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1.
A large difference in thermal expansion coefficient of electrode and electrolyte leads to imperfect electrode/electrolyte interface and hence significant polarization losses in solid oxide fuel cells. To overcome the difficulties associated with electrode and electrode/electrolyte interface, there is need to fabricate the composite cathode. Thus the present paper deals with study of La0.6Sr0.4Co0.2Fe0.8O3−δ(LSCF)–Ce0.9Gd0.1O1.95(GDC) nanocomposite with different fractions of GDC obtained by physical mixing of combustion synthesized nanopowders. No secondary phases were observed upon sintering at 1100 °C for 2 h affirming the chemical compatibility between LSCF and GDC. The composites with relatively high GDC% have higher density as a consequence of rapid grain growth and less conductivity. The nanocomposite with 50% of GDC showed electric conductivity of 30 Scm−1 at 500 °C and low area specific resistance of 106 Ω cm2 with 10 μs relaxation time at 200 °C.  相似文献   

2.
Compressive creep tests have been performed on perovskite-type Ba0.5Sr0.5Co0.8Fe0.2O3 ? δ ceramics. The activation energy, stress exponent and inverse grain size exponent of the steady-state creep rates are evaluated at p(O2) = 0.21 ? 105 Pa and 0.01 ? 105 Pa in the stress, temperature and grain size ranges 5–20 MPa, 1078–1208 K and 2.5–17.4 µm, respectively. The results indicate that the creep rate of Ba0.5Sr0.5Co0.8Fe0.2O3 ? δ is controlled by diffusion of cations via both the oxide lattice (bulk diffusion) and along grain boundaries. The creep rate of Ba0.5Sr0.5Co0.8Fe0.2O3 ? δ increases profoundly by more than one order of magnitude at 1153–1178 K, which is tentatively linked with the onset of the hexagonal-to-cubic phase transition in this compound.  相似文献   

3.
《Solid State Ionics》2006,177(19-25):1949-1953
Partial electronic and oxide ionic conduction in LaGaO3 doped with Sr and Mg, Co for Ga site was studied with the ion blocking method. It was found that doping small amount of Co into Ga site is effective for elevating the oxide ion conductivity. However, it is seen that the partial electronic conduction monotonically increases with increasing Co amount and PO2 at p–n transition was shifted to lower value. Even at X = 0.1, the oxide ion conductivity in LSGMC is still dominant. Calculation on the theoretical leakage of electrolyte of solid oxide fuel cells suggests that the highest efficiency of the electrolyte was achieved around 100 μm in thickness for La0.8Sr0.2Ga0.8Mg0.15Co0.05O3 (LSGMC). Preparation of LSGMC film on Ni–Sm0.2Ce0.8O2 porous anode was studied with the colloidal spray method. In order to prevent the reaction between substrate and film, La doped CeO2 was used for the interlayer film. In accordance with the theoretical calculation, open circuit potential of the cell using LSGMC film electrolyte with 40 μm thickness becomes much smaller than the theoretical value. However, fairly large maximum power density (0.21 W/cm2) can be achieved at 873 K and even at 773 K, the maximum power density of the cell as high as 0.12 W/cm2 was exhibited on the SOFC using 40 μm thickness LSGMC electrolyte.  相似文献   

4.
《Solid State Ionics》2009,180(40):1672-1682
The double perovskite Sr2MgMoO6  δ (SMM) has been proposed as a potential anode material for direct hydrocarbon oxidation in solid oxide fuel cells (SOFCs). The oxygen nonstoichiometry and electrical conductivity dependence of Sr2MgMoO6  δ have been determined as a function of the oxygen partial pressure by coulometric titration and impedance spectroscopy techniques. The chemical compatibility of Sr2MgMoO6  δ with most of the typical electrolytes commonly used in SOFCs i.e. La0.8Sr0.2Ga0.8Mg0.2O3  δ (LSGM), Ce0.8Gd0.2O2  δ (CGO) and Zr0.84Y0.16O2  δ (YSZ), was investigated. Reactivity between SMM and all these electrolytes has been found above 1000 °C, although the reaction is most severe with ZrO2-based electrolytes. Area-specific polarisation resistance of the SMM/LSGM/SMM symmetrical cells indicates that the polarisation resistance increases with the firing temperature of the electrodes due to chemical interaction between LSGM and SMM layers. A CGO buffer layer between the anode and electrolyte was also used to prevent an excessive interdiffusion of ionic species between these components, resulting in better performance. Power densities of 330 and 270 mW cm 2 were reached at 800 °C for SMM/CGO/LSGM/LSCF and SMM/LSGM/LSCF electrolyte-supported cells, respectively; with 600-μm-thick LSGM electrolyte, using humidified H2 as fuel and air as oxidant. XPS and XRPD studies on SMM powders annealed in air and diluted CH4 atmospheres showed that the surface of SMM powders is mainly formed by SrMoO4 and metal carbonates.  相似文献   

5.
Mixed electron hole and oxide ion conducting perovskite-type oxides, La0.8Sr0.2(Ga0.8Mg0.2)1 ? xCrxO3 ? δ (0  x  1.0), were prepared by solid state reaction. The phase stability and the oxygen permeation properties of the oxides were examined as a function of the content of Cr. La0.8Sr0.2(Ga0.8Mg0.2)1 ? xCrxO3 ? δ has a perovskite related tetragonal phase with x = 0.1 to 0.8. The total electrical conductivity of La0.8Sr0.2(Ga0.8Mg0.2)1 ? xCrxO3 ? δ increases with increasing x. The oxygen permeation flux across the La0.8Sr0.2(Ga0.8Mg0.2)1 ? xCrxO3 ? δ membranes at higher temperatures increases with x up to x = 04. The maximum oxygen permeation flux of 1.6 × 10? 7 mol? 1 cm? 2 at 1100 °C in a oxygen activity gradient of air/10? 2 Pa is observed in La0.8Sr0.2(Ga0.8Mg0.2)0.6Cr0.4O3 ? δ. This perovskite-type oxide is stable under an oxygen partial pressure of 7 × 10? 10 Pa at 1000 °C.  相似文献   

6.
Local coordination structure around Yttrium ions in CeO2–Y2O3 binary and [(CeO2)x(ZrO2)1?x]0.8(YO1.5)0.2 (x = 0.0 ~ 1.0) ternary system has been investigated by 89Y MAS-NMR. NMR spectra are found to be consisted of multiple peaks that can be assigned to 6-, 7- and 8-oxygen coordinated Yttrium ions. Compositional dependence of the spectrum was observed and compared with the previous results for ZrO2–Y2O3 binary system. The present investigation suggested the degree of localization of the oxygen vacancy around the cation is in the order of Zr4+ > Y3+ > Ce4+. The degree of the oxygen vacancy preference for each cation was quantitatively determined for CeO2–ZrO2–Y2O3 ternary system the first time.  相似文献   

7.
《Solid State Ionics》2006,177(26-32):2513-2518
Ceria-based thin films are potential materials for use as gas-sensing layers and electrolytes in micro-solid oxide fuel cells. Since the average grain sizes of these films are on the nanocrystalline scale (< 150 nm), it is of fundamental interest whether the electrical conductivity might differ from microcrystalline ceria-based ceramics. In this study, CeO2 and Ce0.8Gd0.2O1.9−x thin films have been fabrication by spray pyrolysis and pulsed laser deposition, and the influence of the ambient average grain size on the total DC conductivity is investigated. Dense and crack-free CeO2 and Ce0.8Gd0.2O1.9−x thin films were produced that withstand annealing up to temperatures of 1100 °C. The dopant concentration and annealing temperature affect highly the grain growth kinetics of ceria-based thin films. Large concentrations of dopant exert Zener drag on grain growth and result in retarded grain growth. An increased total DC conductivity and decreased activation energy was observed when the average grain size of a CeO2 or Ce0.8Gd0.2O1.9−x thin film was decreased.  相似文献   

8.
《Solid State Ionics》2006,177(9-10):907-913
The electrode reaction of the perovskite phases Sr1−xLaxCo0.8Fe0.2O3−δ (x = 0.1 and 0.6) on Ce0.9Gd0.1O1.95 has been investigated by impedance spectroscopy in the temperature range 600  T  800 °C. Thick porous electrodes (t 20 μm) were sprayed on Ce0.9Gd0.1O1.95 and ac impedance spectra were recorded on symmetrical cells at the equilibrium. The analysis of the complex impedance diagrams clearly indicates the presence of two contributions. The low frequency one was assigned to the gas phase oxygen diffusion through the porous electrode and a finite length diffusion (Warburg) impedance was used to describe the high frequency (HF) data. The polarization resistance of the HF impedance contribution (Rw) is higher for x = 0.1 while the activation energy of Rw is higher for x = 0.6. The variations of Rw versus the La content, temperature and thickness indicate that the Warburg-type impedance contains information of both bulk oxygen diffusion and surface processes.  相似文献   

9.
The electrode reaction of porous La0.6Sr0.4Co0.8Fe0.2O3?δ films deposited onto Ce0.9Gd0.1O1.95 (CGO) was investigated by impedance spectroscopy within the temperature and oxygen partial pressure (pO2) ranges of 500  T  700 °C and 10? 4 < pO2 < 1 atm, respectively, using Ar and He as gas carriers. The electrochemical impedance spectroscopy (EIS) measurements reveal a high frequency (HF) and a low frequency (LF) regions in the Nyquist plane. The high frequency (HF) region was fitted with a Warburg-type impedance element, and the low frequency (LF) region was reproduced with a resistance in parallel to a constant phase element. Both, the slight dependence of the polarization resistance (RW) and the small variation of the apex frequency (fv) of the HF Warburg-type element, on pO2, suggest that this contribution corresponds to the oxygen diffusion in the bulk of the La0.6Sr0.4Co0.8Fe0.2O3?δ electrode material. The variation of the polarization resistance of the LF region (Rrcpe) with pO2 indicates that as T increases, the limiting step evolves from dissociative oxygen adsorption to oxygen gas diffusion in the pores of the mixed ionic/electronic conductor (MIEC) electrode.  相似文献   

10.
《Solid State Ionics》2006,177(19-25):1799-1802
Manganese-doped ceria-based oxides, Ce1−xMnxO2−δ (0.05  x  0.3) and Ce1−xyGdxMnyO2−δ˙ (0.05  x 0.2, 0.05  y  0.25) were synthesized, and crystal phase analysis by XRD and measurements of electrical properties were performed. Solubility limit of Mn in Ce1−xMnxO2−δ˙ seemed to be between 5 mol% and 10 mol% and Mn3O4 was the main by-product above the solubility limit in the case of heat treatment at 1300 °C. Judging from the oxygen partial pressure dependence of total conductivity and emf measurements, Ce1−xMnxO2−δ˙ is a single-phase mixed conductor within the composition below the solubility limit, and when the composition of Mn exceeds the solubility limit, it becomes the dual-phase mixed conductor of Ce1−xMnxO2−δ˙ and Mn3O4. The doing of Mn in gadlia-doped ceria, Ce1−xyGdxMnyO2−δ˙ (0.05  x  0.2, 0.05  y  0.25), was more difficult than that in CeO2 presumably due to the preferential reaction between Gd and Mn to give GdMnO3 to the GDC solid solution formation, and the Mn doping seems not to be so effective in preparing the mixed ionic–electronic conductor based on GDC.  相似文献   

11.
《Solid State Ionics》2006,177(19-25):1811-1817
Structural, electronic and transport properties of LFN (LaFe1−zNizO3) and LSCFN (La1−xSrxCo1−y zFeyNizO3) perovskites synthesized by a modified citric acid method were studied. Structure of the samples was characterized by X-ray studies with Rietveld method analysis. Magnetic properties and valence states of iron ions were characterized by 57Fe Moessbauer spectroscopy performed at RT, which were found to be greatly dependent on the chemical composition of the samples. Electrical conductivity was measured in the 20–800 °C temperature range and for some compositions relatively high values (exceeding 100 S cm 1) were observed in the 600–800 °C range. Chemical stability studies in relation to Ce0.8Gd0.2O1.9 electrolyte, performed for selected perovskite samples, revealed decreasing stability with increasing Ni concentration and formation of solid solutions in CGO/perovskite composites. The coefficient of thermal expansion (CTE) of LFN perovskites was found to match that of CGO electrolyte (CTE in the 10–13 · 10 6 K 1 range).  相似文献   

12.
《Solid State Ionics》2006,177(1-2):73-76
Ionic conduction in fluorite-type structure oxide ceramics Ce0.8M0.2O2−δ (M = La, Y, Gd, Sm) at temperature 400–800 °C was systematically studied under wet hydrogen/dry nitrogen atmosphere. On the sintered complex oxides as solid electrolyte, ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in the solid states proton conducting cell reactor by electrochemical methods, which directly evidenced the protonic conduction in those oxides at intermediate temperature. The rate of evolution of ammonia in Ce0.8M0.2O2−δ (M = La, Y, Gd, Sm) is up to 7.2 × 10 9, 7.5 × 10 9, 7.7 × 10 9, 8.2 × 10 9 mol s 1 cm 2, respectively.  相似文献   

13.
Ni-containing anode is currently used with many electrolytes of solid oxide fuel cells (SOFCs). However, Ni is easily oxidized and deteriorates the LaGaO3-based electrolyte. A La-doped SrTiO3 (LST, La0.2Sr0.8TiO3) is a candidate as an anode material to solve the Ni poisoning problem in LaGaO3-based SOFC. In this study, a single-phase LST and an LST-Gd0.2Ce0.8O2 ? δ (GDC) composite were tested as the possible anodes on La0.9Sr0.1Ga0.8Mg0.2O3 ? δ (LSGM) electrolyte. In order to further improve the anodic performance, Ni was impregnated into the LST-GDC composite anode. The performance was examined from 600 °C to 800 °C by measuring impedance of the electrolyte-supported, symmetric (anode/electrolyte/anode) cells. A polarization resistance (Rp) of LST-GDC anode was much reduced from that of LST anode. When Ni was impregnated into LST-GDC composite, the Rp value was further reduced to ~ 10% of the single-phase LST anode, and it was 1 Ωcm2 at 800 °C in 97% H2 + 3% H2O atmosphere. A single cell with Ni-impregnated LST-GDC as an anode, Ba0.5Sr0.5Co0.8Fe0.2O3 ? δ (BSCF) as a cathode and LSGM as an electrolyte exhibited the maximum power density of 275 mW/cm2 at 800 °C, increased from ~ 60 mW/cm2 for the cell using the LST-GDC as an anode. Thus, LST-GDC composite is promising as a component of anode.  相似文献   

14.
《Solid State Ionics》2006,177(26-32):2407-2411
Electrical conduction of Sr-doped LaP3O9 ([Sr]/{[La] + [Sr]} = 2–10 mol%) was investigated under 0.4–5 kPa of p(H2O) and 0.01–100 kPa of p(O2) or 0.3–3 kPa of p(H2) at 573–973 K. Sr-doped LaP3O9 showed apparent H/D isotope effect on conductivity regardless of the Sr-doping level under both H2O/O2 oxidizing and H2/H2O reducing conditions at investigated temperatures. Conductivities of the material were almost independent of p(O2) and p(H2O). These results demonstrated that the Sr-doped LaP3O9 exhibited protonic conduction under wide ranges of p(O2), p(H2O) and temperature. The conductivity of the Sr-doped LaP3O9 increased with increasing Sr concentration up to its solubility limit, ca. 3 mol%, while the further Sr-doping slightly degraded the conductivity. These indicate that Sr2+ substitution for La3+ leads to proton dissolution into the material and induced protonic conduction. Conductivities of the 3 mol% Sr-doped sample were 2 × 10- 6–5 × 10 4 S cm 1 at 573–973 K.  相似文献   

15.
《Solid State Ionics》2006,177(19-25):1803-1806
Defect chemistry for a mixed conductor, La0.6Sr0.4Co0.2Fe0.8O3−δ was studied. Samples were treated under controlled oxygen partial pressure, P(O2), conditions at 1273 K [10 11.1  P(O2)/atm  1], and cooled to room temperature. Oxygen nonstoichiometry and valences of transition metal ions for the treated samples were evaluated by iodometry and X-ray absorption spectroscopy, respectively. With decreasing P(O2), preferential reduction of Co3+ to Co2+ was observed, while iron preserved its higher valence above 3 under conditions studied. A dependency of its electrical conductivity on P(O2) was discussed along with a change in concentration of oxygen vacancies and mixed valences.  相似文献   

16.
《Solid State Ionics》2006,177(9-10):833-842
The phase stability, oxygen stoichiometry and expansion properties of SrCo0.8Fe0.2O3−δ (SCF) were determined by in situ neutron diffraction between 873 and 1173 K and oxygen partial pressures of 5 × 10 4 to 1 atm. At a pO2 of 1 atm, SCF adopts a cubic perovskite structure, space group Pmm, across the whole temperature range investigated. At a pO2 of 10 1 atm, a two-phase region exists below 922 K, where the cubic perovskite phase coexists with a vacancy ordered brownmillerite phase, Sr2Co1.6Fe0.4O5, space group Icmm. A pure brownmillerite phase is present at pO2 of 10 2 and 5 × 10 4 atm below 1020 K. Above 1020 K, the brownmillerite phase transforms to cubic perovskite through a two-phase region with no brownmillerite structure observed above 1064 K. Large distortion of the BO6 (B = Co, Fe) octahedra is present in the brownmillerite structure with apical bond lengths of 2.2974(4) Å and equatorial bond lengths of 1.9737(3) Å at 1021 K and a pO2 of 10 2 atm. SCF is highly oxygen deficient with a maximum oxygen stoichiometry, 3  δ, measured in this study of 2.58(2) at 873 K and a pO2 of 1 atm and a minimum of 2.33(2) at 1173 K and a pO2 of 5 × 10 4 atm. Significant differences in lattice volume and expansion behavior between the brownmillerite and cubic perovskite phases suggest potential difficulties in thermal cycling of SrCo0.8Fe0.2O3−δ membranes.  相似文献   

17.
《Solid State Ionics》2006,177(19-25):1843-1848
The electrochemical performance of La0.58Sr0.4Co0.2Fe0.8O3−δ (L58SCF), La0.9Sr1.1FeO4−δ (LS2F) and LSM (La0.65Sr0.3MnO3−δ)/LSM–YSZ (50 wt.% LSM–50 wt.% ZrO2 (8 mol% Y2O3)) cathode electrodes interfaced to a double layer Ce0.8Gd0.2O2−δ (CGO)/YSZ electrolyte was studied in the temperature range of 600 to 850 °C and under flow of 21% O2/He mixture, using impedance spectroscopy and current density–overpotential measurements. The L58SCF cathode exhibited the highest electrocatalytic activity for oxygen reduction, according to the order: LS2F/CGO/YSZ  LSM/LSM–YSZ/CGO/YSZ < L58SCF/CGO/YSZ.  相似文献   

18.
《Solid State Ionics》2006,177(26-32):2269-2273
Iron-doped Pr2Ni0.8Cu0.2O4 was studied as a new mixed electronic and oxide-ionic conductor for use as an oxygen-permeating membrane. An X-ray diffraction analysis suggested that a single phase K2NiF4-type structure was obtained in the composition range from x = 0 to 0.05 in Pr2Ni0.8  xCu0.2FexO4. It is considered that the doped Fe is partially substituted at the Ni position in Pr2NiO4. The prepared Pr2NiO4-based oxide exhibited a dominant hole conduction in the PO2 range from 1 to 10 21 atm. The electrical conductivity of Pr2Ni0.8−xCu0.2FexO4 is as high as 102 S cm 1 in the temperature range of 873–1223 K and it gradually decreased with the increasing amount of Fe substituted for Ni. The oxygen permeation rate was significantly enhanced by the Fe doping and it was found that the highest oxygen permeation rate (60 μmol min 1 cm 2) from air to He was achieved for x = 0.05 in Pr2Ni0.8  xCu0.2FexO4. Since the chemical stability of the Pr2NiO4-based oxide is high, Pr2Ni0.75Cu0.2Fe0.05O4 can be used as the oxygen-separating membrane for the partial oxidation of CH4. It was observed that the oxygen permeation rate was significantly improved by changing from He to CH4 and the observed permeation rate reached a value of 225 μmol min 1 cm 2 at 1273 K for the CH4 partial oxidation.  相似文献   

19.
Composites containing La0.8Sr0.2Cr1 ? xRuxO3 ? δ (LSCrRu) with x = 0–0.25 and Gd0.1Ce0.9O1.95 (GDC) were studied as anodes in solid oxide fuel cells (SOFCs) with La0.9Sr0.1Ga0.8Mg0.2O3 ? δ (LSGM) electrolytes. Electrode polarization resistance RP decreased during initial SOFC operation before reaching a minimum. The decrease was more rapid, and the ultimate RP value reached was generally lower, with increasing temperature and Ru content x. RP was stable at longer times except for x = 0.25 where it increased slightly. SOFCs with x = 0.18 anodes at 800 °C yielded power densities as high as 0.53 W/cm2 with an RP value, including the (La,Sr)(Co,Fe)O3–GDC cathode, of < 0.15 Ω cm2. Transmission electron microscopy revealed Ru nano-particles on LSCrRu surfaces; their size increased and their density decreased with increasing temperature. Increasing the Ru content increased the density of Ru surface particles at a given time and temperature. Measured early-stage Ru surface coverage values were consistent with a model where Ru supply to the LSCrRu surface was limited by Ru bulk out-diffusion, but the coverage saturated at longer times. There was surprisingly little Ru particle coarsening over times up to 1000 h at 800 °C, with Ru particles sizes remaining < 10 nm. The cell RP values generally decreased with increasing Ru nano-particle surface area.  相似文献   

20.
Ke Li  Changyu Shen 《Optik》2012,123(7):621-623
Nano-YAG:Ce3+ and YAG:Ce3+,Gd3+ phosphors were synthesized by glycothermal method. The X-ray diffraction (XRD) measurements showed that the samples can be well-crystallized at 600 °C. The transition electron microscope (TEM) showed that the particles have sizes mostly in the range between 35 and 100 nm. The YAG:Ce nano-phosphor had a wide emission band ranging from blue to yellow peaking at 532 nm, due to the transition from the lowest 5d band to 2F7/2, 2F5/2 states of the Ce3+ ion. Red-shift of emission peak wavelength from 532 nm to 568 nm has been achieved as doping Gd3+ ions into the YAG:Ce3+ to substitute some Y3+ ions. White LEDs were fabricated by combining GaN (460 nm) chip with the YAG:Ce3+ and YAG:Ce3+,Gd3+. Color rendering index of the white LED as a function of the ratios of theses two kinds of phosphors was studied. As the ratio of YAG:Ce3+,Gd3+ phosphor increased, the color rendering index of the LED improved significantly under the forward bias of 20 mA. As the ratio of YAG:Ce3+ and YAG:Ce3+,Gd3+ was 11:9, the white LED had a color rendering index, CIE chromaticity coordinates and color temperature Tc of 85, (0.3116, 0.3202) and 6564 K, respectively.  相似文献   

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