新型固体电解质Ce5.9Ga0.1MoO15-δ的溶胶-凝胶制备及其导电性能

采用溶胶-凝胶法和固相法制备了Ce5.9Ga0.1MoO15-δ.通过差热-热重分析、X射线粉末衍射、X射线光电子能谱和交流阻抗谱等手段对其进行结构表征和导电性能测试.结果表明:Ga的掺杂可增加氧离子空位浓度,改善母体的电导率;测试温度为800℃时溶胶-凝胶法合成Ce5.9Ga0.1MoO15-δ的电导率为6.5×10-3S/cm,高于固相法制备材料的电导率(1.8×10-3S/cm).     

不同方法制备的Ce0.8Sm0.2O1.9(SDC)性能对比

分别采用沉淀法、凝胶辅助的固相反应法和甘氨酸-硝酸盐法制备了钐掺杂的氧化铈材料,结果表明,用后两种方法制备的粉体能够满足固体电解质的要求,其中,凝胶辅助的固相反应法制备的粉体粒度约为20~100nm,甘氨酸-硝酸盐法制备的粉体粒度更小,表现为许多超细纳米颗粒的团聚体.二者烧结体的致密度分别可以达到95%和97%,800℃时的电导率分别为0.071S/cm和0.074S/cm.     

新型固体电解质Ce6- x Sm x MoO15- δ (0≤x≤1.2)的合成及电性质

采用溶胶-凝胶方法合成系列新型氧化物 Ce6- x Sm x MoO15- δ (0≤x≤1.2). 通过TG-DTA, XRD和XPS等手段对氧化物结构进行了表征. 结果表明, 氧化物的最低成相温度为400 ℃, 具有立方莹石结构. Sm的掺杂可增加氧离子空位浓度, 改善母体电导率. 阻抗谱表明, 采用溶胶-凝胶法合成固体电解质可减少或消除其晶界电阻. 800 ℃时, Ce5.2Sm0.8MoO15- δ的电导率高达6.67×10-3 S/cm.     

Preparation and performance of (Co,Mn)3O4 spinel coating on Crofer alloy by composite electrodeposition and step-heating thermal conversion

The preparation and performance improvement of the spinel coating on the surface of ferritic alloy is of wide interest for its application in the metallic interconnects of the solid oxide fuel cells (SOFCs). The Co Mn₂O₃ composite coating is prepared on the surface of the Crofer alloy by the composite electrodeposition method. A step-heating thermal conversion process is subsequently used to convert the composite coating into a spinel coating, while a direct-heating process is implemented as the control experiment. Isothermal oxidation tests are then carried out for the prepared samples in order to present the high temperature performance. Scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and area-specific resistance (ASR) are used to analyze the properties of the matrix and coatings. The experimental results reveal that the coatings by step-heating thermal conversion exhibit better performance of electrical conductivity and oxidation resistance than the coatings by direct-heating process. Furthermore, with the increase of oxidation time, the atomic proportion of Cr element diffusing to the surface of the matrix is maintained at about 3%–4% for the samples with spinel coatings by step heating, which effectively prevent the Cr volatilization in the matrix. The preparation of spinel coatings on the ferritic alloy by composite electrodeposition and step-heating thermal conversion is helpful to stimulate new ideas for the development of reliable and cost-effective metallic interconnect.     

Operando Isotopic Exchange in Solid Oxide Fuel Cells: Oxygen-Transport Dependency on Applied Potential

The oxygen isotopic exchange technique is a powerful tool to investigate the oxygen transport kinetics in an oxide solid. In a solid oxide fuel cell, isotopic surface exchange and diffusion coefficients are classically determined by using the Isotopic Exchange Depth Profiling method followed by ex situ SIMS characterizations. Despite its relevance, the utilization of in situ or operando techniques to measure the isotopic exchange under an electrical bias remains marginal. We developed here a set-up which enables operando monitoring of oxygen exchange in SOFC type cells under polarization. The system has been used for studying the oxygen mobility dependency upon polarization on a symmetrical Pt/YSZ/Pt cell (YSZ: yttria-stabilized zirconia). Homomolecular and heterolytic exchange reactions were undertaken to investigate the oxygen activation step and discriminate the limiting step among the sequence of elementary steps which constitute the oxygen transport process in the SOFC system. Oxygen ions incorporation into the dense ionic conductor was identified to be the rate determining step, and its first order rate constant dependency on applied potential was established.     

新型氧离子导体La_2Mo_2O_9

La2Mo2O9是一种具有高离子导电性的新型氧离子导体,其氧离子电导率在1073K时高达0.06S/cm,与YSZ在1273K时的电导率相当。这种高的离子导电性使它在中温固体氧化物燃料电池、氧传感器、透氧膜、固态离子器件等领域有着重要的潜在应用前景。本文从La2Mo2O9的结构、性质、氧离子扩散机理及其掺杂改性4个方面综述了近年来La2Mo2O9基固体电解质的研究热点和新进展,为该固体电解质材料的研究提供了有价值的信息。     

固体氧化物燃料电池（SOFC）电池稳定性分析

固体氧化物燃料电池(SOFC)要长期可靠运行,必须具有较高的稳定性。本文从SOFC内阻的主要来源出发,详细分析了影响电池长期稳定性、特别是引起性能衰减的主要因素,并研究其衰减机理。通过对电解质、阴极、阳极及连接材料等关键材料的选择及性能稳定性进行分析,系统论述了阴极与其它材料的相互反应、阳极性能变化以及连接材料表面氧化层等诸多引起SOFC性能衰减的不利因素。在氧化、还原气氛和密封效果等方面对电池长期稳定性的影响也进行了阐述。通过对电池性能衰减的原因及其衰减机理进行分析,对于SOFC长期运行稳定性、进而商业化应用具有一定的理论和实际意义。     

Electrical properties of triple-doped bismuth oxide electrolyte for solid oxide fuel cells

In this study, the quaternary solid solutions of (Bi₂O₃)_(0.8?x)(Tb₄O₇)_0.1(Ho₂O₃)_0.1(Dy₂O₃)_x (x = 0.05, 0.10, 0.15, 0.20) as an electrolyte were synthesized for solid oxide fuel cells by the technique of solid-state synthesis.

The products were characterized by X-ray powder diffraction, differential thermal analysis/thermal gravimetry and the four-point probe technique (4PPT). The total electrical conductivity is measured on the temperature and the doped concentration by 4PPT.

All samples have been obtained as the δ-phase. According to the measurements of the 4PPT, the electrical conductivities of the samples increase with the temperature but decrease with the amount of doping rate. The value of the highest conductivity (σ) is found as 1.02?×?10^?1 S cm^?1 for the system of (Bi₂O₃)_0.75(Tb₄O₇)_0.1(Ho₂O₃)_0.1(Dy₂O₃)_0.05 at 850 °C. The thermal gravimetry (TG) curve shows that there is no mass loss of sample during the measurement. The analyses of differential thermal reveal that there are neither endothermic peaks nor exothermic peaks during the heating and cooling cycles (ranging from 30 to 1000 °C).     

Electrochemical properties of nanostructured lanthanum strontium manganite cathode fabricated by electrostatic spray deposition

Electrostatic spray deposition was applied to prepare nanoporous lanthanum strontium manganite (LSM) films with high specific surface area (37.34 m²/g) for the cathode application in solid oxide fuel cell (SOFC). The electrochemical characteristics were investigated at a temperature range from 546 to 777 °C and oxygen partial pressure from 0.01 to 1.0 atm. The diffusion of atomic oxygen and oxygen ion transfer from three-phase boundary to the YSZ electrolyte were found to be the rate-determining steps for oxygen reduction reaction on LSM cathode. The polarization resistance of the LSM prepared using electrostatic spray deposition decreased from 15 to 1.2 Ωcm² with increasing temperature from 546 to 777 °C and the activation energy was 0.81 eV. It was demonstrated that the ESD method offers a promising approach for the preparation of electrochemically active nanoporous layers, particularly applicable for solid oxide fuel cells.     

Copper coated nickel foam as current collector for H2S-containing syngas solid oxide fuel cells

Copper coated nickel foam with Cu/Ni ratio of 2.5 was fabricated using electrochemical plating and characterized using XRD, SEM, EDS and Van der Pauw four point conductivity measurements. Copper coated nickel foam exhibited good stability of electronic conductivity and mechanical strength during more than 150 h exposure to 500 ppm H₂S-containing syngas at 750 °C. In contrast, uncoated nickel foam readily underwent severe carbon deposition and brittle fracture resulting in dramatic increase of electronic resistance under the same testing conditions. Copper coated nickel foam is a promising current collector for H₂S-containing syngas solid oxide fuel cells (SOFCs).