新型阴极材料Ba0.5Sr0.5Co0.8Fe0.2O3-σ制备与性能研究

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-σ(BSCF), a new cathode material for solid oxide fuel cell (SOFC), was synthesized by polyacrylicacid (PAA) method. The lattice structures of samples calcined at different temperatures were characte-rized by XRD. Shrinkage, porosity and pore size of the porous BSCF as a function of sintering temperature were investigated. It was found that the cubic perovskite structure could be formed after calcination at 800 ℃ for 2 h, but not well crystallized as seen from some unknown phases, and the pure cubic perovskite structure was formed after calcination at 1 150 ℃ for 2 h. The particle size of BSCF was less than 1～2 μm. The shrinkage of the porous BSCF increased with sintering temperature, but the opposite was true for the porosity. After sintering at 1 100 ℃ for 4 h, the porous BSCF was still in an appropriate structure, with porosity of 29% and electrical conductivity above 400 S·cm^-1.     

新型中温固体氧化物燃料电池阴极材料Fe掺杂Sm0.5Sr0.5CoO3性能研究

本文系统研究了新型中温固体氧化物燃料电池(IT-SOFC)阴极材料Sm_0.5Sr_0.5Co_1-xFe_xO_3－δ(SSCF)的晶体结构、热膨胀系数、导电率及电化学性能。固相合成的Sm_0.5Sr_0.5Co_1-xFe_xO_3－δ化合物均为单相材料，随着掺Fe量的不同，SSCF的晶体结构发生变化，在0≤x≤0.4时，SSCF为正交晶系钙钛矿结构，在0.5≤x≤0.9时，SSCF为立方晶系钙钛矿结构。Fe掺杂可以显著的改善Sm_0.5Sr_0.5CoO₃的热膨胀系数，随着Fe含量的增加，热膨胀系数减小。在800℃下，SSCF导电率均大于100 S·cm^-1。随着Fe含量的增加，极化电阻增大；含量x=0.4时，极化电阻达到最大值；之后，随Fe含量的增加，极化电阻减小，在700～800 ℃时，Sm_0.5Sr_0.5Co_0.2Fe_0.8O_3－δ表现出了良好的氧催化活性。     

质子导体BaCe0.8Lu0.2O3-α的电性能

采用高温固相法制备了BaCe_0.8Lu_0.2O_3-α质子导体。运用X射线衍射仪（XRD）、扫描电镜（SEM）对该材料的物相结构、微观形貌进行了表征。在500~900℃温度范围内,应用交流阻抗谱和气体浓差电池方法研究了材料在不同气体气氛中的离子导电性和氢-空气燃料电池性能。结果表明,BaCe_0.8Lu_0.2O_3-α材料为单一斜方晶结构,具有良好的致密性。在500~900℃温度范围内,干燥或湿润的氮气、空气和氧气中,材料的电导率随着氧分压增大稍有增大。在湿润的氢气中,材料表现为纯的质子导电性。在以该材料为固体电解质的氢-空气燃料电池条件下,材料表现为质子、氧离子和电子的混合导电性,其中离子导电性始终占主导;氢-空气燃料电池在900℃下的最大输出功率密度为92.2mW·cm^-2,高于我们以前报道的BaCe_0.8RE_0.2O_3-α（RE=Pr,Eu,Ho,Er,等）材料。     

La0.8Sr0.2Ga0.8Mg0.2O3－α陶瓷的质子导电性能研究

采用溶胶-凝胶法合成了La_0.8Sr_0.2Ga_0.8Mg_0.2O_3－a陶瓷样品, 用XRD, DSC-TGA, SEM, 交流阻抗谱, 气体浓差电池及气体电化学透过等方法对样品的结构和性质进行了表征和测试. 首次对该样品的质子导电性能进行了研究. 该陶瓷样品具有良好的微观结构, 相对密度达95.1%; 氢浓差电池电动势的实测值与理论值吻合, 离子迁移数为1; 在干燥的氧气气氛中是一个纯的氧离子导体; 氢的电化学透过速率的实测值与理论值吻合, 证明该样品在氢气气氛中几乎是一个纯的质子导体, 质子电导率在1000 ℃时高达0.14 S•cm^－1.     

La0.9Sr0.1Ga0.8Mg0.2O3-α的微乳液法合成及其质子导电性研究

采用微乳液法合成了La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-α的共沉淀前驱体，经初烧和烧结后制得La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-α陶瓷样品，TEM和SEM分析结果表明陶瓷样品具有良好的微观结构，XRD分析结果表明陶瓷样品已形成了单相的LaGaO₃钙钛     

固-溶法制备中温固体氧化物燃料电池高性能La_(0.8)Sr_(0.2)MnO_3-Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_3阴极（英文）

研究了新型固溶法合成La0.8Sr0.2MnO3(LSM)包覆Ba0.5Sr0.5Co0.8Fe0.2O3(BSCF)复合粉体(LSM-BSCF),并探讨了其作为中温固体氧化物燃料电池阴极材料的电化学性能.LSM-BSCF阴极结合了LSM和BSCF阴极的优点,不仅增大了三相界面,而且稳定了微观结构.当温度为600儃750°C时,其极化阻抗为0.61儃0.09Ω·cm2.与溶液注入法制备的高性能电极相比,极大地提高了性能稳定性.     

Ba1.03Ce0.8Dy0.2O3-α固体电解质的合成及其离子导电性

用高温固相反应法首次合成了非化学计量组成的Ba_1.03Ce_0.8Dy_0.2O_3-α固体电解质样品,对其进行了X-射线衍射晶体结构测定,该样品为钙钛矿型斜方晶单相结构。分别用气体浓差电池方法和氢泵(氢的电化学透过)方法研究了它在600～1000℃下的质子和氧离子导电特性,并与化学计量组成的BaCe_0.8Dy_0.2O_3-α固体电解质样品进行了比较。实验结果表明,Ba_1.03Ce_0.8Dy_0.2O_3-α的质子导电性优于BaCe_0.8Dy_0.2O_3-α。Ba_1.03Ce_0.8Dy_0.2O_3-α在600～1000℃下氢气氛中的质子迁移数约为1,几乎是一个纯质子导体,而BaCe_0.8Dy_0.2O_3-α在氢气氛中600～800℃下是一个纯质子导体,在高于800℃时是一个质子与电子的混合导体。这两个样品在氧气氛中均是氧离子与电子空穴的混合导体,具有几乎相同的氧离子迁移数。     

La0.8Sr0.2Ga0.8Mg0.2O3－α陶瓷的质子导电性能研究

采用溶胶-凝胶法合成了La_0.8Sr_0.2Ga_0.8Mg_0.2O_3－a陶瓷样品, 用XRD, DSC-TGA, SEM, 交流阻抗谱, 气体浓差电池及气体电化学透过等方法对样品的结构和性质进行了表征和测试. 首次对该样品的质子导电性能进行了研究. 该陶瓷样品具有良好的微观结构, 相对密度达95.1%; 氢浓差电池电动势的实测值与理论值吻合, 离子迁移数为1; 在干燥的氧气气氛中是一个纯的氧离子导体; 氢的电化学透过速率的实测值与理论值吻合, 证明该样品在氢气气氛中几乎是一个纯的质子导体, 质子电导率在1000 ℃时高达0.14 S•cm^－1.     

Ba0.4Sr0.6Co1-xFexO3-δ系阴极材料的制备和表征

采用甘氨酸-硝酸盐(GNP)法合成了中温固体氧化物燃料电池阴极材料Ba_0.4Sr_0.6Co_1-xFe_xO_3-δ(x=0.0～0.8)系列粉体。利用XRD和SEM对材料的结构和微观形貌进行分析,用直流四端子法测量了烧结陶瓷体在中温(450～800 ℃)范围内的电导率。结果表明,制备的样品为单一钙钛矿相,随着Fe含量增加,XRD衍射峰值向高角度方向稍有偏移。电导率随着温度及Fe含量的变化出现极大值,在x＜0.2时,Ba_0.4Sr_0.6Co_1-xFe_xO_3-δ系列烧结体在中温(450～800 ℃)区的电导率,随Fe掺入量的增大而增大,x=0.2样品的电导率最高,800 ℃时达244.7 S·cm^-1,远超过文献报道值,进一步增大Fe含量导电性能变差。     

异质双碳源对LiMn0.8Fe0.2PO4复合材料电化学性能的影响

采用水基流变相辅助的固相法,以异质碳蔗糖和石墨为碳源,合成了LiMn_0.8Fe_0.2PO₄/C复合材料,研究了不同石墨加入方式对所制复合材料电化学性能的影响,并对所制备的LiMn_0.8Fe_0.2PO₄/C复合材料进行了X射线衍射(XRD)、N₂吸附-脱附测试、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等表征。结果表明,不同石墨包覆工艺对材料结构和电化学性能具有显著影响。前驱体煅烧后再加入石墨获得的样品纯度高,形貌呈均一的椭圆形,在0.1C下的放电比容量为149 mAh·g^-1,达到其理论比容量的87%;在5C下最大的放电比容量为133 mAh·g^-1;在2C倍率下经过300次循环后比容量维持在127 mAh·g^-1,衰减率仅为1.9%,表现出了优良的循环稳定性。     

High performance protonic ceramic membrane fuel cells (PCMFCs) with Ba0.5Sr0.5Zn0.2Fe0.8O3−δ perovskite cathode

Protonic ceramic membrane fuel cells (PCMFCs) based on proton-conducting electrolytes have attracted much attention because of many advantages, such as low activation energy and high energy efficiency. BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7) electrolyte based PCMFCs with stable Ba_0.5Sr_0.5Zn_0.2Fe_0.8O_3−δ (BSZF) perovskite cathode were investigated. Using thin membrane BZCY7 electrolyte (about 15 μm in thickness) synthesized by a modified Pechini method on NiO-BZCY7 anode support, PCMFCs were assembled and tested by selecting stable BSZF perovskite cathode. An open-circuit potential of 1.015 V, a maximum power density of 486 mW cm⁻², and a low polarization resistance of the electrodes of 0.08 Ω cm² was achieved at 700 °C. The results have indicated that BZCY7 proton-conducting electrolyte with BSZF cathode is a promising material system for the next generation solid oxide fuel cells.     

Effect of stoichiometric ratio of organic fuel to oxidizer on performance of La0.8Sr0.2CoO3 catalysts for CH4 combustion

Perovskite-type La_0.8Sr_0.2CoO₃ mixed oxides were prepared by d,l-alanine solution combustion synthesis and used successfully in CH₄ combustion as catalysts. These samples were characterized by means of XRD, FTIR, BET, and H₂-TPR methods. The effects of stoichiometric ratio (φ) of organic fuel to oxidizer on the structure and catalytic activities of the catalysts were studied. The results indicate that all La_0.8Sr_0.2CoO₃ mixed oxides with different φ have perovskite structures. Their structures and catalytic activities vary along with the change of φ. The catalytic activity of La_0.8Sr_0.2CoO₃ mixed oxide with φ = 1.52 is the best among all the samples, whose T ₅₀ and T ₁₀₀ (the temperatures of methane conversions reaching 50 and 100%, respectively) are respectively 470 °C and 550 °C, which can be explained in terms of the smaller of average crystal size, higher specific surface area, bigger lattice distortion, lower activation energy, and higher mobility of chemically adsorbed oxygen on the surface and vacancy of the catalysts.     

Composite cathode materials Ag-Ba0.5Sr0.5Co0.8Fe0.2O3 for solid oxide fuel cells

Silver-Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-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 Sm_0.2Ce_0.8O_1.9 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 Sm_0.2Ce_0.8O_1.9 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-Gd_0.2Ce_0.8O_1.9 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.     

(La0.8Sr0.2)0.9MnO3–Gd0.2Ce0.8O1.9 composite cathodes prepared from (Gd, Ce)(NO3) x -modified (La0.8Sr0.2)0.9MnO3 for intermediate-temperature solid oxide fuel cells

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, (La_0.8Sr_0.2)_0.9MnO₃ (LSM)–Gd_0.2Ce_0.8O_1.9(GDC) composite powder (LSM ~70 wt%, GDC ~30 wt%) was prepared through modification of LSM powder by Gd_0.2Ce_0.8(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. Gd_0.2Ce_0.8(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)O_2-δ, leading to the significant reduction of electrode polarization resistance of LSM cathode.     

La0.6Sr1.4MnO4 layered perovskite anode material for intermediate temperature solid oxide fuel cells

La_0.6Sr_1.4MnO₄ (LSMO₄) layered perovskite with K₂NiF₄ structure was prepared and evaluated as anode material for La_0.8Sr_0.2Ga_0.83Mg_0.17O_3 − δ (LSGM) electrolyte supported intermediate temperature solid oxide fuel cells (IT-SOFCs). X-ray diffraction results show that LSMO₄ is redox stability. Thermal expansion coefficient of LSMO₄ is close to that of LSGM electrolyte. By adopting LSMO₄ as anode and La_0.6Sr_0.4Co_0.8Fe_0.2O₃ (LSCF) as cathode, maxium power densities of 146.6, 110.9 mW cm^− 2 with H₂ fuel at 850, 800 °C and 47.3 mW cm^− 2 with CH₄ fuel at 800 °C were obtained, respectively. Further, the cell demonstrated a reasonably stable performance under 180 mA cm^− 2 for over 40 h with H₂ fuel at 800 °C.     

A simple and effective strategy to synthesize Al2O3-coated LiNi0.8Co0.2O2 cathode materials for lithium ion battery

A facile method has been developed to synthesize Al₂O₃-coated LiNi_0.8Co_0.2O₂ cathode materials. The sample was characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and energy dispersive analysis of X-rays (EDAX). Electrochemical tests show that the cycling stability of LiNi_0.8Co_0.2O₂ at room temperature is effectively improved by Al₂O₃ coating. The differential scanning calorimetry (DSC) and high temperature (60 °C) cycling tests indicate that Al₂O₃ coating can also improve the thermal stability of LiNi_0.8Co_0.2O₂, which is attributed to that the coating layer can protect the LiNi_0.8Co_0.2O₂ particles from reacting with the electrolyte.     

中温固体氧化物燃料电池La1.6Sr0.4Ni1-xCuxO4阴极材料的制备及电化学性能

采用甘氨酸-硝酸盐法合成了中温固体氧化物燃料电池阴极材料La_1.6Sr_0.4Ni_1-xCu_xO₄ (x=0.2, 0.4, 0.6,0.8), 利用X射线衍射(XRD)和扫描电子显微镜(SEM)对其结构和微观形貌进行了表征. 结果表明, 该阴极材料与固体电解质Ce_0.9Gd_0.1O_1.95(CGO)在1000 °C烧结时不发生化学反应, 且烧结4 h 后, 二者之间可形成良好的接触界面. 利用电化学交流阻抗谱技术对阴极材料的电化学性能进行研究, 结果显示, 当Cu离子掺杂量(x)为0.6 时, La_1.6Sr_0.4Ni_0.4Cu_0.6O₄阴极具有最小的极化电阻, 在空气中当测试温度为750 °C时, 极化电阻为0.35 Ω·cm². 在不同氧分压条件下电化学阻抗谱分析结果表明, 电极上的两个氧还原反应主要包含氧离子从三相界面向电解质CGO 转移的过程和电荷的迁移过程, 其中电荷的迁移过程为电极反应的速率控制步骤.La_1.6Sr_0.4Ni_0.4Cu_0.6O₄电极在空气中700 °C和阴极电流密度为45 mA·cm^-2时, 阴极过电位为45 mV. 本研究的初步结果表明La_1.6Sr_0.4Ni_1-xCu_xO₄材料是一种电化学性能较为优良的新型中温固体氧化物燃料电池(IT-SOFC)阴极材料.     

The chemical and dielectric properties of epoxy/(Ba0.8Sr0.2)(Ti0.9Zr0.1)O3 composites for embedded capacitor application

The characteristics of epoxy/(Ba_0.8Sr_0.2)(Ti_0.9Zr_0.1)O₃ (BSTZ) composites are investigated for the further application in embedded capacitor device. The effects of BSTZ ceramic powder filler ratio on the chemical, physical and dielectric properties of epoxy/BSTZ composites are studied. Differential scanning calorimeter (DSC) thermal analysis is conducted to determine the optimum values of hardener agent, curing temperature, reaction heat, and glass transition temperature (T_g). The hardener reaction process starts at about 115 °C and completes at about 200 °C, for that it is appropriate to process of epoxy/BSTZ composites in the range of temperature. The highest glass transition temperature (T_g) of 155 °C is obtained at one equivalent weight ratio (hardener/epoxy). Only the BSTZ phase can be detected in the XRD patterns of epoxy/BSTZ composites. The more BSTZ ceramic powder is mixed with epoxy, the higher crystalline intensity of tetragonal BSTZ phase are revealed in the XRD patterns. The dielectric constant measured at 1 MHz increases from 5.8 to 23.6 as the content of BSTZ ceramic powder in the epoxy/BSTZ composites increases from 10 to 70 wt%. The loss tangents of the epoxy/BSTZ composites slightly increase with the increase of measurement frequency.     

负载型La0.8Sr0.2MnO3燃烧催化剂的载体效应

Combustion catalysts La0.8Sr0.2MnO3 supported on γ-Al2O3, α-Al2O3, cordierite (2MgO•2Al2O3•5SiO2) and ZrO2 were compared. Further investigation was focused on LSM/ γ-Al2O3 catalyst. It was observed that LSM/γ－Al2O3 catalyst loaded with 20% (mass fraction) LSM (La0.8Sr0.2MnO3 or corresponding oxides), heated at 750℃ or above, perovskite-type oxides were found by XRD examination, whereas, the same catalyst loaded with 10% or less LSM, perovskite oxides were absent, calcination temperature about 750℃ is necessary for the formation of perovskite structure in LSM/γ-Al2O3 catalysts. High activity of complete oxidation of xylen will be obtained when perovskite-type oxides.
Investigation of TPR showed that neat LSM or LSM/γ-Al2O3(20%) was reduced by H2-N2 mixed gas. Two degradation processes took place. In the first, reduced temperature peak was about 350 - 450℃. If reduction ended at 400℃, perovskite structure was retained, which may be due to the reduction of Mn3+to Mn2+ on the surface of LSM only. In the second process, perovskite structure was destroied, and La2O3, Mn2O3, Mn - Sr - O oxides could be obtained, which took place in the temperature range 685 - 750℃ and ended at 800℃. This was proved by TPR experiments (Fig. 3, 5) and XRD patterns (Fig. 4)
Catalysts LSM/γ-Al2O3(10% or 20%) heated at 500℃ have only one TPR peak, i. e. lower temperature peak. This is due to the absence of perovskite-type oxides in the catalysts. However, neat LSM or LSM/γ-Al2O3(20%) heated 750℃ or above, not only the first low temperature TPR peak but also the second peak, which is contributed by the perovskite-type oxides in these catalysts appeared. Therefore, the second TPR peak, i. e. the higher temperatue peak is a characteristic peak for perovskite-type oxides in the reduced process. When LSM/ γ-Al2O3 (10%) catalys is heated at 750℃, no perovskite-type oxides were detected by XRD, and the second reduction peak was absent also in TPR process. \
The order of the second reduction peak temperature(characteristic peak of perovskite - type ox- ides) is: neat LSM(750℃）> LSM/γ-Al2O3 20% (685-698℃) -deposited LSM/γ-Al2O3 (698℃) > LSM/γ-Al2O3 15% (677 - 680℃) >(LSM/γ-AL2O3 10% 620 - 630℃, for Mn - Al - O medium oxides on surface). It is correleted with the increasing of the effect of support sequentially.
When LSM/γ-Al2O3 catalysts were heated at 900℃, more stable phase, spinel MnAl2O4 appeared, which could be proved by TPR of model catalyst MnAl2O4/γ-Al2O3.     

Sol-gel synthesized semiconducting LaCo0.8Fe0.2O3-based powder for thick film NH3 gas sensor

Perovskite type LaCo_xFe_1−xO₃ nanoparticles was synthesized by a sol-gel citrate method. The structural, electrical and sensing characteristics of the LaCo_xFe_1−xO₃ system were investigated. The structural characteristics were performed by using X-ray diffraction (XRD) and transmission electron microscopy (TEM) to examine the phase and morphology of the resultant powder. The XRD pattern shows nanocrystalline solid solution of LaCo_xFe_1−xO₃ with perovskite phase. Electrical properties of synthesized nanoparticles are studied by DC conductivity measurement. The sensor shows high response towards ammonia gas in spite of other reducing gases when x = 0.8. The effect of 0.3 wt.% Pd-doped LaCo_0.8Fe_0.2O₃ on the response and a recovery time was also addressed.