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1.
The structure, phase stability, and electrical properties of BaCe1−xYxO3−δ (x = 0-0.4) in humidity air and CO2 atmosphere are investigated. XRD results indicate that the BaCe0.9Y0.1O3−δ sample has a symmetric cubic structure, and its phase changes to tetragonal as the Y3+ doping amount increases to 20 mol%. The conductivity of BaCe1−xYxO3−δ increases with temperature, and it depends on the amount of yttrium doping and the atmosphere. BaCe0.8Y0.2O3−δ exhibits the highest conductivity of 0.026 S cm−1 at 750 °C. The activation energy for conductivity depends on yttrium doping amount and temperature. The conductivity of BaCe0.8Y0.2O3−δ is 0.025 S cm−1 in CO2 atmosphere at 750 °C which is 3.8% lower than that in air due to reactions with CO2 and BaCO3 and the CeO2 impure phases formed. The structure of BaCe0.8Y0.2O3−δ is unstable in water and decomposes to Ba(OH)2 and CeO2 phases. It is found that the activation energy of samples in CO2 atmosphere is higher than that of sample in air. Sr-doped Ba1−ySryCe0.8Y0.2O3−δ (y = 0-0.2) is prepared to improve the phase stability of BaCe0.8Y0.2O3−δ in water. The conductivity of Ba0.9Sr0.1Ce0.8Y0.2O3−δ is 0.023 S cm−1 at 750 °C which was 11% lower than that of BaCe0.8Y0.2O3−δ, however, the phase stability of Ba0.9Sr0.1Ce0.8Y0.2O3−δ is much better than that of BaCe0.8Y0.2O3−δ in water.  相似文献   

2.
BaxSr1−xCoyFe1−yO3−δ (BSCF) materials with perovskite structure were synthesized via solid-state reaction. Their structural characteristics, electrical-conduction behavior and cathode performance were investigated. Compared to A-site elements, B-site elements show a wide solid-solution range in BSCF. The electrical-conduction behavior of BSCF obeys the small polaron-hopping mechanism. An increase of Ba or Co content in the BSCF samples results in a decrease of electrical conductivity, which is mainly attributable to the preferential existence of B3+ rather than B4+ in Ba- or Co-rich samples. At the same time, this leads to increases in the lattice parameter a and the number of oxygen vacancies. BSCF samples with high Ba content show a high structural stability (high oxygen-loss temperature). Ba0.6Sr0.4Co0.8Fe0.2O3−δ and Ba0.5Sr0.5Co0.8Fe0.2O3−δ materials present good thermal-cycling stability of the electrical conductivity. Compared with Ba0.5Sr0.5Co0.8Fe0.2O3−δ, Ba0.6Sr0.4Co0.8Fe0.2O3−δ exhibits a better cathode performance in a Ce0.8Gd0.2O2−δ (GDC)-supported half cell. The cell performance can be improved by introducing a certain amount of GDC electrolyte into the BSCF cathode material.  相似文献   

3.
Double-perovskite Sr2−xSmxMgMoO6−δ (SSMM, 0 ≤ x ≤ 0.8) is investigated as a possible anode material for solid-oxide fuel cells on La0.9Sr0.1Ga0.8Mg0.2O3−δ (LSGM) electrolytes. Single-phase SSMM samples with 0 ≤ x ≤ 0.4 are prepared. At x ≥ 0.6, a small amount of SrMoO4 and Sm2O3 impurities are observed. The Mg/Mo ordering in SSMM decreases with increasing Sm content. Substitution of Sm for Sr significantly improves the electrical conductivity of SSMM. At x = 0.6, the sample yields the highest conductivity, with values reaching 16 S cm−1 in H2 at 800 °C. The maximum power densities of single cells achieved with x = 0.0, 0.2, 0.4, 0.6, and 0.8 anodes on a 300 μm-thick LSGM electrolyte are 693, 770, 860, 907, and 672 mW cm−2, respectively, in H2 at 850 °C. The SSMM sample with x = 0.4 is considered as the best anode candidate because of the impurity formation seen in x ≥ 0.6 samples. The x = 0.4 sample not only has a thermal-expansion coefficient closer to that of the LSGM electrolyte but also exhibits good electrochemical performance and stability in commercial city gas containing H2S, where the maximum power density achieved is 726 mW cm−2 at 850 °C.  相似文献   

4.
Oxides of composition SrMo1−xCrxO3−δ (x = 0.1, 0.2) have been prepared, characterized and tested as anode materials in single solid-oxide fuel cells, yielding output powers higher than 700 mW cm−2 at 850 °C with pure H2 as a fuel. All the materials are suggested to present mixed ionic–electronic conductivity (MIEC) from neutron powder diffraction (NPD) experiments, complemented with transport measurements; the presence of a Mo4+/Mo5+ mixed valence at room temperature, combined with a huge metal-like electronic conductivity, as high as 340 S cm−1 at T = 50 °C for x = 0.1, could make these oxides good materials for solid-oxide fuel cells. The magnitude of the electronic conductivity decreases with increasing Cr-doping content. The reversibility of the reduction–oxidation between the oxidized Sr(Mo,Cr)O4−δ scheelite and the reduced Sr(Mo,Cr)O3 perovskite phases was studied by thermogravimetric analysis, which exhibit the required cyclability for fuel cells. An adequate thermal expansion coefficient, without abrupt changes, and a chemical compatibility with electrolytes make these oxides good candidates for anodes in intermediate-temperature SOFC (IT-SOFCs).  相似文献   

5.
Perovskite oxides SrCo1−yNbyO3−δ (SCNy, y = 0.00-0.20) are investigated as potential cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs) on La0.9Sr0.1Ga0.8Mg0.2O3−δ (LSGM) electrolyte. Compared to the undoped SrCoO3−δ, the Nb doping significantly improves the thermal stability and enhances the electrical conductivity of the SCNy oxides. The cubic phase of the SCNy oxides with high thermal stability can be totally obtained when the Nb doping content y ≥ 0.10. Among the investigated compositions, the SrCo0.9Nb0.1O3−δ oxide exhibits the highest electrical conductivity of 461-145 S cm−1 over the temperature range of 300-800 °C in air. The SCNy cathode has a good chemical compatibility with the LSGM electrolyte for temperatures up to 1050 °C for 5 h. The area specific resistances of SCNy with y = 0.10, 0.15 and 0.20 cathodes on LSGM electrolyte are 0.083, 0.099 and 0.110 Ω cm2 at 700 °C, respectively. At y = 0.10, 0.15 and 0.20, the maximum power densities of a single-cell with SCNy cathodes on 300-μm thick LSGM electrolyte achieve 675, 642 and 625 mW cm−2 at 800 °C, respectively. These results indicate that SCNy perovskite oxides with cubic phase are potential cathode materials for application in IT-SOFCs.  相似文献   

6.
The SrCo1−xSbxO3−δ (x = 0.05, 0.1, 0.15 and 0.2) system was tested as possible cathode for solid oxide fuel cells (SOFCs). X-ray diffraction results show the stabilization of a tetragonal P4/mmm structure with Sb contents between x = 0.05 and x = 0.15. At x = 0.2 a phase transition takes place and the material is defined in the cubic Pm-3m space group. In comparison with the undoped hexagonal SrCoO3 phase, the obtained compounds present high thermal stability without abrupt changes in the expansion coefficient. In addition, a great enhancement of the electrical conductivity was observed at low and intermediate temperatures (T ≤ 800 °C). The sample with x = 0.05 displays the highest conductivity value that reaches 500 S cm−1 at 400 °C and is over 160 S cm−1 in the usual working conditions of a cathode in SOFC (650-900 °C). Moreover, the impedance spectra of the SrCo1−xSbxO3−δ/Ce0.8Nd0.2O2−δ/SrCo1−xSbxO3−δ (x ≥ 0.05) symmetrical cells reveal polarization resistances below 0.09 Ω cm2 at 750 °C which are much smaller than that displayed by the pristine SrCoO3−δ sample. The composition with x = 0.05 shows the lowest ASR values ranging from 0.009 to 0.23 Ω cm2 in the 900-600 °C temperature interval with an activation energy of 0.82 eV.  相似文献   

7.
(Pr–Nd)1−ySryMnO3−δ (P-NSM, y = 0.2, 0.25, 0.3, 0.35) powders made from commercial Pr–Nd mixed oxide, as well as (Pr1−xNdx)0.7Sr0.3MnO3−δ (PN3SM, x = 0, 0.5, 0.7, 1) were synthesized by a glycine-nitrate process and characterized as cathode materials for intermediate temperature solid oxide fuel cell (IT-SOFC). XRD patterns showed the powders had formed pure perovskite phase after being calcined at 800 °C for 2 h. (Pr–Nd)0.7Sr0.3MnO3−δ (P-N3SM) achieved a high conductivity of 194 S cm−1 at 500 °C and showed a good chemical stability against YSZ at 1150 °C. And the thermal expansion coefficient of P-N3SM/YSZ cathode was 11.1 × 10−6 K−1, which well matched YSZ electrolyte film. The tubular SOFC with P-N3SM/YSZ cathode exhibited the maximum power densities of 415, 367, 327 and 282 mW cm−2 at 850, 800, 750 and 700 °C, respectively, which indicated P-N3SM was potentially applied in SOFC for low cost.  相似文献   

8.
Scandium-doped PrBaCo2−xScxO6−δ(PBCS-x, x = 0.00–1.00) oxides have been evaluated as cathode materials of intermediate-temperature solid oxide fuel cells (IT-SOFCs) with respect to phase structure, oxygen content, thermal expansion behavior and electrical and electrochemical properties. The XRD results have demonstrated a phase transition in PBCS-x due to Sc3+ doping from tetragonal double-layered perovskite structure at x = 0.00–0.20, bi-phase mixtures at x = 0.30–0.40, to cubic perovskite structure at x = 0.50–0.90. The oxygen contents (6-δ) and average valences of cobalt ions in PBCS-x decrease with the higher Sc3+ content and increasing temperatures in air. Sc3+ doping has also led to decreased thermal expansion coefficients, lowered electrical conductivities and enhanced electrochemical reaction activities for PBCS-x characterized by decreased area-specific resistances (ASRs) and smaller reaction activation energies. Among the studied samples, the PBCS-0.50 oxide with Sc3+-doping content of x = 0.50 exhibits the best electrochemical performance on Ce0.9Gd0.1O1.95 electrolyte. Its ASR values range from 0.123 Ω cm2 at 600 °C to 0.022 Ω cm2 at 750 °C, which are much lower than the related cathode materials. These results have demonstrated that the PBCS-0.50 oxide is a promising cathode material for IT-SOFCs.  相似文献   

9.
The SrTixCo1−xO3−δ (STC, x = 0.05, 0.1, 0.15, 0.2) perovskite-type oxides synthesized by the polymerized complex (PC) method have been investigated as cathode materials for low-temperature solid oxide fuel cells (SOFCs) with composite electrolyte for the first time. Thermogravimetry-differential thermal analysis (TG-DTA) shows the crystallization of SrTi0.1Co0.9O3−δ occurs at 780 °C. The oxides have been stabilized to be a cubic perovskite phase after the B-site is doped with Ti ion. The maximum power density reaches as high as 613 mW cm−2 at 600 °C for SOFC with SrTi0.2Co0.8O3−δ cathode. The maximum power densities increase with the increasing Ti content in the cathode, which can be attributed to the enhancement of conductivity and electrocatalytic activity. The stability of the fuel cell with SrTi0.1Co0.9O3−δ cathode has been examined for 18 h at 600 °C. Only a slight decline in the cell performance can be observed with increasing time. The high performance cathodes together with the low-cost fabrication technology are highly encouraging for development of low-temperature SOFCs.  相似文献   

10.
Cobalt-free perovskite oxides Ba1−xLaxFeO3−δ (x = 0.1–0.4) were synthesized by glycine-nitrate combustion method and investigated as a candidate cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs). Cubic perovskite structure was obtained when 10–20 mol% La was substituted at Ba-site in Ba1−xLaxFeO3−δ, and the crystal structure was transformed from cubic structure into orthorhombic one at x ≥ 0.2 with an addition of lanthanum doping. The thermal expansion coefficients of Ba1−xLaxFeO3−δ oxides decreased gradually with La content due to increasing electrostatic attraction forces. A gradual increase existed in electrical conductivity tendency with La content due to disproportionation of Fe3+ and the larger extent of electron clouds. The electrode redox performance was investigated by electrochemical impedance spectroscopy. Among Ba1−xLaxFeO3−δ series oxides, Ba0.9La0.1FeO3−δ exhibited the best electrochemical performance. The area specific resistance (ASR) of Ba0.9La0.1FeO3−δ was 0.079 Ω cm2, 0.37 Ω cm2, and 2.15 Ω cm2 at 800, 700 and 600 °C under open circuit potential. To investigate electrochemical performances after cathodic polarization, bias potentials were employed on Ba1−xLaxFeO3−δ cathode at 650–800 °C. The results demonstrated the potential applications for Ba0.9La0.1FeO3−δ as cathode materials for IT-SOFCs as a tradeoff between electrochemical and thermal expansion performance.  相似文献   

11.
Perovskite-type La1−xSrxNiyFe1−yO3−δ (x = 0.3, 0.4, 0.5, 0.6, y = 0.2; x = 0.3, y = 0.2, 0.3, 0.4) oxides have been synthesized and employed as cathodes for low-temperature solid oxide fuel cells (SOFCs) with composite electrolyte. The segregation of La2NiOδ is observed to increase with the increasing Sr2+ incorporation content according to X-ray diffraction (XRD) results. The as-prepared powders appear porous foam-like agglomeration with particle size less than 1 μm. Maximum power densities yield as high as 725 mW cm−2 and 671 mW cm−2 at 600 °C for fuel cells with the LSNF4628 and LSNF7337 composite cathodes. The maximum power densities continuously increase with the increasing Sr2+ content in LSNF cathodes, which can be mainly ascribed to the possible charge compensating mechanism. The maximum power densities first increase with the Ni ion incorporation content up to y = 0.3 due to the increased oxygen vacancy, ionic conductivity and oxygen permeability. Further increase in Ni ion content results in a further lowering of fuel cell performance, which can be explained by the association of oxygen vacancies and divalent B-site cations in the cathode.  相似文献   

12.
LaCrO3 doped with calcium and cerium on the A-site in the series of La0.9−xCaxCe0.1CrO3−δ (LCCC3060, LCCC4050, LCCC5040, LCCC6030 corresponding to x = 0.6, 0.5, 0.4, and 0.3 respectively), is synthesized by a sol–gel combustion method and evaluated as anode material for solid oxide fuel cells (SOFCs). Relatively higher Ca-doping on La in LaCrO3 is found to improve both electronic and ionic conductivity. LCCC compositions have demonstrated good chemical stability in reducing atmospheres. Evaluation of the LCCC material as anode in symmetrical cell configuration shows that the highest Ca-doping composition results in the lowest activation energy and the lowest polarization resistance. La0.8Sr0.2Ga0.83Mg0.17O3−δ (LSGM) electrolyte-supported single cells with LCCC3060 as the anode and La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) as the cathode show that LCCC3060 can be a potential anode material for H2, but not for CH4.  相似文献   

13.
BaZr0.9−xPrxGd0.1O3−δ (x = 0.3 and 0.6) was prepared by combustion synthesis and characterised with respect to conductivity and stability in an attempt to combine the desirable properties of the end members. The polycrystalline materials exhibit a cubic or pseudo-cubic structure as determined by X-ray synchrotron radiation and transmission electron microscopy. The chemical stability of the compositions is strongly dependent on the praseodymium content, the materials with more Pr present lower stability. Electron holes dominate the conductivity under oxidising atmospheres in BaZr0.3Pr0.6Gd0.1O3−δ, while BaZr0.6Pr0.3Gd0.1O3−δ exhibits a mixed electron hole-proton conducting behaviour. Substitution of Zr by Pr in acceptor-doped BaZrO3 decreases the sintering temperature and increases the grain growth rate.  相似文献   

14.
A series of new oxides with the nominal composition of SmxSr1−xCo1−yCeyO3−δ (x = 0.1, 0.3, 0.5; y = 0.05, 0.1) were synthesized. Their crystal structure, morphology, thermal expansion and electrochemical properties were systematically investigated. A phase-pure perovskite-type Sm0.3Sr0.7Co0.95Ce0.05O3−δ oxide is obtained, while the other samples are actually composed of B-site cation deficient SmxSr1−xCo1−yCeyzO3−δ (0 < z < y) and CeO2 mixed phases. These two-phase samples exhibit larger oxygen nonstoichiometry (δ) and higher average thermal expansion coefficients (TEC), while the single-phase Sm0.3Sr0.7Co0.95Ce0.05O3−δ oxide shows a smaller δ and a lower TEC as compared to Sm0.3Sr0.7CoO3−δ. The introduction of cerium also effectively suppresses the chemical expansion and the growth of grain particles. The smaller grain size is beneficial in improving the electrode surface area. In addition, the electrical conductivities of Ce-doped SmxSr1−xCoO3−δ are all higher than 200 S cm−1. EIS tests demonstrate that partially substituting Co with Ce and the B-site deficiency improve the cathode performance. Sm0.3Sr0.7Co0.95Ce0.05O3−δ shows the lowest area specific resistance (ASR) among the others. Through proper cobalt-site cerium doping, the SmxSr1−xCoO3−δ related oxides could be developed into promising cathode materials for SOFC.  相似文献   

15.
The aim of this study was to develop La1−xBaxGa1−yMgyO3−δ (x = 0.03–0.1, y = 0.2–0.25) (LBGM) electrolytes for intermediate-temperature solid-oxide fuel cells (SOFCs); these electrolytes were synthesized via a solid-state reaction. In the study, the La1−xBaxGa1−yMgyO3−δ samples crystallized in an orthorhombic (Imma) structure, and a BaLaGa3O7 phase was detected for x ≥ 0.08 at a fixed y = 0.2. The solubility limit of the Ba ions increased with an increase in the Mg content in the matrix. Two active Raman bands at ca. 677 and 739 cm−1 were observed, and they were attributed to the oxygen vacancies. The La0.95Ba0.05Ga0.75Mg0.25O3−δ sample had a higher conductivity ca. 0.1 S/cm at 800 °C, and an activation energy of ca. 0.83–1.27 eV at 500–800 °C. The thermal expansion coefficient (TEC) of the LBGM samples at 200–800 °C was in the range of 10 × 10−6 to 14 × 10−6/°C.  相似文献   

16.
A family of iron perovskites with the general formula AFeO3−δ (A = Ln1−xMx; Ln = La, Nd and/or Pr; M = Sr or/and Ca) has been prepared keeping fixed the A cation radius 〈rA〉 and cation size mismatch to isolate the effect of divalent dopant concentration from the A-cation steric effects. The electrochemical behaviour of these compounds for their application as SOFC cathodes was evaluated by using I-V curve measurements and ac impedance spectroscopy over three electrodes electrolyte supported cells processed under identical conditions. In contrast with the bulk behaviour, trends are more difficult to observe due to microstructural effects, but results seem to indicate that the doping level, x, does not influence in a significant way the electrochemical performance of iron perovskites with identical 〈rA〉 and σ2(rA).  相似文献   

17.
In the present work, we have explored novel Nd2WO6-type structure Sm2−xAxM1−yByO6−δ (A = Ca, Sr; M = Mo, W; B = Ce, Ni) as precursor for the development of solid oxide fuel cells (SOFCs) anodes. The formation of single-phase monoclinic structure was confirmed by powder X-ray diffraction (PXRD) for the A- and B-doped Sm2MO6 (SMO). Samples after AC measurements under wet H2 up to 850 °C changed from Nd2WO6-type structure into Sm2MoO5 due to the reduction of MoVI that was confirmed by PXRD and is consistent with literature. The electrical conductivity was determined using 2-probe AC impedance and DC method and was compared with 4-probe DC method. The total electrical conductivity obtained from these two different techniques was found to vary within the experimental error over the investigated temperature of 350-650 °C. Ionic and electronic conductivity were studied using electron-blocking electrodes technique. Among the samples studied, Sm1.8Ca0.2MoO6−δ exhibits total conductivity of 0.12 S cm−1 at 550 °C in wet H2 with an activation energy of 0.06 eV. Ca-doped SMO appears to be chemically stable against reaction with YSZ electrolyte at 800 °C for 24 h in wet H2. The ionic transference number (ti) of Sm1.9Ca0.1MoO6−δ in wet H2 at 550 °C (pO2 = 10−25.5 atm) was found to be about 0.012 after subtraction of electrical lead resistance from the 2-probe AC data and showed predominate electronic conductors.  相似文献   

18.
This study reports the synthesis of proton-conducting BaZr0.2Ce0.8−xYxO3−δ (x = 0–0.4) oxides by using a combination of citrate-EDTA complexing sol–gel process and composition-exchange method. Compared to those oxides prepared from conventional sol–gel powders, the sintered BaZr0.2Ce0.8−xYxO3−δ pellets synthesized by sol–gel combined with composition-exchange method are found to exhibit improved sinterability, a higher relative density, higher conduction, and excellent thermodynamic stability against CO2. Moreover, the Pt/electrolyte/Pt single cell using such a BaZr0.2Ce0.6Y0.2O3−δ electrolyte shows an obviously higher maximum powder density in the hydrogen-air fuel cell experiments. Based on the experimental results, we discuss the improvement mechanism in terms of calcined particle characteristics. This work demonstrates that the BaZr0.2Ce0.8−xYxO3−δ oxides synthesized by sol–gel combined with composition-exchange method would be a promising electrolyte for the use in H+-SOFC applications. More importantly, this new fabrication approach could be applied to other similar ABO3-perovskite material systems.  相似文献   

19.
La2−xSrxCoO4−δ (x = 0.9, 1.0, 1.1) compounds with Ruddlesden-Popper K2NiF4-type structure have been investigated as potential cathode materials for IT-SOFC application. Materials have been prepared by citrate-nitrate combustion method. Structural evolution analysed by XRD shows a shortened Co–O–Co bond length within the perovskite layer as Sr substitution increases, while the interlayer distance at the same time increases. An oxygen stoichiometry close to 4 has been found for all compositions at room temperature. Thermal expansion coefficients have been obtained from temperature-dependent XRD analysis and show large values (>20 × 10−6 K−1) compared to the currently utilized electrolyte materials. Electrochemical characterisation has been performed by means of impedance spectroscopy on symmetric cells with CGO electrolyte. Pure electrodes have a high Area Specific Resistance, probably due to limited oxygen ion diffusion. By using composite electrode (50 wt.% CGO), an Area Specific Resistance of 0.25 Ω cm2 is obtained at approximately 700 °C for all the three compounds suggesting promising electrochemical properties for IT-SOFCs.  相似文献   

20.
Scandium-doped lanthanum strontium manganate La0.8Sr0.2Mn1−xScxO3−δ (LSMS) combined with YSZ as composite cathode for anode-supported solid oxide fuel cell is investigated. The LSMS powders are prepared using the modified Pechini method. The XRD and H2-TPR results reveal that non-stoichiometric defects are introduced into the perovskite lattice of LSMS samples as a result of Sc substitution, which leads to increased oxygen ion mobility in the Sc containing samples. But high level doping of Sc may results in the segregation of the Sc2O3 secondary phase at elevated temperature. The cells with the LSMS-containing cathodes exhibit higher performances, especially at lower temperatures, which can be ascribed to the increased oxygen anionic vacancies in the LSMS.  相似文献   

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