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1.
Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) perovskite was synthesized by the sol–gel process based on EDTA–citrate (EC) complexing method, nitric acid modified EC route (NEC) and nitric acid aided EDTA–citrate combustion process (NECC). A crystallite size of 27, 38 and 42 nm, respectively, was observed for the powders of NECC-BSCF, NEC-BSCF and EC-BSCF calcined at 1000 °C, suggesting the suppression effect of nitric acid on the crystallite size growth of BSCF. The smaller crystallite size of the powders resulted in the higher degree of sintering of the cathode. Oxygen permeation study of the corresponding membranes demonstrated that in the powder synthesis, nitric acid also had a noticeable detrimental effect on the oxygen surface exchange kinetics and on the oxygen bulk diffusion rate of the BSCF oxides. The effect of powder synthesis route on the bulk properties of the oxide was validated by the oxygen temperature-programmed desorption technique. On the whole, a decreasing cathode performance in the sequence of EC-BSCF, NEC-BSCF and NECC-BSCF was observed. A peak power density of 693 mW cm−2 was achieved for an anode-supported cell with an EC-BSCF cathode at 600 °C, which was significantly higher than that with an NEC-BSCF cathode (571 mW cm−2) or an NECC-BSCF cathode (543 mW cm−2) under similar operation conditions.  相似文献   

2.
A novel Ba0.5Sr0.5Co0.8Fe0.2O3 − δ + LaCoO3 (BSCF + LC) composite oxide was investigated for the potential application as a cathode for intermediate-temperature solid-oxide fuel cells based on a Sm0.2Ce0.8O1.9 (SDC) electrolyte. The LC oxide was added to BSCF cathode in order to improve its electrical conductivity. X-ray diffraction examination demonstrated that the solid-state reaction between LC and BSCF phases occurred at temperatures above 950 °C and formed the final product with the composition: La0.316Ba0.342Sr0.342Co0.863Fe0.137O3 − δ at 1100 °C. The inter-diffusion between BSCF and LC was identified by the environmental scanning electron microscopy and energy dispersive X-ray examination. The electrical conductivity of the BSCF + LC composite oxide increased with increasing calcination temperature, and reached a maximum value of ∼300 S cm−1 at a calcination temperature of 1050 °C, while the electrical conductivity of the pure BSCF was only ∼40 S cm−1. The improved conductivity resulted in attractive cathode performance. An area-specific resistance as low as 0.21 Ω cm2 was achieved at 600 °C for the BSCF (70 vol.%) + LC (30 vol.%) composite cathode calcined at 950 °C for 5 h. Peak power densities as high as ∼700 mW cm−2 at 650 °C and ∼525 mW cm−2 at 600 °C were reached for the thin-film fuel cells with the optimized cathode composition and calcination temperatures.  相似文献   

3.
In this study, dense La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) electrodes decorated with the novel hetero-structured ceramic oxide mixture in four different ratios of Ce0.8Gd0.2O2-δ (GDC) and La2Mo2O9 (LMO). The time-dependent conductivity transients were acquire using electrical conductivity relaxation (ECR) technique at a chosen conditions of temperature in the range of 650–850 °C and instantaneous pO2 step change between 0.2 and 0.8. Fitting of time-dependent conductivity to the appropriate non-equilibrium solutions of Fick's diffusion equation has yielded the chemical diffusion coefficient, Dchem, and oxygen surface exchange coefficient, kchem. As expected, the Dchem of the coated samples remained invariant, whilst the kchem is found to vary with the change in GDC-LMO coating mixture ratio. Substantial increase of a factor of 10 in the surface exchange coefficient is noticed for the LSCF coated with a 1:0.75 mixing ratio as compared to bare sample at 850 °C. The enhancement in kchem is attributed to the optimal triple-phase boundary (TPB) regions which promotes oxygen surface exchange kinetics. Thus, coating of selective ratio of hetero-structured oxide in a form of nano-particulate layer over the LSCF surface is considered to be a promising candidate for solid oxide fuel cell (SOFC) cathode.  相似文献   

4.
Sm0.5Sr0.5CoO3 (SSC)-Sm0.2Ce0.8O1.9 (SDC) core-shell composite cathodes are synthesized via a polymerizable complex method, and the durability of a cell incorporating the cathodes is examined. Nanocrystalline SSC powders have been coated onto the surfaces of SDC cores to enable the formation of a rigid backbone structure, over which the catalyst phase is effectively dispersed. A symmetrical SSC-SDC |SDC| SSC-SDC half-cell exhibits a polarization resistance of 0.098 Ω cm2 at 650 °C. The durability and microstructure of the cathode are investigated by electrochemical impedance spectroscopy and thermo-cycle tests at temperatures in the range of 100 °C-650 °C. After 30 cycles, the polarization resistance is found to increase by 9.04 × 10−2 Ω cm2, a 3.56% rise with respect to the initial resistance. Coarsening of the SSC catalyst phase has been prevented with the use of core-shell type powders, as confirmed by a nearly constant low frequency polarization resistance and a microstructural analysis. The performance of a unit cell comprised of the core-shell type cathode exhibits 1.07 W cm−2 at 600 °C and 0.62 W cm−2 at 550 °C.  相似文献   

5.
Ba0.5Sr0.5Co0.8Fe0.2O3 perovskite oxide has been synthesized by a sol–gel method, and characterized by XRD, SEM, BET. This oxide has a porous structure and a specific surface area of 2.78 m2 g−1. The catalytic activity of the oxide for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in 0.1 M KOH solution has been studied by using a rotating ring-disk electrode (RRDE) technique. RRDE results show that the ORR mainly favors a direct four electron pathway, and a maximum cathodic current density of 6.25 mA cm−2 at 2500 rpm was obtained, which is close to the behavior of Pt/C (20 wt% Pt on carbon) electrocatalyst in the same testing conditions. Compared with pure C electrode, BSCF is more active for OER, a lower onset potential for OER and a bigger anodic current at the same applied potential are observed.  相似文献   

6.
Ba0.5Sr0.5Co0.6Fe0.4O3−δ(BSCF5564) was synthesized by nitric acid aided EDTA–citric acid complexing sol-gel method (NECC). Both, the phase formation temperature and time of BSCF5564 synthesized NECC were found to be low i.e. single perovskite phase formation temperature is 200 °C less as compared to the conventional method of synthesis. The orthorhombic perovskite structure has been formed after calcination at 800 °C for 5 h. Scanning electron microscopy reveals the formation of porous material constituting nano-sized and irregularly shaped rod-like structure with particle size approximately ranges from 90 to 160 nm. The total weight loss of the BSCF5564 sample comes out to be 6.6%, indicating that quadrivalence state Co4+ and Fe4+ in the sample have been completely reduced to the trivalent state Co3+ and Fe3+ due to thermal analysis. The value of Ea for BSCF5564 prepared by NECC was 0.2288 eV. The electrical conductivity of BSCF5564 synthesized by NECC is observed to be steady at high temperature (above 700 °C).  相似文献   

7.
The Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) cathode for solid oxide fuel cell has been prepared by glycine–nitrate combustion process. Crystal structure and chemical state of BSCF have been studied by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). XRD pattern indicates that a single cubic perovskite phase of BSCF oxide is successfully obtained after calcination at 850 °C for 2 h. XPS results show there exists a little amount of SrCO3 in the surface of BSCF. Co2p spectra indicate that some Co3+ ions have changed into Co4+ ions to maintain the electrical neutrality. O1s spectra present that adsorbed oxygen species appear in the surface BSCF oxide.  相似文献   

8.
A stable, easily sintered perovskite oxide BaCe0.5Zr0.3Y0.16Zn0.04O3−δ (BCZYZn) as an electrolyte for protonic ceramic membrane fuel cells (PCMFCs) with Ba0.5Sr0.5Zn0.2Fe0.8O3−δ (BSZF) perovskite cathode was investigated. The BCZYZn perovskite electrolyte synthesized by a modified Pechini method exhibited higher sinterability and reached 97.4% relative density at 1200 °C for 5 h in air, which is about 200 °C lower than that without Zn dopant. By fabricating thin membrane BCZYZn electrolyte (about 30 μm in thickness) on NiO–BCZYZn anode support, PCMFCs were assembled and tested by selecting stable BSZF perovskite cathode. An open-circuit potential of 1.00 V, a maximum power density of 236 mW cm−2, and a low polarization resistance of the electrodes of 0.17 Ω cm2 were achieved at 700 °C. This investigation indicated that proton conducting electrolyte BCZYZn with BSZF perovskite cathode is a promising material system for the next generation solid oxide fuel cells.  相似文献   

9.
Ba1−xSrxCo0.8Fe0.2O3−δ (BSCF)(0 ≤ x ≤ 1) composite oxides were prepared and tested as cathodes for low-temperature solid oxide fuel cells (SOFCs) both in the absence and presence of CO2. It is found that the BSCF cathodes in the whole range of strontium doping levels show promising performance at 500–600 °C in the absence of CO2, among which the SrCo0.8Fe0.2O3−δ (SCF) cathode gives the highest power density while BaCo0.8Fe0.2O3−δ (BCF) cathode shows the lowest performance. The impedance analysis reveals that both the ohmic resistance and polarization resistance of the fuel cell increases when the strontium content decreases. It is believed that the microstructure and electrical conductivity simultaneously affect the process of oxygen reduction. The presence of CO2 deteriorates the BSCF performance by adsorbing on the cathode surface and thus obstructing the oxygen surface exchange reaction. The CO2 exerts a more intense influence on BSCF with higher barium content.  相似文献   

10.
Silver-modified Ba0.5Sr0.5Co0.8Fe0.2O3−δ (Ag/BSCF) electrodes were prepared using an electroless deposition technique. The morphology, microstructure and oxygen reduction reaction activity of the resulted Ag/BSCF electrodes were comparatively studied using Fourier transform infrared spectra, environmental scanning electron microscopy, temperature-programmed oxygen desorption, X-ray diffraction, and electrochemical impedance spectroscopy. An area-specific resistance as low as 0.038 Ω cm2 was achieved for N2H4-reduced Ag/BSCF cathode at 600 °C. Carbonates were detected over the BSCF surface during the reduction of silver, which deteriorated both the charge-transfer process and diffusion process of HCHO-reduced Ag/BSCF cathode for the oxygen electrochemical reduction reaction. An anode-supported single cell with an N2H4-reduced Ag/BSCF cathode showed a peak power of 826 mW cm−2 at 600 °C. In comparison, only 672 mW cm−2 was observed with the HCHO-reduced Ag/BSCF cathode.  相似文献   

11.
The effects of the current collection material and method on the performance of SOFCs with Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) cathodes are investigated. Ag paste and LaCoO3 (LC) oxide are studied as current collection materials, and five different current collecting techniques are attempted. Cell performances are evaluated using a current-voltage test and electrochemical impedance spectra (EIS) based on two types of anode-supported fuel cells, i.e., NiO + SDC|SDC|BSCF and NiO + YSZ|YSZ|SDC|BSCF. The cell with diluted Ag paste as the current collector exhibits the highest peak power density, nearly 16 times that of a similar cell without current collector. The electrochemical characteristics of the BSCF cathode with different current collectors are further determined by EIS at 600 °C using symmetrical cells. The cell with diluted Ag paste as the current collector displays the lowest ohmic resistance (1.4 Ω cm2) and polarization resistance (0.1 Ω cm2). Meanwhile, the surface conductivities of various current collectors are measured by a four-probe DC conductivity technique. The surface conductivity of diluted Ag paste is 2-3 orders of magnitude higher than that of LC or BSCF. The outstanding surface conductivity of silver may reduce the contact resistance at the current collector/electrode interface and, thus, contributes to better electrode performance.  相似文献   

12.
Co is doped to Sr2Fe1.5Mo0.5O6 to enhance its electrochemical activity as the cathode for intermediate-temperature solid oxide fuel cells. Pure cubic perovskites of Sr2Fe1.5−xCoxMo0.5O6 (SF1.5−xCxM, x = 0, 0.5, 1) are synthesized using a glycine-nitrate combustion progress. The average thermal expansion coefficient varies from 15.8 to 19.8 × 10−6 K−1. The electrical conductivity increases while its activation energy decreases with increasing Co content. X-ray photoelectron spectroscopy analysis demonstrates mixed valences of Fe, Co and Mo, suggesting small polaron hopping mechanism. Electrical conductivity relaxation (ECR) measurement shows that the surface exchange coefficient increases about two orders of magnitude when the content increases from x = 0 to x = 1.0, i.e. from 2.55 × 10−5 to 2.20 × 10−3 cm s−1 at 750 °C. ECR also exhibits that chemical diffusion coefficient increases with Co content. Density Functional Theory calculation demonstrates that oxygen vacancy formation energy decreases with Co content, suggesting high oxygen vacancy concentration at high Co content. Impedance spectroscopy on symmetric cells consisting of SF1.5−xCxM electrodes and La0.8Sr0.2Ga0.8Mg0.2O3−δ electrolytes shows that Co doping is very effective in reducing the interfacial polarization resistance, from 0.105 Ω cm2 to 0.056 Ω cm2 at 750 °C. These results suggest that Co doping into Sr2Fe1.5Mo0.5O6 can substantially improve its electrochemical performance.  相似文献   

13.
This study presents the electrochemical performance of (Ba0.5Sr0.5)0.9Sm0.1Co0.8Fe0.2O3−δ (BSSCF) as a cathode material for intermediate temperature solid oxide fuel cells (IT-SOFC). AC-impedance analyses were carried on an electrolyte supported BSSCF/Sm0.2Ce0.8O1.9 (SDC)/Ag half-cell and a Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF)/SDC/Ag half-cell. In contrast to the BSCF cathode half-cell, the total resistance of the BSSCF cathode half-cell was lower, e.g., at 550 °C; the values for the BSSCF and BSCF were 1.54 and 2.33 Ω cm2, respectively. The cell performance measurements were conducted on a Ni-SDC anode supported single cell using a SDC thin film as electrolyte, and BSSCF layer as cathode. The maximum power densities were 681 mW cm−2 at 600 °C and 820 mW cm−2 at 650 °C.  相似文献   

14.
The optimization of electrodes for solid oxide fuel cells (SOFCs) has been achieved via a wet impregnation method. Pure La0.75Sr0.25Cr0.5Mn0.5O3−δ (LSCrM) anodes are modified using Ni(NO3)2 and/or Ce(NO3)3/(Sm,Ce)(NO3)x solution. Several yttria-stabilized zirconia (YSZ) electrolyte-supported fuel cells are tested to clarify the contribution of Ni and/or CeO2 to the cell performance. For the cell using pure-LSCrM anodes, the maximum power density (Pmax) at 850 °C is 198 mW cm−2 when dry H2 and air are used as the fuel and oxidant, respectively. When H2 is changed to CH4, the value of Pmax is 32 mW cm−2. After 8.9 wt.% Ni and 5.8 wt.% CeO2 are introduced into the LSCrM anode, the cell exhibits increased values of Pmax 432, 681, 948 and 1135 mW cm−2 at 700, 750, 800 and 850 °C, respectively, with dry H2 as fuel and air as oxidant. When O2 at 50 mL min−1 is used as the oxidant, the value of Pmax increases to 1450 mW cm−2 at 850 °C. When dry CH4 is used as fuel and air as oxidant, the values of Pmax reach 95, 197, 421 and 645 mW cm−2 at 750, 800, 850 and 900 °C, respectively. The introduction of Ni greatly improves the performance of the LSCrM anode but does not cause any carbon deposit.  相似文献   

15.
The role of porosity on the equilibration kinetics in electrical conductivity relaxation (ECR) experiments is highlighted. Both porous and dense conductivity bars are used to determine the chemical oxygen surface exchange coefficient (kchem) of neodymium nickelate Nd2NiO4+δ (NNO) from 600 to 800 °C. Using porous bars allows for quicker ECR experiments during which the conductivity transient is rate limited only by oxygen surface exchange which enables the use of a simple transient model. Additionally, porous bars have similar microstructures to porous electrodes which means they are critical for determining the oxygen exchange kinetics of realistic electrodes. ECR results on dense bars with porous coatings are also presented. The conductivity transients of dense and porous bars both show similar trends with oxygen partial pressure. Additionally, both porous and dense bars show a difference between oxidation and reduction transients with oxidation transients being faster than reduction transients.  相似文献   

16.
The influence of chromium poisoning on the long-term stability of the oxygen exchange kinetics of the promising IT-SOFC cathode materials La0.6Sr0.4CoO3−δ (LSC) and Nd2NiO4+δ (NDN) is investigated in-situ by dc-conductivity relaxation experiments. The as-prepared LSC and NDN samples show high chemical oxygen surface exchange coefficients kchem. After the deposition of a 10 nm thick Cr-layer onto the surface, kchem of LSC decreases to 50% of the initial value. Additional chromium deposition of 20 nm on LSC leads to a further decrease of kchem to 27% of the initial value. In contrast, the effect of a 10 nm thick Cr-layer on kchem of NDN is negligible. Even with additional 20 nm of chromium and a total testing time of 1750 h, the nickelate retains a kchem of 60% of the initial value. X-ray photoelectron spectroscopy (XPS) of the degraded. LSC shows a significantly altered surface cation composition with Sr-enrichment down to 30 nm depth while XPS analysis of the degraded NDN reveals a thin surface zone of approximately 30 nm containing nickel and chromium. In contrast to LSC, the changes in the surface composition of NDN due to Cr-poisoning ultimately had only a minor influence on the surface exchange properties.  相似文献   

17.
Metal oxide compounds containing bismuth are considered as potential candidates for photocatalysis in both contaminant degradation and H2 generation, due to the interesting lone electron pairs and the band gap narrowing effect of Bi3+. Quaternary perovskite oxide Bi0.5Na0.5TiO3 was thus synthesized at low temperature via a soft chemical route. The influence of alkaline concentrations on the structure, morphology, and optical properties of the samples has been systematically investigated. All samples existed as hierarchical microspheres, which are consisted of cubic nanocrystallines. For the first time, the photocatalytic water splitting for H2 evolution over Bi0.5Na0.5TiO3 has been studied. A high H2 evolution rate of 325.4 μmol h−1 g cat−1 under the irradiation of a 500 W xenon lamp was obtained. More importantly, no decrease in the catalytic performance was observed after three consecutive runs of 15 h, suggesting new possibility in designing multi-component photocatalysts for future applications.  相似文献   

18.
Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) was synthesized successfully by a novel citric acid–nitrate combustion method and employed as the anode of solid oxide electrolysis cells (SOEC) for hydrogen production for the first time in this paper. The crystal structure, chemical composition and electrochemical properties of BSCF were investigated in detail. The results showed that BSCF is in good stoichiometry of Ba0.5Sr0.5Co0.8Fe0.2O3−σ formation. ASR of BSCF/YSZ is only 0.077 Ω cm2 at 850 °C, remarkably lower than the commonly used oxygen materials LSM as well as the current focus materials LSC and LSCF. Also, BSCF electrode exhibited much better performance than LSM under both SOEC and SOFC operating modes. The hydrogen production rate of BSCF/YSZ/Ni-YSZ can be up to 147.2 mL cm−2 h−1, about three times higher than that of LSM/YSZ/Ni-YSZ, which indicates that BSCF could be a very promising candidate for the practical application of SOEC technology.  相似文献   

19.
Series of Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) samples have been prepared by modified citrate-nitrate combustion method from the precursor solutions with different pH values and citrate/metal ion ratios. The XRD results reveal that BSCF oxide free of impurity phases can be obtained from a precursor solution with a suitable pH value and a suitable C/M value, whereas CO2-TPD profiles show that there are minor carbonates species present in all BSCF samples, but the amount of these carbonates varies with the pH and C/M values of precursor solutions. The current density–voltage characteristics indicate that carbonates in the BSCF samples reduce the cell performance. The electrochemical impedance spectra (EIS) show that carbonates in BSCF lead to increases in ohmic and polarization resistances. High performance is achieved on the cell with a cathode using a pure BSCF calcined under O2 flow at 900 °C.  相似文献   

20.
A novel Ir0.5Mn0.5O2 cathode has been synthesized by thermal decomposition of mixed H2IrCl6 and Mn(NO3)2 water solution. The Ir0.5Mn0.5O2 cathode has been characterized by XRD, field emission SEM (FESEM) and AC impedance spectroscopy. XRD result shows that rutile-structured Ir0.5Mn0.5O2 phase is formed by thermal decomposition of mixed H2IrCl6 and Mn(NO3)2 water solution. FESEM micrographs show that a porous structure with well-necked particles forms in the cathode after sintering at 1000 °C. The average grain size is between 20 and 30 nm. Two depressed arcs appear in the medium-frequency and low-frequency region, indicating that there are at least two different processes in the cathode reaction: charge transfer and molecular oxygen dissociation followed by surface diffusion. The minimum area specific resistance (ASR) is 0.67 Ω cm2 at 800 °C. The activation energy for the total oxygen reduction reaction is 93.7 kJ mol−1. The maximum power densities of the Ir0.5Mn0.5O2/LSGM/Pt cell are 43.2 and 80.7 mW cm−2 at 600 and 700 °C, respectively.  相似文献   

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