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1.
This paper reports on the composition and flow rate of outlet gas and current density during the reforming of CH4 with CO2 using three different electrochemical cells: cell A, with Ni−GDC (Gd-doped ceria: Ce0.8Gd0.2O1.9) cathode/porous GDC electrolyte/Cu−GDC anode, cell B, with Cu−GDC cathode/ porous GDC electrolyte/Cu−GDC anode and cell C, with Ru−GDC cathode/ porous GDC electrolyte/ Cu−GDC anode. In the cathode, CO2 reacts with supplied electrons to form CO fuel and O2− ions (CO2+2e→CO+O2−). Too low affinity of Cu cathode to CO2 in cell B reduced the reactivity of the CO2 with electrons. The CO fuel, O2− ions and CH4 gas were transported to the anode through the porous GDC mixed conductor of O2− ions and electrons. In the anode, CH4 reacts with O2− ions to produce CO and H2 fuels (CH4+O2−→2 H2+CO+2e). The reforming efficiency at 700−800 °C was lowest in cell B and highest in cell A. The Cu anode in cells A and C worked well to oxidize CH4 with O2− ions (2Cu+O2−→Cu2O+2e, Cu2O+CH4→2Cu+CO+2H2). However, a blockage of the outlet gas occurred in all the cells at 700−800 °C. The gas flow is inhibited due to a reduction in pore size in the cermet cathode, as well as sintering and grain growth of Cu metal in the anode during the reforming.  相似文献   

2.
The poor activity of cathode materials for electrochemical reduction of oxygen in intermediate and low temperature regime (<700 °C) is a key obstacle to reduced-temperature operation of solid oxide fuel cells (SOFCs). In our previous work, the direct methane fuel cell exhibits approximately 1 W cm−2 at 650 °C in hydrogen atmosphere without any functional layers when the electrospun LSCF–GDC cathode was applied into the La2Sn2O7–Ni–GDC anode-supported cell, which is approximately two times higher performance than 0.45 W cm−2 of the cell with the conventional LSCF–GDC cathode. For detailed analysis of the fibrous cathode, the symmetrical cells with the electrospun and conventional LSCF–GDC cathode are fabricated, and then their electrochemical characteristics are measured by using electrochemical impedance spectroscopy (EIS). Each resistance contribution is determined by equivalent circuit consisting of a series resistance (Rs) and three arcs to describe the polarization resistance of the cathode. Total polarization resistance of the electrospun LSCF–GDC cathode is approximately two times lower than that of the conventional LSCF–GDC cathode at 650 °C, which is attributed to fibrous microstructures and large amount of pores in 100–200 nm. The results correspond to the difference in the cell performances obtained from our previous work.  相似文献   

3.
A series of compounds La2Mo2−xWxO9 (x = 0-2) were synthesized using a freeze-dried precursor method at relatively low temperatures (673-823 K). These materials were characterised by thermogravimetric and differential thermal analysis (TG/DTA), differential scanning calorimetric (DSC), X-ray diffraction (XRD), and transmission electron microscopy (TEM) and dilatometric measurements. Oxygen stoichiometry was evaluated by coulometric titration and thermogravimetric analysis at 873-1273 K. The ionic and electronic conductivities of these materials were analysed by impedance spectroscopy and a Hebb-Wagner ion-blocking method under moderately reducing conditions. The presence of W6+ leads to an increase of the stability range (about 10−16 Pa for La2Mo0.5W1.5O9 at 1073 K) and prevents oxygen loss and amorphisation. Within the stability range, the electronic conductivity increases gradually as the temperature increases and as the oxygen partial pressure reduces. This indicates that the electronic transport is mainly n-type as a result of the oxygen-content decreasing in the molybdate lattice. Further reduction of the oxygen partial pressure gave rise to the decomposition of La2Mo2−xWxO9, leading to the formation of new phases with molybdenum in lower oxidation states, which further enhances the electronic conductivity. The results of the coulometric titration and the thermogravimetric studies under a dry 5% H2/Ar flow suggest that tungsten doped lanthanum molybdate materials can be used as electrolyte only at low temperature and under moderate reducing conditions.  相似文献   

4.
The electrochemical properties of Sr1−xCexMnO3 (SCM, 0.1≤x≤0.4)–Gd0.2Ce0.8O2−x (GDC) composite cathodes were determined by impedance spectroscopy. The study focused on the doping effect of Ce in the composite cathodes. Single-phase perovskite was obtained for 0.1≤x≤0.3 in SCM. No reaction occurred between the Sr0.7Ce0.3MnO3 electrode and the GDC electrolyte at an operating temperature of 800 °C for 100 h. In the single phase perovskite region, lattice expansion occurred due to the reduction of Mn4+ to Mn3+ at B-sites, and this was attributed to an increase in Ce content. Ce doping enhanced the electrode performance of SCM–GDC composite cathodes, and best electrode performance was achieved for the Sr0.7Ce0.3MnO3–GDC composite cathode (0.93 Ω cm2 and 0.47 Ω cm2 at 750 °C and 800 °C, respectively). The improvement in electrode performance was attributed to increases in charge carriers induced by a shift of some Mn from +4 to +3 and to the formation of surface oxygen vacancies caused by Mn4+ to Mn3+ conversion at high temperatures.  相似文献   

5.
Gadolinia doped ceria (GDC) is an attractive electrolyte material for intermediate temperature solid oxide fuel cells (IT-SOFCs) for its high ionic conductivity at low temperature (500-700 °C). A number of different methods are currently used to prepare nano-sized doped-ceria powder. Among the others, precipitation in solution remains the best method to obtain well-dispersed particles of controlled properties. In this work, nanocrystalline Ce1−xGdxO2−δ (GDC) particles were produced by polyol microwave assisted method in very mild conditions (170 °C, 2 h, 1 atm). The as-synthesized powder showed good sinterability and ionic conductivity comparable to the ones of the corresponding nanometric commercial GDC.  相似文献   

6.
Composite cathodes based on La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) are investigated for lower operating temperature (<750 °C) applications of a solid oxide fuel cell (SOFC). To enhance a charge transfer, a bi-layer SOFC cathode is proposed, which has a LSCF–Ce0.9Gd0.1O1.95 (GDC) composite layer and a pure LSCF layer. The bi-layer cathode SOFC shows a current density of 0.65 A cm−2 at 0.8 V and 660 °C, which is higher than a LSCF–GDC composite single-layer cathode SOFC cell of 0.35 A cm−2. The charge transfer polarizations in the bi-layer cathode SOFC are 0.14 Ω cm2 and 0.35 Ω cm2 at 760 °C and 660 °C, respectively, which are lower than those in the single-layer cathode cell of 0.23 Ω cm2 and 0.66 Ω cm2. The impedances characterized with a fitting model show that the lowered charge transfer polarization in the bi-layer cathode is a dominant factor in reducing the total polarization of SOFC.  相似文献   

7.
Ceria-based materials are prospective electrolytes for low and intermediate temperature solid oxide fuel cells. In the present work, fully dense CeO2 ceramics doped with 10 mol% gadolinium (Gd0.1Ce0.9O1.95, GDC) have been prepared with a Pechini method. Characterization studies were realized with thermo-gravimetric analysis (TGA), differential thermal analysis (DTA), mass spectroscopy (MS), high temperature FT-IR (HT-FTIR) and X-ray diffraction analysis (XRD). A single-phase with a fluorite type structure was found to form at a relatively low calcination temperature of 500 °C. Dense GDC pellets having 98% of the relative density were obtained at sintering temperature of 1400 °C/6 h, which gave significantly higher total ionic conductivity of 3.4×10−2 S cm−1 at 500 °C in air. The present work showed that the Pechini method is a relatively low-temperature preparation technique to synthesize Gd0.1Ce0.9O1.95 powders that provided high sinterability and good ionic conductivity.  相似文献   

8.
The La2−xAxMo2O9−δ (A = Ca2+, Sr2+, Ba2+ and K+) series has been synthesised as nanocrystalline materials via a modification of the freeze-drying method. The resulting materials have been characterised by X-ray diffraction (XRD), thermal analysis (TG/DTA, DSC), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The high-temperature β-polymorph is stabilised for dopant content x > 0.01. The nanocrystalline powders were used to obtain dense ceramic materials with optimised microstructure and relative density >95%. The overall conductivity determined by impedance spectroscopy depends on both the ionic radius and dopant content. The conductivity decreases slightly as the dopant content increases in addition a maximum conductivity value was found for Sr2+ substitution, which show an ionic radii slightly higher than La3+ (e.g. 0.08 S cm−1 for La2Mo2O9 and 0.06 S cm−1 for La1.9Sr0.1Mo2O9−δ at 973 K). The creation of extrinsic vacancies upon substitution results in a wider stability range under reducing conditions and prevents amorphisation, although the stability is not enhanced significantly when compared to samples with higher tungsten content. These materials present high thermal expansion coefficients in the range of (13-16) × 10−6 K−1 between room temperature and 753 K and (18-20) × 10−6 K−1 above 823 K. The ionic transport numbers determined by a modified emf method remain above 0.98 under an oxygen partial pressure gradient of O2/air and decreases substantially under wet 5% H2-Ar/air when approaching to the degradation temperature above 973 K due to an increase of the electronic contribution to the overall conductivity.  相似文献   

9.
The structure and thermal properties of La0.6Sr0.4Co0.2Fe0.8O3−δ-SDC carbonate (LSCF-SDC carbonate) composite cathodes were investigated with respect to the calcination temperatures and the weight content of the samarium-doped ceria (SDC) carbonate electrolyte. The composite cathode powder has been prepared from La0.6Sr0.4Co0.2Fe0.8O3−δ and SDC carbonate powders using the high-energy ball milling technique in air at room temperature. Different powder mixtures at 30 wt%, 40 wt% and 50 wt% of SDC carbonate were calcined at 750-900 °C. The findings indicated that the structure and thermal properties of the composite cathodes were responsive to the calcination temperature and the content of SDC carbonate. The absence of any new phases as confirmed via XRD analysis demonstrated the excellent compatibility between the cathode and electrolyte materials. The particle size of the composite cathode powder was ∼0.3-0.9 μm having a surface area of 4-15 m2 g−1. SEM investigation revealed the presence of large particles in the resultant powders resulting from the increased calcination temperature. The composite cathode containing 50 wt% SDC carbonate was found to exhibit the best thermal expansion compatibility with the electrolyte.  相似文献   

10.
Gd0.1Ce0.9O1.95 and Gd0.2Ce0.8O1.9 powders were prepared through the polyol process without using any protective agent. Microstructural and physical properties of the samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry (TG) and impedance analysis methods. The results of the thermogravimetry/differential thermal analysis (TG/DTA) and XRD indicated that a single-phase fluorite structure formed at the relatively low calcination temperature of 500 °C. The XRD patterns of the samples revealed that the crystallite size of the samples increased as calcination temperatures increased. The sintering behavior and ionic conductivity of pellets prepared from gadolinia doped ceria (GDC) powders, which were calcined at 500 °C, were also investigated. The relative densities of the pellets, which were sintered at temperatures above 1300 °C, were higher than 95%. The results of the impedance spectroscopy revealed that the GDC-20 sample that was sintered at 1400 °C exhibited an ionic conductivity of 3.25×10−2 S cm−1 at 800 °C in air. This result clearly indicates that GDC powder with adequate ionic conductivity can be prepared through the polyol process at low temperatures.  相似文献   

11.
Anode-supported solid oxide fuel cells (SOFCs) comprising NiO-samarium-doped ceria (SDC) (Sm0.2Ce0.8O1.9) composite anode, thin tri-layer electrolyte, and La0.6Sr0.4Co0.8Fe0.2O3 (LSCF)-La0.9Sr0.1Ga0.8Mg0.2O3−δ (LSGM) composite cathode were fabricated. The thin tri-layer consisting of an 11-μm thick LSGM electrolyte layer and a 12-μm thick La0.4Ce0.6O1.8 (LDC) layer on each side of the LSGM was prepared by centrifugal casting and co-firing technique. The performance of the cells operated with humidified H2 as fuel and ambient air as oxidant showed a maximum power density of 1.23 W cm−2 at 800 °C. A stability test of about 100 h was carried out and some deterioration of output power was observed, while the open circuit voltage (OCV) kept unchanged. Impedance measurements showed that both the electrolyte ohmic resistance and the electrode polarization increased with time and the latter dominated the degradation.  相似文献   

12.
In this study, a ceria-based composite electrolyte was investigated for intermediate-temperature solid oxide fuel cells (SOFCs) based on SDC-25 wt.% K2CO3. Sodium carbonate co-precipitation process by which SDC powder was adopted and sound cubic fluorite structure was formed after SDC powders were sintered at 750 °C for 3 h. The crystallite size of the particle was 21 nm in diameter as calculated from data obtained through X-ray diffraction. The conductivity of the composite electrolyte proposed in this study was much higher than that of pure SDC at the comparable temperature of 550-700 °C. The transition of the ionic conductivity occurred at 650 °C. Based on this type of composite electrolyte, single cell with the electrolyte thickness of 0.3 mm were fabricated using dry pressing, with nickel oxide adopted as anode and SSC as cathode. The single cell was then tested at 550-700 °C on home-made equipment in this study, using hydrogen/air. The maximum power density and open circuit voltage (OCV) achieved 600 mW cm−2 and 1.05 V at 700 °C, respectively.  相似文献   

13.
A novel multiscale Pd-Ag catalyzed porous cathode for the magnesium-hydrogen peroxide fuel cell was prepared by electrodeposition of Pd onto Ag coated nickel foam surface from an aqueous solution of palladium chloride. The structure, morphology and composition of the electrodeposited catalyst layer were characterized using SEM, EDS and XPS analysis. Magnesium-hydrogen peroxide fuel cell tests with the Pd-Ag deposited cathode were carried out and compared with the Ag-deposited electrode. The effects of temperature, H2O2 flow rate and H2O2 concentration on cell performance were investigated, and the electrode stability test was carried out. The Pd-Ag deposited electrode showed higher catalytic activity for the reduction of hydrogen peroxide than that of the Ag-deposited Ni foam cathode, and gave much improved fuel cell performance. The magnesium-hydrogen peroxide fuel cell with nanostructured Pd-Ag coated nickel foam cathode presented a maximum power density of 140 mW cm−2, but the Mg-H2O2 fuel cell with Ag coated Ni foam cathode gave only 110 mW cm−2 under the same operation condition.  相似文献   

14.
《Ceramics International》2015,41(6):7651-7660
We describe the manufacture and electrochemical characterization of micro-tubular anode supported solid oxide fuel cells (mT-SOFC) operating at intermediate temperatures (IT) using porous gadolinium-doped ceria (GDC: Ce0.9Gd0.1O2−δ) barrier layers. Rheological studies were performed to determine the deposition conditions by dip coating of the GDC and cathode layers. Two cell configurations (anode/electrolyte/barrier layer/cathode): single-layer cathode (Ni–YSZ/YSZ/GDC/LSCF) and double-layer cathode (Ni–YSZ/YSZ/GDC/LSCF–GDC/LSCF) were fabricated (YSZ: Zr0.92Y0.16O2.08; LSCF: La0.6Sr0.4Co0.2Fe0.8O3−δ). Effect of sintering conditions and microstructure features for the GDC layer and cathode layer in cell performance was studied. Current density–voltage (j–V) curves and impedance spectroscopy measurements were performed between 650–800 °C, using wet H2 as fuel and air as oxidant. The double-cathode cells using a GDC layer sintered at 1400 °C with porosity about 50% and pores and grain sizes about 1 μm, showed the best electrochemical response, achieving maximum power densities of up to 160 mW cm−2 at 650 °C and about 700 mW cm−2 at 800 °C. In this case GDC electrical bridges between cathode and electrolyte are preserved free of insulating phases. A preliminary test under operation at 800 °C shows no degradation at least during the first 100 h. These results demonstrated that these cells could compete with standard IT-SOFC, and the presented fabrication method is applicable for industrial-scale.  相似文献   

15.
To achieve a high-energy-density lithium electrode, high-density LiFePO4/C composite cathode material for a lithium-ion battery was synthesized using self-produced high-density FePO4 as a precursor, glucose as a C source, and Li2CO3 as a Li source, in a pipe furnace under an atmosphere of 5% H2-95% N2. The structure of the synthesized material was analyzed and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical properties of the synthesized LiFePO4/carbon composite were investigated by cyclic voltammetry (CV) and the charge/discharge process. The tap-density of the synthesized LiFePO4/carbon composite powder with a carbon content of 7% reached 1.80 g m−3. The charge/discharge tests show that the cathode material has initial charge/discharge capacities of 190.5 and 167.0 mAh g−1, respectively, with a volume capacity of 300.6 mAh cm−3, at a 0.1C rate. At a rate of 5C, the LiFePO4/carbon composite shows a high discharge capacity of 98.3 mAh g−1 and a volume capacity of 176.94 mAh cm−3.  相似文献   

16.
A kind of composite cathode, La0.58Sr0.4Co0.2Fe0.8O3−δ-Ce0.8Sm0.2O2−δ (LSCF-SDC), was presented in this paper. The electrochemical performance of the cathode on the electrolyte of SDC and YSZ coated with a thin SDC (YSZ/SDC) layer was studied by electrochemical impedance spectroscopy (EIS) and cathodic polarization techniques for their potential utilization in the intermediate temperature solid oxide fuel cell (IT-SOFC). Also studied was the relationship between the electro-catalytic characteristics and the electrode microstructure. Results showed that the LSCF-SDC composite electrode performed better on the SDC electrolyte than on the electrolyte of YSZ/SDC. The polarization resistance, Rp, of the cathode on the SDC electrolyte was 0.23 Ω cm2 at 700 °C and 0.067 Ω cm2 at 750 °C, much lower than the corresponding Rp of the same cathode on the YSZ/SDC electrolyte. At 750 °C, the cathodic overpotential of the composite cathode on the SDC electrolyte was 99.7 mV at the current density of 1.0 A cm−2.  相似文献   

17.
The performance of the LaBaCuFeO5+δ-Ce0.8Sm0.2O1.9 (LBCF-SDC) composite cathodes was studied in this paper. Electrical conductivity, thermal expansion and electrochemical properties were investigated by four probing DC technique, dilatometry, AC impedance and polarization techniques, respectively. The thermal expansion coefficients of the LBCF-SDC were between (16.3 and 13.4) × 10−6 K−1 from 30 to 850 °C, which was lower value than LBCF (17.0 × 10−6 K−1). AC Impedance spectroscopy measurements of LBCF-SDC/SDC/LBCF-SDC test cell were carried out. Polarization resistance values for the LBCF-SDC10 cathode was as low as 0.097 Ω cm2 at 750 °C.  相似文献   

18.
Solid state glass electrolyte, xLi2O-(1 − x)(yB2O3-(1 − y)P2O5) glasses were prepared with wide range of composition, i.e. x = 0.35 - 0.5 and y = 0.17 - 0.67. This material system is one of the parent compositions for chemically and electrochemically stable solid-state electrolyte applicable to thin film battery. Lithium ion conductivity of Li2O-B2O3-P2O5 glasses was studied in the correlation to the structural variation of glass network by using FTIR and Raman spectroscopy. The measured ionic conductivity of the electrolyte at room temperature increased with x and y. The maximum conductivity of this glass system was 1.6 × 10−7 Ω−1 cm−1 for 0.45Li2O-0.275B2O3-0.275P2O5 at room temperature. It was shown that the addition of P2O5 reduces the tendency of devitrification and increases the maximum amount of Li2O added into glass former without devitrification. As Li2O and B2O3 contents increased, the conductivity of glass electrolyte increased due to the increase of three-coordinated [BO3] with a non-bridging oxygen (NBO).  相似文献   

19.
The mixed ionic and electronic conductors of La0.9Ca0.1Ni0.5Co0.5O3-Ce0.8Sm0.2O1.9 (LCNC-SDC) are investigated systematically for potential application as a cathode for solid oxide fuel cells based on a Ce0.8Sm0.2O1.9 (SDC) electrolyte. The electrochemical impedance spectroscopy (EIS) measurements are performed in air over the temperature range of 600-850 °C to determine the cathode polarization resistance. The exchange current densities for oxygen reduction reaction (ORR), determined from the low-field cyclic voltammetry, high-field cyclic voltammetry, and EIS data are systematically investigated. The activation energies (Ea) for ORR determined from the slope of Arrhenius plots are in the range of 102.33-150.73 kJ mol−1 for LCNC-SDC composite cathodes. The experimental results found that LCNC-SDC (70:30) composite cathode has a maximum exchange current density and a minimum polarization resistance of 0.30 Ω cm2 for 850 °C among LCNC-SDC composite cathodes.  相似文献   

20.
Several compositions of NdYb1−xGdxZr2O7 (0 ≤ x ≤ 1.0) ceramics were prepared by pressureless-sintering method at 1973 K for 10 h in air. The relative density, microstructure and electrical conductivity of NdYb1−xGdxZr2O7 ceramics were analyzed by the Archimedes method, X-ray diffraction, scanning electron microscopy and impedance plots measurements. NdYb1−xGdxZr2O7 (0 ≤ x ≤ 0.3) ceramics have a single phase of defect fluorite-type structure, and NdYb1−xGdxZr2O7 (0.7 ≤ x ≤ 1.0) ceramics exhibit a single phase of pyrochlore-type structure; however, the NdYb0.5Gd0.5Zr2O7 composition shows mixed phases of both defect fluorite-type and pyrochlore-type structures. The measured values of the grain conductivity obey the Arrhenius relation. The grain conductivity of each composition in NdYb1−xGdxZr2O7 ceramics gradually increases with increasing temperature from 673 to 1173 K. NdYb1−xGdxZr2O7 ceramics are oxide-ion conductor in the oxygen partial pressure range of 1.0 × 10−4 to 1.0 atm at all test temperature levels. The highest grain conductivity value obtained in this work is 1.79 × 10−2 S cm−1 at 1173 K for NdYb0.3Gd0.7Zr2O7 composition.  相似文献   

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