EuxO3 phosphor powder was exploited to obtain the highly stable and effective luminescent films onto the glass substrate. After heating as-prepared Y1.9−xLi0.1EuxO3 films at 700 °C for 1 h, the phosphor films exhibit a high luminescent brightness as well as a strong adhesiveness on the glass substrate. The emission spectra of spin-coated and pulse-laser deposited Y1.82Li0.1Eu0.08O3 films were compared. The cathodoluminescence of the phosphor films was carried out at the anode voltage 1 kV.  相似文献   

16.
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   

17.
Physical and electrical properties of sputtered deposited Y2O3 films on NH4OH treated n-GaAs substrate are investigated. The as-deposited films and interfacial layer formation have been analyzed by using X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS). It is found that directly deposited Y2O3 on n-GaAs exhibits excellent electrical properties with low frequency dispersion (<5%), hysteresis voltage (0.24 V), and interface trap density (3 × 1012 eV−1 cm−2). The results show that the deposition of Y2O3 on n-GaAs can be an effective way to improve the interface quality by the suppression on native oxides formation, especially arsenic oxide which causes Fermi level pinning at high-k/GaAs interface. The Al/Y2O3/n-GaAs stack with an equivalent oxide thickness (EOT) of 2.1 nm shows a leakage current density of 3.6 × 10−6 A cm−2 at a VFB of 1 V. While the low-field leakage current conduction mechanism has been found to be dominated by the Schottky emission, Poole-Frenkel emission takes over at high electric fields. The energy band alignment of Y2O3 films on n-GaAs substrate is extracted from detailed XPS measurements. The valence and conduction band offsets at Y2O3/n-GaAs interfaces are found to be 2.14 and 2.21 eV, respectively.  相似文献   

18.
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   

19.
The results of oxygen nonstoichiometry, δ, measured by means of coulometric technique as a function of oxygen partial pressure, po2, in temperature range 1223 ≤ T, K ≤ 1323 are presented for the perovskite-type doped with chromium solely LaCo0.7Cr0.3O3 − δ and simultaneously doped both with strontium and chromium La0.7Sr0.3Co0.7Cr0.3O3 − δ cobaltites. The limit stability of the latter was found to exceed that of undoped cobaltite LaCoO3 − δ on six orders of magnitude of po2 at a given temperature. The modeling of the defect structure of these perovskites was carried out and its adequate model was found. Chemical and self-diffusion coefficients of oxygen vacancies and oxygen ionic conductivity and ionic transport numbers were measured for the first time for La0.7Sr0.3Co0.7Cr0.3O3 − δ as a function of oxygen partial pressure po2and temperature in the ranges − 4 ≤ log(po2, atm) ≤ 0 and 1223 ≤ T, K ≤ 1323, respectively. The additional substitution of Sr for La in LaCo0.7Cr0.3O3 − δ was shown to lead to noticeable increase of ionic conductivity and oxygen chemical diffusion coefficient at given values of oxygen partial pressure and temperature as compared to lanthanum cobaltite doped with chromium solely. Self-diffusion coefficient of oxygen vacancies and their mobility in La0.7Sr0.3Co0.7Cr0.3O3 − δ were found to be dependent on oxygen partial pressure and nonstoichiometry unlike undoped and doped with chromium lanthanum cobaltites.  相似文献   

20.
Ce-substituted barium ferrite with chemical composition BaCe0.05Fe11.95O19 has been prepared by the citrate sol-gel method. The phase composition of BaCe0.05Fe11.95O19 was characterized by X-ray powder diffraction analysis (XRD). The complex permittivity and complex permeability, microwave absorption properties of the resulting powder were measured by the transmission/reflection coaxial line method in the range of 8-13 GHz. The results show that the resulting powder has a minimum reflection loss value of - 37.4 dB at 12.8 GHz with a matching thickness of 3.5 mm.  相似文献   

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