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1.
Full conductivity, diffusion and oxygen exchange processes in composites (100 − x)La0.8Sr0.2Fe0.7Ni0.3O3 − δxCe0.9Gd0.1O1.95 (x is the volume fraction, 0 ≤ x ≤ 71.1%) at 700°C over the oxygen partial pressure range from 0.2 to 3 × 10−3 atm are studied by the electrical conductivity relaxation method. The composites’ conductivity was shown to decrease monotonically with the increasing of Ce0.9Gd0.1O1.95 fraction, while the oxygen chemical diffusion coefficient increased. The oxygen exchange constant is higher for the composites than for the individual phases of La0.8Sr0.2Fe0.7Ni0.3O3 − δ and Ce0.9Gd0.1O1.95. Possible reason of the dependence of the parameters D chem and k chem on the temperature, oxygen pressure, and the composite composition is the effect of the interface on the oxygen transfer processes. Most effective oxygen transfer occurs in the composites whose composition approaches La0.8Sr0.2Fe0.7Ni0.3O3 − δ-Ce0.9Gd0.1O1.95 (x = 71%).  相似文献   

2.
The solid electrolytes, BaCe_(0.8) Ln_(0.2)O_(2.9) (Ln: Gd, Sm, Eu), were prepared by the sol-gel method. XRD indicated that a pure orthorhombic phase was formed at 900℃. The synthesis temperature by the sol-gel method was about 600℃ lower than the high temperature solid phase reaction method, The electrical conductivity and impedance spectra were measured and the conduction mechanism was studied. The grain-boundary resistance of the solid electrolyte could be reduced or eliminated by the sol-gel method. The conductivity of BaCe_(0.8)Gd_(0.2)O_(2.9) is 7.87×10~(-2) S·cm~(-1) at 800℃. The open-circuit voltage of hydrogen-oxygen fuel cell using BaCe_(0.8) Gd_(0.2)O_(2.9) as electrolyte was near to 1 V and its maximum power density was 30 mW·cm~(-2).  相似文献   

3.
The oxidation-reduction behaviour of transition metal and rare earth oxide systems in oxygen potential controlled atmospheres was investigated by means of a solid electrolyte-based coulometric technique (SEC) in carrier gas mode to obtain information concerning the extent of oxygen stoichiometry, thep-T-x diagram of any mixed oxide phase, the kinetics of the oxygen exchange and the phase transitions.The direct coupling of SEC and electrical conductivity measurements provides further information about the relationship between oxygen deficiency and conductivity, especially as concerns the oxygen mobility and the transition from ionic to mixed ionic/electronic conductivity in any system.In the fluorite-type phases PrO2–x, Ce0.8Pr0.2Oy–x and Ce0.8Sr0.08Pr0.12Oy–x, the higher oxidation state of Pr is stabilized and the electrical conductivity increases in this sequence. The perovskite-type phase Sr1–yCeyFeO3–x, shows transitions and a second phase reflected in the temperature-programmed spectrum of this substance. The electrical conductivity of Sr0.9Ce0.1FeO3–x changes fromn-type top-type with increasing oxygen pressure.  相似文献   

4.
Ba1.03Ce0.8Tm0.2O3?α ceramic with orthorhombic perovskite structure was prepared by conventional solid‐state reaction. The conductivity and ionic transport number of Ba1.03Ce0.8Tm0.2O3?α were measured by ac impedance spectroscopy and gas concentration cell methods in the temperature range of 500–900°C in wet hydrogen and wet air. Using the ceramic as solid electrolyte and porous platinum as electrodes, the hydrogen‐air fuel cell was constructed, and the cell performance was examined at 500–900°C. The results indicate that the specimen is a pure ionic conductor with the ionic transport number of 1 at 500–900°C in wet hydrogen. In wet air, the specimen is a mixed conductor of proton, oxide ion and electron hole. The protonic transport numbers are 0.071–0.018, and the oxide ionic transport numbers are 0.273–0.365. The conductivities of Ba1.03Ce0.8Tm0.2O3?α under wet hydrogen, wet air or fuel cell atmosphere are higher than those of Ba1.03Ce0.8RE0.2O3?α (RE?Y, Eu, Ho) reported previously by us. The fuel cell can work stably. At 900°C, the maximum power output density is 122.7 mW·cm?2, which is higher than that of our previous cell using Ba1.03Ce0.8RE0.2O3?α (RE?Y, Eu, Ho) as electrolyte.  相似文献   

5.
We propose a new way to develop high-performance cathodes for IT-SOFCs by utilizing the interfacial reactions. SrCoOx was selected as the starting electrode material, which took a vacancy-ordered 2H BaNiO3-type structure and showed negligible ionic conductivity and low electrical conductivity. Phase reactions between SrCoOx and Sm0.2Ce0.8O1.9 happened at 900 °C or higher, resulting in the incorporation of Sm and Ce into its lattice structure. This promoted the phase transition to a cubic perovskite and led to substantial increase in the electrical conductivity and oxygen mobility of the electrode. By utilizing such phase reactions, the SrCoOx + Sm0.2Ce0.8O1.9 composite was developed into a high performance electrode with a low area specific resistance of 0.08 Ω cm?2 at 650 °C. An anode-supported cell with such electrode delivered a peak power density of 795 mW cm?2 at 600 °C.  相似文献   

6.
CeO2-based solid solutions with a fluorite structure are promising materials as electrolytes of medium-temperature electrochemical devices. This work presents the results of systematic studies of structural and electric properties and oxygen nonstoichiometry of the Ce0.8(Sm1 − x Ca x )0.2O2 − δ system in a wide range of concentrations of 0 < x < 1 performed in order to establish the causes affecting the system conductivity and its behavior in a reducing medium. It is found that a single-phase solid solution of the fluorite type is formed in the whole concentration range. Parameters of its lattice cells decrease linearly at an increase in the concentration of Ca2+. Conductivity in air grows when calcium is added due to a decrease in the grain boundary resistance. The maximum conductivity in air was obtained for the composition of Ce0.8(Sm0.8Ca0.2)0.2O2 − δ and is 13.71 × 10−3 S/cm at 873 K. Studies of the dependence of conductivity of the partial pressure of oxygen showed that electron conductivity is observed at a higher oxygen partial pressure at an increase in the temperature and calcium concentration. The critical partial pressure of oxygen ( pO2 * )\left( {p_{O_2 }^* } \right) for the compositions of Ce0.8(Sm1 − x Ca x )0.2O2 − δ with x = 0; 0.2, and 0.5 is 1.83 × 10−16, 1.73 × 10−13, and 3.63 × 10−13 atm at 1173 K, respectively, and 2.76 × 10−21, 5.05 × 10−18, and 1.31 × 10−18 atm at 1023 K.  相似文献   

7.
Development of high performance cathodes with low polarization resistance is critical to the success of solid oxide fuel cell (SOFC) development and commercialization. In this paper, (La0.8Sr0.2)0.9MnO3 (LSM)–Gd0.2Ce0.8O1.9(GDC) composite powder (LSM ~70 wt%, GDC ~30 wt%) was prepared through modification of LSM powder by Gd0.2Ce0.8(NO3) x solution impregnation, followed by calcination. The electrode polarization resistance of the LSM–GDC cathode prepared from the composite powder was ~0.60 Ω cm2 at 750 °C, which is ~13 times lower than that of pure LSM cathode (~8.19 Ω cm2 at 750 °C) on YSZ electrolyte substrates. The electrode polarization resistance of the LSM–GDC composite cathode at 700 °C under 500 mA/cm2 was ~0.42 Ω cm2, which is close to that of pure LSM cathode at 850 °C. Gd0.2Ce0.8(NO3) x solution impregnation modification not only inhibits the growth of LSM grains during sintering but also increases the triple-phase-boundary (TPB) area through introducing ionic conducting phase (Gd,Ce)O2-δ, leading to the significant reduction of electrode polarization resistance of LSM cathode.  相似文献   

8.
Ba0.95Ce0.8Ho0.2O3-a was prepared by high temperature solid-state reaction. X-ray diffraction (XRD) pattern showed that the material was of a single perovskite-type orthorhombic phase. Using the material as solid electrolyte and porous platinum as electrodes, the measurements of ionic transport number and conductivity of Ba0.95Ce0.8Ho0.2O3-a were performed by gas concentration cell and ac impedance spectroscopy methods in the temperature range of 600---1000 ℃in wet hydrogen, dry and wet air respectively. Ionic conduction of the material was investigated and compared with that of BaCe0.8Ho0.2O3-a. The results indicated that Ba0.95Ce0.8Ho0.2O3-a was a pure protonic conductor with the protonic transport number of 1 during 600---700℃ in wet hydrogen, a mixed conductor of protons and electrons with the protonic transport number of 0.97--0.93 in 800---1000 ℃. But BaCe0.8Ho0.2O3-a was almost a pure protonic conductor with the protonic transport number of 1 in 600---900 ℃ and 0.99 at 1000 ℃ in wet hydrogen. In dry air and in the temperature range of 600---1000 ℃, they were both mixed conductors of oxide ions and electronic holes, and the oxide-ionic transport numbers were 0.24--0.33 and 0.17--0.30 respectively. In wet air and in the temperature range of 600---1000 ℃, they were both mixed conductors of protons, oxide ions and electronic holes, the protonic transport numbers were 0.11--0.00 and 0.09--0.01 respectively, and the oxide-ionic transport numbers were 0.41--0.33 and 0.27--0.30 respectively. Protonic conductivity of Ba0.95Ce0.8Ho0.2O3-a in both wet hydrogen and wet air was higher than that of BaCe0.8Ho0.2O3-a in 600--- 800 ℃, but lower in 900--1000 ℃. Oxide-ionic conductivity of the material was higher than that of BaCe0.8Ho0.2O3-a in both dry air and wet air in 600---1000 ℃.  相似文献   

9.
仇立干  马桂林 《中国化学》2006,24(11):1564-1569
BaxCe0.8Tb0.2O3-a (x=0.98-1.03) solid electrolytes were synthesized and characterized by using X-ray diffraction (XRD). By using AC impedance spectroscopy and gas concentration cell electromotive force (EMF) measurements, the electrical conduction behavior of the specimens was investigated in different gases during 500-1000 ℃ The influence of nonstoichiometry in the specimens with x ≠ 1 on conduction properties was studied and compared with that in the specimen with x = 1. The results show that the specimens are all of perovskite-type orthorhombic structure. In 500-1000 ℃, electronic hole conduction is dominant in dry and wet oxygen, air or nitrogen. Protonic conduction is dominant in wet hydrogen and it is about two orders of magnitude higher than that in hydrogen-free atmospheres (oxygen, air and nitrogen). The electrical conductivity of the same specimen in water vapor-saturated oxygen, air or nitrogen is slightly higher than that in corresponding gas without water vapor. The electrical conductivities of the nonstoichiometric specimens are higher than those of the stoichiometric one.  相似文献   

10.
Electrochemical properties of composite cathodes consisting of La0.8Sr0.2Mn1?x Cu x O3 (LSMCu, 0?≤?x?≤?0.2) and Ce0.8Gd0.2O2?x (GDC) were determined by impedance spectroscopy, and conduction mechanism for the composite cathodes was investigated by a near-edge X-ray absorption fine-structure analysis (NEXAFS). LSMCu–GDC cathodes showed lower polarization resistance (R p) than LSM–GDC up to 750 °C, whereas they exhibited better performance at higher temperature (≥800 °C). The best performance was achieved with the LSMCu10–GDC cathode: 0.27 and 0.08?Ω cm2 at 800 °C and 850 °C, respectively. NEXAFS and refinement results confirmed that Cu doping caused the oxidation of Mn3+ to Mn4+ and lattice contraction. This additional Mn4+ can lead to the formation of oxygen vacancies when Mn4+ is converted to Mn3+ at relatively high temperatures (above 600 °C). This in turn contributes to improved oxygen ion transport in LSM. The LSMCu–GDC composite cathode can thus be considered a suitable potential cathode for SOFC applications.  相似文献   

11.
A system consisting of a solid oxide electrolyte of the Ce0.9Gd0.1O2 − x (CGO) composition in contact with a two-layer cathode based on a nonstoichiometric composition (La0.8Sr0.2)0.95MnO3 ± δ (LSM1) and a stoichiometric perovskite La0.8Sr0.2MnO3 ± δ (LSM2) is prepared by the tape-casting process. It was shown that the best electrochemical characteristics are achieved for a three-layer system LSM2/{CGO-LSM1}/CGO sintered at 1410°C. The use of Ce-modified perovskites La0.8Sr0.2MnO3 ± δ and La0.6Sr0.6CoO3 ± δ as the collector layer of two-layer electrodes allows the electrochemical characteristics at moderately high temperatures (600–750°C) to be improved.  相似文献   

12.
Silver-Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) cathodes were prepared in two ways. In the first method, Ag-BSCF composite powder was prepared in ethanol solution, where Ag nanoparticles serving as a component in the preparation of Ag-BSCF composite cathodes had been previously obtained via one-step synthesis in absolute ethanol using a neutral polymer (polyvinylpyrrolidone). To the best of our knowledge, this is the first study to use a Ag sol obtained by the above method for preparation of Ag-BSCF composite powder. Then, a paste containing this powder was screen-printed on a Sm0.2Ce0.8O1.9 electrolyte and sintered at 1,000 °C. In the second technique, an aqueous solution of AgNO3 was added to a previously sintered BSCF cathode, which was then sintered again at 800 °C. The oxygen reduction reaction at the quasi-point BSCF cathode on the Sm0.2Ce0.8O1.9 electrolyte was tested by electrochemical impedance spectroscopy at different oxygen concentrations in three electrode setup. The continuous decrease of polarization resistance was observed under polarization ?0.5 V at 600 °C. The comparative studies of both obtained composite Ag-BSCF materials were performed in hydrogen-oxygen IT-SOFC involving samaria-doped ceria as an electrolyte and Ni-Gd0.2Ce0.8O1.9 anode. In both cases, the addition of silver to the cathode caused an increase in current and power density compared with an IT-SOFC built with the same components but involving a monophase BSFC cathode material.  相似文献   

13.
The method of isotopic exchange was used to study the oxygen exchange kinetics in the oxides of La0.88Sr0.12Ga0.82Mg0.18O3 − δ and La0.80Sr0.20Ga0.85−x Mg0.15Co x O3 − δ (x = 0.05, 0.15, 0.20, 0.25). The rates of oxygen exchange and its diffusion coefficients were determined in the temperature range of 600–900°C at the oxygen pressure of 5 torr. The fractions of the three exchange types for the oxides studied were determined at the temperature of 817°C and oxygen pressure of 5 torr. The total conductivity of the oxides of La0.80Sr0.20Ga0.85−x Mg0.15Co x O3 − δ (x = 0.05, 0.15, 0.20, 0.25) was measured in the temperature range of 550–850°C in air and at the temperature of 800°C in the range of oxygen pressures of 1–760 torr. It was shown that an increase in the electronic conductivity component due to an increase in the cobalt fraction in the gallium sublattice results in growing interfacial exchange rate, total conductivity of the studied systems, and a decrease in the effective conductivity activation energy.  相似文献   

14.
Highly compact (99%) solid electrolyte Ce0.8Gd0.2O1.9 with submicron (0.3 μm) grains is synthesized. The dilatometric (20–850°C) and conductivity (180–350°C) measurements are performed on the electrolyte in air and as a function of the partial oxygen pressure \(p_{O_2 } \) (0.21?1×10?25 atm) at 600, 700, and 800°C. An inflection is found in the temperature dependences of the thermal coefficient of linear expansion and conductivity (impedance measurements) at ~230°C, which is the evidence for a phase transition. The activation energies for conduction in the grain bulk and boundaries differ only slightly, indicating that the grain boundaries’ resistance is caused not by the precipitation of the second phase at the boundaries, but most probably by the presence of intergranular nanopores. The dilatometric measurements confirm a significant increase in the linear dimensions of Ce0.8Gd0.2O1.9 in the reducing atmospheres with a parallel increase in its electron conductivity. The electron conductivity and specific elongation increase proportionally to \(p_{O_2 }^{ - 1/4} \) at all temperatures. The \(p_{O_2 } \) values, at which the transport numbers of ions t i = 0.5, are determined. They are 10?22.5, 10?20, and 10?18 atm at 600, 700, and 800°C, respectively.  相似文献   

15.
Samaria-doped ceria Ce0.8Sm0.2O2−δ (SDC) and SmFe0.7Cu0.3−x Ni x O3 have been synthesized by the sol-gel method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The electrochemical synthesis of ammonia was investigated at atmospheric pressure and low temperature, using the SFCN materials as the cathode, a Nafion membrane as the electrolyte, nickel-doped SDC (Ni-SDC) as the anode and silver-platinum paste as the current collector. Ammonia was synthesized from 25 to 100°C when the SFCN materials were used as cathode, with SmFe0.7Cu0.1Ni0.2O3 giving the highest rates of ammonia formation. The maximum rate of evolution of ammonia was 1.13 × 10−8 mol·cm−2·s−1 at 80°C, and the current efficiency reached as high as 90.4%. Supported by the National Natural Science Foundation of China (Grant No. 20863007)  相似文献   

16.
This work is devoted to the studying of effects of La2NiO4 doping with alkaline-earth elements: Ca, Sr, and Ba (at an amount of 15 mol %) on its structural, electrical, and electrochemical properties. The effects of the alkaline-earth element nature, introduction of the Ce0.8Sm0.2O1.9-electrolyte (SDC) component to the functional layer, and the presence of collecting film onto electrochemical activity of the electrodes contacting the Ce0.8Sm0.2O1.9-electrolyte are examined. The doping was found to increase the La2NiO4 full conductivity due to increase in the hole conductivity. The maximal conductivity (at the sample density of 86–89%) was obtained for the Ca-doped composition: 85 S/сm at 700°C, as compared with 65 S/сm for undoped La2NiO4. at the same time, the doping was found to deteriorate the electrodes’ electrochemical activity which is likely to be due to loss of interstitial oxygen as a result of the doping. The using of composite electrodes allows increasing polarization conductivity markedly. For instance, at 700°С the conductivity of La2NiO4 is 0.25 S/сm2; of its based composite, 0.67 S/сm2.  相似文献   

17.
The effect of introducing 1–3 wt % copper oxide sintering additive on the electrical and electrochemical characteristics of promising anode materials for solid oxide fuel cells based on Sr2Fe1.5Mo0.5O6–δ was studied. The total conductivity increases with increasing amount of copper oxide. The maximum conductivity in humid hydrogen at 800°C, 45 S cm–1, was reached on introducing 3 wt % CuO. The sintering additive enhances the electrochemical activity of Sr2Fe1.5Mo0.5O6–δ and Sr2Fe1.5Mo0.5O6–δCe0.8Sm0.2O1.9 anodes. A decrease in the sintering temperature of the anodes containing CuO with the electrolyte based on lanthanum gallate directly correlates with the electrochemical activity of the anodes. The minimum value of the polarization resistivity, 0.15 Ω cm2 at 800°С in a humid hydrogen atmosphere, was obtained for the composite anode with 3 wt % CuO sintered at a temperature of 1050°С.  相似文献   

18.
Sol-gel process was employed to synthesize the Pb-BSCCO system having general composition Bi2−xPbxSr2Ca2Cu3O10−δ, where x=0.2, 0.4 and 0.8. Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), dilatometry and vibrating sample magnetometer (VSM) were employed to study the materials produced at different stages. Two-stage heating firstly at 300 and then 800°C was adopted in order to avoid the burning of the materials and formation of carbonates. The carbonate formation was avoided by heating the materials firstly at 300°C for 2 h and without intermediate cooling moved to the furnace having temperature 800°C and hold for 2 h. The sintering behaviour of samples was studied by dilatometry and the results revealed that the sample having x=0.4 was stabled up to a temperature of 700°C while samples having x=0.2 and 0.8 to a temperature of 625°C. The maximum shrinkage was observed at 850°C in all the samples. On the basis of dilatometry results, the samples were sintered at 845°C for 60 h to observe the superconducting phases. The highest volume fraction of high superconducting phase (2223) was noticed in the sample containing x=0.4 having onset T c=110 K.  相似文献   

19.
A cobalt-free cubic perovskite oxide, SrFe0.9Nb0.1O3?δ (SFN) was investigated as a cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). XRD results showed that SFN cathode was chemically compatible with the electrolyte Sm0.2Ce0.8O1.9 (SDC) for temperatures up to 1050 °C. The electrical conductivity of SFN sample reached 34–70 S cm?1 in the commonly operated temperatures of IT-SOFCs (600–800 °C). The area specific resistance was 0.138 Ω cm2 for SFN cathode on SDC electrolyte at 750 °C. A maximum power density of 407 mW cm?2 was obtained at 800 °C for single-cell with 300 μm thick SDC electrolyte and SFN cathode.  相似文献   

20.
The possibility of using the LnO x mischmetal (Ln = Ce, La, Nd, Pr, Sm) for preparation of cathodes for solid-oxide fuel cells with the supported YSZ electrolyte is studied. The electrical and electrochemical characteristics of Ln-Mn-O electrodes with the ratio of all lanthanides contained in the mischmetal except for cerium to manganese Ln: Mn = 1: 1 and also of a material comprised of Ln-Mn-O and La0.8Sr0.2MnO3 are studied. The latter electrode material that contains 35?C40 wt % of Ln-Mn-O and was sintered at 1200°C has the specific ohmic resistance of 0.1 ?? cm at 800°C. The polarization conductivity is compared for electrodes made of 100% Ln-Mn-O, 40 wt % Ln-Mn-O + 60 wt % La0.8Sr0.2MnO3, and 100% La0.8Sr0.2MnO3 in the initial state and after their modification through the introduction of an electrocatalyst (PrO2 ? x ). The highest polarization conductivity is typical of Ln-Mn-O + (La, Sr)MnO3 electrodes containing 40 wt % Ln-Mn-O and PrO2 ? x . The polarization conductivity of these electrodes is found to be 25 S/cm2 at 800°C.  相似文献   

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