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1.
Impedance spectroscopy was used to study the electrochemical performance of pure and ion-impregnated La0.7Sr0.3MnO3 (LSM) cathodes on YSZ (Y2O3-stabilized ZrO2) electrolytes in single chamber fuel cell conditions, i.e. a mixture gas with oxygen as oxidant, methane as fuel and nitrogen as dilute gas. Measurements were taken at the furnace temperature range of 550-750 °C and the CH4/O2 ratios from 1 to 2. Polarization resistances (Rp) for pure and impregnated LSM cathodes increased obviously as the CH4/O2 ratio increased at 650-750 °C. Polarization resistances of Sm0.2Ce0.8O1.9 (SDC) impregnated LSM cathode were much smaller than the ones of pure LSM cathode under the same conditions. Overtemperatures were occurred at both cathodes due to the partial oxidation of methane.  相似文献   

2.
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   

3.
We have developed double layer-type (catalyst layer/current collecting layer) oxygen electrodes (DLE) for reversible SOFCs. As the catalyst layer (cathode for SOFC and anode for steam electrolysis) interfaced with a samaria-doped ceria [(CeO2)0.8(SmO1.5)0.2, SDC] interlayer/YSZ solid electrolyte, mixed conducting La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) and SDC particles were employed. The current collecting porous LSCF layer was formed on the catalyst layer. By controlling the SDC content, as well as the thickness and porosity of the catalyst layer, the gas diffusion rate and the conduction networks for electrons and oxide ions were optimized, resulting in a marked reduction of the overpotential. The LSCF + SDC/LSCF DLE exhibited higher performance than single-layer electrodes of LSCF + SDC or LSCF; the IR-free anode potential vs. an air reference electrode was 0.12 V (corresponding to an overpotential of 0.08 V) at 0.5 A cm−2 and 900 °C under an atmosphere of O2 (1 atm).  相似文献   

4.
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   

5.
An enhanced electrochemical performance LiCoO2 cathode was synthesized by coating with various wt.% of La2O3 to the LiCoO2 particle surfaces by a polymeric method, followed by calcination at 923 K for 4 h in air. The surface-coated materials were characterized by XRD, TGA, SEM, TEM, BET and XPS/ESCA techniques. XRD patterns of La2O3-coated LiCoO2 revealed that the coating did not affect the crystal structure, α-NaFeO2, of the cathode material compared to pristine LiCoO2. TEM images showed a compact coating layer on the surface of the core material that had an average thickness of about ∼15 nm. XPS data illustrated that the presence of two different environmental O 1s ions corresponds to the surface-coated La2O3 and core material. The electrochemical performance of the coated materials by galvanostatic cycling studies suggest that 2.0 wt.% coated La2O3 on LiCoO2 improved cycle stability (284 cycles) by a factor of ∼7 times over the pristine LiCoO2 cathode material and also demonstrated excellent cell cycle stability when charged at high voltages (4.4, 4.5 and 4.6 V). Impedance spectroscopy demonstrated that the enhanced performance of the coated materials is attributed to slower impedance growth during the charge-discharge processes. The DSC curve revealed that the exothermic peak corresponding to the release of oxygen at ∼464 K was significantly smaller for the La2O3-coated cathode material and recognized its high thermal stability.  相似文献   

6.
Nano-sized Sm0.5Sr0.5CoO3−δ (SSC) was fabricated onto the inner face of porous BaCe0.8Sm0.2O2.9 (BCS) backbone by ion impregnation technique to form a composite cathode for solid oxide fuel cells (SOFCs) with BCS, a proton conductor, as electrolyte. The electro-performance of the composite cathodes was investigated as function of fabricating conditions, and the lowest polarization resistance, about 0.21 Ω cm2 at 600 °C, was achieved with BCS backbone sintered at 1100 °C, SSC layer fired at 800 °C, and SSC loading of 55 wt.%. Impedance spectra of the composite cathodes consisted of two depressed arcs with peak frequency of 1 kHz and 30 Hz, respectively, which might correspond to the migration of proton and the dissociative adsorption and diffusion of oxygen, respectively. There was an additional arc peaking at 1 Hz in the Nyquist plots of a single cell, which should correspond to the anode reactions. With electrolyte about 70 μm in thickness, the simulated anode, cathode and bulk resistances of cells were 0.021, 0.055 and 0.68 Ω cm2 at 700 °C, relatively, and the maximum power density was 307 mW cm−2 at 700 °C.  相似文献   

7.
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   

8.
Electrochemical and thermal properties of Co3(PO4)2- and AlPO4-coated LiNi0.8Co0.2O2 cathode materials were compared. AlPO4-coated LiNi0.8Co0.2O2 cathodes exhibited an original specific capacity of 170.8 mAh g−1 and had a capacity retention (89.1% of its initial capacity) between 4.35 and 3.0 V after 60 cycles at 150 mA g−1. Co3(PO4)2-coated LiNi0.8Co0.2O2 cathodes exhibited an original specific capacity of 177.6 mAh g−1 and excellent capacity retention (91.8% of its initial capacity), which was attributed to a lithium-reactive Co3(PO4)2 coating. The Co3(PO4)2 coating material could react with LiOH and Li2CO3 impurities during annealing to form an olivine LixCoPO4 phase on the bulk surface, which minimized any side reactions with electrolytes and the dissolution of Ni4+ ions compared to the AlPO4-coated cathode. Differential scanning calorimetry results showed Co3(PO4)2-coated LiNi0.8Co0.2O2 cathode material had a much improved onset temperature of the oxygen evolution of about 218 °C, and a much lower amount of exothermic-heat release compared to the AlPO4-coated sample.  相似文献   

9.
This work considers the oxidation of ammonia (NH3) by selective catalytic oxidation (SCO) over a CuO/La2O3 composite catalyst at temperatures between 150 and 400 °C. A CuO/La2O3 composite catalyst was prepared by co-precipitation of copper nitrate and lanthanum nitrate at various molar concentrations. This study also considers how the concentration of influent NH3 (C0 = 1000 ppm), the space velocity (GHSV = 92,000 l/h), the relative humidity (RH = 12%) and the concentration of oxygen (O2 = 4%) affect the operational stability and the capacity for removing NH3. The catalysts that were characterized using FTIR, XRD, UV-Vis, BET and PSA, have shown that the catalytic behavior is related to the copper (II) oxide, while lanthanum (III) oxide may serve only to provide active sites for the reaction during a catalyzed oxidation run. The experimental results show that the extent of conversion of ammonia by SCO in the presence of the CuO/La2O3 composite catalyst was a function of the molar ratio. The ammonia was removed by oxidation in the absence of CuO/La2O3 composite catalyst, and around 93.0% NH3 reduction was achieved during catalytic oxidation over the CuO/La2O3 (8:2, molar/molar) catalyst at 400 °C with an oxygen content of 4.0%. Moreover, the effect of the reaction temperature on the removal of NH3 in the gaseous phase was also monitored at a gas hourly space velocity of under 92,000 h− 1.  相似文献   

10.
A double-layer composite electrode based on Ba0.5Sr0.5Co0.8Fe0.2O3−δ + Sm0.2Ce0.8O1.9 (BSCF + SDC) and BSCF + SDC + Ag was investigated to be a promising cathode and also anode for the electrochemical oxygen generator based on samaria doped ceria electrolyte. The Ag particles in the second layer were not only the current collector but also the improver for the oxygen adsorption at the electrode. a.c. impedance results indicated that the electrode polarization resistance, as low as 0.0058 Ω cm2 was reached at 800 °C under air. In oxygen generator cell performance test, the electrode resistance dropped to half of the value at zero current density under an applied current density of 2.34 A cm−2 at 700 °C, and on the same conditions the oxygen generator cell was continual working for more than 900 min with a Faradic efficiency of ∼100%.  相似文献   

11.
YBaCo3ZnO7 + Gd0.2Ce0.8O1.9 (GDC) composites with various GDC contents (0-70 wt.%) have been investigated as cathode materials for intermediate temperature solid oxide fuel cells (SOFC). The effect of GDC incorporation on the microstructure, electrochemical properties, and thermal expansion behavior of the YBaCo3ZnO7 + GDC composites has been studied. The composite cathodes consist of smaller particles with larger surface area compared to the pure YBaCo3ZnO7 cathode, which is beneficial for providing extended triple-phase boundary (TPB) where the oxygen reduction reaction (ORR) occurs. Among the various compositions investigated, the YBaCo3ZnO7 + GDC (50:50 wt.%) composite is found to be optimum with the lowest polarization resistance (0.28 Ω cm2 at 600 °C) compared to that of pure YBaCo3ZnO7 (0.62 Ω cm2 at 600 °C). Anode-supported single cell SOFC fabricated with the YBaCo3ZnO7 + GDC (50:50 wt.%) composite cathode also exhibits excellent performance with a maximum power density of 743 mW/cm2 at 750 °C. Additionally, the YBaCo3ZnO7 + GDC (50:50 wt.%) composite shows a low thermal expansion coefficient (TEC) of 10.7 × 10−6 °C−1, which provides good compatibility with those of standard SOFC electrolytes.  相似文献   

12.
Ba0.8Sr0.2Ti1−5x/4NbxO3 ceramics, x = 0, 0.01, 0.05, 0.10, were fabricated by conventional solid-state reaction. With increasing niobium content the ferroelectric phase transition temperature decreases linearly, and the dispersivity of the transition increases. Niobium B-site decreases transition temperature more pronounced than Sr2+ at A-site. The heterovalent substitution of Nb5+ in low content causes local defect dipole, while more substitutions introduce disorder to disturb the long-range dipole correlation. Ba0.8Sr0.2Ti1−0.5/4Nb0.1O3 ceramic shows weak ferroelectric loop at room temperature far from its transition temperature, 153 K.  相似文献   

13.
This study investigates Sm0.5Sr0.5CoO3−δ (SSC)-Ce0.8Sm0.2O1.9 (SDC) composite cathodes with a gradual change in composition from electrolyte to the cathode in an attempt to discover a potential approach applicable to solid oxide fuel cells (SOFCs). The gradual change in composition from electrolyte to cathode shows the decline in charge transfer resistance (R2) and gas phase diffusion resistance (R3). Because the value of R3 is always larger than R2 and R3 significantly dominates the total cathode polarization resistance (RP) at temperatures within the range of 750-850 °C, i.e., in this temperature range, the rate-determining step is dominated by the diffusion or dissociative adsorption of oxygen. The functionally gradient cathode with a graded interface between cathode and electrolyte reveals both a higher exchange current density (i0) and a lower activation energy for oxygen reduction reaction (ORR), which suggests that the ORR kinetics can be improved by using the configuration of a functionally gradient cathode.  相似文献   

14.
A series of Eu2+ and Ce3+ doped/co-doped Sr3Al2O5Cl2 afterglow phosphors that presented various bright colors were successfully synthesized via high temperature solid state reaction. The structure and luminescence properties of the obtained samples were characterized by X-ray powder diffraction (XRD), photoluminescence (PL) spectra and decay curves as well as the thermoluminescence (TL) glow curves. The XRD results showed that all the phase could be indexed to the orthorhombic structure with the space group P212121. After being exposed to a 254 nm or 365 nm mercury lamp, blue/yellow-orange afterglow emissions with broad bands peaking around 620 nm/435 nm, which were ascribed to the characteristic 4f65d–4f7/5d1–4f1 transitions of Eu2+/Ce3+, could be observed in phosphors of Sr3Al2O5Cl2:Eu2+/Sr3Al2O5Cl2:Ce3+, respectively. Because of the overlap spectral range between the Sr3Al2O5Cl2:Eu2+ and Sr3Al2O5Cl2:Ce3+ phosphors, the energy transfer (ET) from Ce3+ to Eu2+ occurred. The related ET process was discussed in detail. Moreover, the incorporation of Ce3+ could significantly prolong the afterglow duration of Sr3Al2O5Cl2:Eu2+ phosphor, which was due to the increase of trap concentration. Consequently, 6 h of the afterglow duration could be observed in Sr3Al2O5Cl2:1.0%Eu2+, 0.5%Ce3+ sample, exhibiting much longer than that of Sr3Al2O5Cl2: 1.0%Eu2+ (3 h). From the afterglow decay curves and the fitting results, the optimal concentration of Ce3+ for the enhanced afterglow property was experimentally determined to be 0.5%.  相似文献   

15.
The paper reports the use of La2O3 and ZrO2 co-doping as a composite sintering aid for the fabrication of Tm:Y2O3 transparent ceramics. Two groups of experiments were conducted for investigating the influences of composite sintering aids on the microstructures and the optical properties of Tm:Y2O3 transparent ceramics in contrast to single La3+ and single Zr4+ doped Tm:Y2O3. Samples with composite sintering aids could realize fine microstructures and good optical properties at relatively low sintering temperatures. Grain sizes around 10 μm and transmittances close to theoretical value at wavelength of 2 μm were achieved for the 9 at.% La3+, 3 at.% Zr4+ co-doped samples sintered at 1500-1600 °C. The influences of the composite sintering aids on the emission intensities and the phonon energies of Tm:Y2O3 ceramics were also investigated.  相似文献   

16.
The metal‐supported intermediate temperature solid oxide fuel cells with a porous nickel substrate, a nano‐structured LDC (Ce0.55La0.45O2–δ)–Ni composite anode, an LDC diffusion barrier layer, an LSGM (La0.8Sr0.2Ga0.8Mg0.2O3–δ) electrolyte, an LSCF (La0.58Sr0.4Co0.2Fe0.8O3–δ)–LSGM composite cathode interlayer and an LSCF cathode current collector are fabricated by atmospheric plasma spraying. Four different plasma spraying powers of 26, 28, 30, and 34 kW are used to fabricate the LSCF–LSGM composite cathode interlayers. Each cell with a prepared LSCF–LSGM composite cathode interlayer has been post‐heat treated at 960 °C for 2 h in air with an applied pressure of 450 g cm–2. The current‐voltage‐power and AC impedance measurements indicate that the LSCF–LSGM composite cathode interlayer formed at 28 kW plasma spraying power has the best power performance and the smallest polarization resistance at temperatures from 600 to 800 °C. The microstructure of the LSCF–LSGM composite cathode interlayer shows to be less dense and composed of smaller dense regions as the plasma spraying power decreases to 28 kW. The durability test of the cell with an optimized LSCF–LSGM composite cathode interlayer gives a degradation rate of 1.1% kh–1 at the 0.3 A cm–2 constant current density and 750 °C test temperature.  相似文献   

17.
Ramsdellite Li2Ti3O7 was first synthesized via sol-gel process with good crystallity of an average particle size of 0.175 μm. The product was thoroughly investigated as a lithium intercalation compound, and as an active anode material in asymmetric supercapacitors coupling with activated carbon as cathode. Lithium intercalation reactions were found occurring at 1.32 and 1.62 V versus Li/Li+, respectively. A reversible specific capacity of 150 mA h g−1 at 1C was obtained on Li2Ti3O7 electrode in a nonaqueous electrolyte. The charge current was found to strongly influence the anodic discharge capacity in the asymmetric cell. The capacity retention at 10C charge-discharge rate was found to be 75.9% in comparison with that at 1C.  相似文献   

18.
Composite G/PPy/PPy(La1−xSrxMnO3)/PPy electrodes made of the perovskite La1−xSrxMnO3 embedded into a polypyrrole (PPy) layer, sandwiched between two pure PPy films, electrodeposited on a graphite support were investigated for electrocatalysis of the oxygen reduction reaction (ORR). PPy and PPy(La1−xSrxMnO3) (0≤ x ≤0.4) successive layers have been obtained on polished and pretreated graphite electrodes following sequential electrodeposition technique. The electrolytes used in the electrodeposition process were Ar saturated 0.1 mol dm−3 pyrrole (Py) plus 0.05 mol dm−3 K2SO4 with and without containing a suspension of 8.33 g L−1 oxide powder. Films were characterized by XRD, SEM, linear sweep voltammetry, cyclic voltammetry (CV) and electrochemical impedance (EI) spectroscopy. Electrochemical investigations were carried out at pH 12 in a 0.5 mol dm−3 K2SO4 plus 5 mmol dm−3 KOH, under both oxygenated and deoxygenated conditions. Results indicate that the porosity of the PPy matrix is considerably enhanced in presence of oxide particles. Sr substitution is found to have little influence on the electrocatalytic activity of the composite electrode towards the ORR. However, the rate of oxygen reduction decreases with decreasing pH of the electrolyte from pH 12 to pH 6. It is noteworthy that in contrast to a non-composite electrode of the same oxide in film form, the composite electrode exhibits much better electrocatalytic activity for the ORR.  相似文献   

19.
This paper examines the important mechanical properties of commercially purchased La0.8Sr0.2Ga0.8Mg0.2O3 at room temperature and 800 °C. Sr and Mg-doped lanthanum gallates (LSGM) are strong candidates for use as solid electrolytes in lower temperature solid oxide fuel cells operating at or below 800 °C. The material was found to be phase pure with a Young's modulus value of ∼175 GPa. The four point bending strength of the LSGM samples remained almost constant from 121 ± 35 MPa at room temperature to 126 ± 20 MPa at 800 °C. The fracture toughness, as measured by the single edge V notch beam (SEVNB) method, was 1.22 ± 0.06 MPa√m at room temperature, 1.04 ± 0.09 MPa√m at 700 °C followed by a small increase 1.31 ± 0.16 MPa√m at 800 °C. We also report, for the first time, the static subcritical (or slow) crack-growth (SCG) behavior of natural cracks in LSGM performed in four point bending tests at room temperature. The exponent of a power-law representation in the SCG tests was found to be n = 15, a rather low value showing LSGM to be highly susceptible to room temperature SCG.  相似文献   

20.
The electrochemical response of infiltrated La0.5Ba0.5CoO3-δ (LBC) in porous La0.8Sr0.2Ga0.8Mg0.2O2.8 (LSGM) has been investigated. The thermal expansion coefficient (TEC) of the resulting electrode was measured, obtaining α?=?12.5?×?10?6 K?1, a value similar to that of LSGM. The polarization resistance (Rp) and the processes involved in the oxygen reduction reaction (ORR) for the new electrode were studied and analyzed through complex impedance spectroscopy measurements as a function of temperature and oxygen partial pressure (pO2), using a symmetrical cell. The value of Rp for the infiltrated LBC turned out to be lower than that measured for an electrode prepared with a composite LBC-LSGM (1:1?wt%) by an order of magnitude, for the temperature range 750?°C ≤ T?≤?900?°C, and about 5 times lower for the temperature range 450?°C≤ T?≤?650?°C. At 600?°C, the LBC infiltrated cathode exhibits a polarization resistance Rp =?0.22?Ω?cm2, in air. The complex impedance spectra show two processes, one identified as low frequency (LF),with a characteristic frequency of 10?Hz, and the other as intermediate frequency (IF), with a range between 0.05 and 2000?Hz. The LF process could be associated to the diffusion of oxygen in the gas phase through the pores of the electrode. Its resistance, RLF =?0.01?Ωc?m2, was found to be independent of the temperature and half of that obtained for the LBC composite cathode. On the other hand, the IF process is related to charge transfer at the electrode surface and the electrode-electrolyte interface. The LBC cobaltite infiltrated in the LSGM scaffolds offers an adequate thermal expansion coefficient and good electrocatalytic activity for the ORR.  相似文献   

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