玻璃密封胶与固体氧化物燃料电池元件相容性分析

采用高温熔融法制备了用于固体氧化物燃料电池的一系列SrCO3-Al2O3-SiO2(SAS)系统玻璃陶瓷材料.通过调节封接材料中的SrCO3的含量可以控制玻璃陶瓷的热膨胀性能.结果表明,SrCO3含量为19.85mol%的玻璃陶瓷密封胶在25～850 ℃之间的平均热膨胀系数α为12.52×10-6 K-1,这与La0.8Sr0.2MnO3(LSM)阴极,YSZ电解质和Fe-Cr合金连接体等电池元件之间有良好的热膨胀匹配性.在800～900 ℃范围内,SAS体系密封胶与上述的电池元件有很好的相容性,该密封胶与LSM和YSZ电解质等电池材料之间有很好界面接合性,并且在电池的工作温度下有很好的热稳定性,在850℃烧结120 h以后其失重率基本不再发生变化,在烧结140 h后的失重率仅为0.378%.经放电实验检测,该密封材料的封接性能良好,开路电压为1.03V,放电的最大功率密度为183 mW/cm2.结果表明,SrCO3-Al2O3-SiO2系统玻璃陶瓷密封胶可以作为固体氧化物燃料的封接材料.     

氧化铝、硝酸铝复合YSZ的烧结性能、电性能及力学性能研究

分别以Al2O3、Al(NO3)3为铝源与氧化钇稳定氧化锆（YSZ）机械混合,经干压技术和高温烧结制得YSZ/Al2O3复合材料。通过扫描电子显微镜、电化学交流阻抗谱和三点弯曲测试等方法对样品进行分析,研究了不同铝源和添加量对YSZ电解质烧结性能、电导率及力学性能的影响。结果表明：适量的Al2O3或Al(NO3)3复合均能够促进YSZ的烧结,提高其电导率和弯曲强度;Al2O3作铝源的复合样品的烧结性能和电导率优于Al(NO3)3铝源的,但其强度低于同比例Al(NO3)3铝源。其中,加入0.5 wt.%Al2O3时,所制备的复合电解质经1350 ℃烧结10 h后的相对密度为98.8%;800 ℃时的电导率达0.0703 S·cm-1。基于该材料制备的电解质支撑型单元电池在800 ℃时以氢气为燃料的最大功率密度为308 mW·cm-2,高于纯YSZ电解质电池的,并表现出良好的稳定性。     

三层共烧制备LaCrO3基连接体/复合阳极/YsZ电解质的研究

将La_0.7Ca_0.3Cr_0.97O_3-δ（LCC）连接材料引入到NiO/YSZ阳极中,制备NiO/YSZ/LCC三相复合阳极,并进行烧结特性、微观结构、电导率、热嘭胀系数等性能对比测试.结果表明,NiO/YSZ/LCC新型复合阳极具有优良的综合性能.采用浆料浸渍法在NiO/YSZ/LCC阳极戈撑体两个表面上分别制备LCC和YSZ湿膜,1400℃空气条件下三层共烧4 h后,获得致密LCC连接体和YSZ电解质薄膜.     

纳米NiO-YSZ复合粉体原位合成及电极微结构修饰

采用氨水沉淀原位合成法制备了NiO-YSZ(Y_2O_3稳定的ZrO_2)复合粉体,通过XRD、FESEM研究了溶液pH值对粉体性能的影响,并用干压法和丝网印刷法将氢电极分为支撑层(500 μm)、过渡层(20 μm)和功能层(10 μm)三层进行梯度化制备,采用YSZ/SDC双层电解质,通过共烧结技术将SDC(Sc掺杂CeO_2)(6 μm)作为YSZ(4 μm)电解质和Ba_0.5Sr_0.5Co_0.8Fe_0.2O_(3-δ)(BSCF,20 ìm)氧电极的隔离层.结果表明,合成NiO-YSZ复合粉体的最佳pH值为8.5,粉体呈泡沫状团聚,NiO的平均晶粒粒径为13 nm,产率为94.5%.850 ℃时制备的单体SOEC在70%、80%和90% 3种水蒸气含量的氢电极气氛下,电解池在1.5 V的产氢速率分别为266、381和558 N·mL/cm~2·h.在850 ℃、90%水蒸气含量的氢电极气氛下,以0.33 A/cm~2恒流电解1 h前、后的电解电压分别为1.09和1.16 V,电解池具备较好的稳定性.     

阳极支撑SOFC薄膜电解质制备与性能研究

阳极支撑SOFC具有低阻抗、高功率密度的优点,成为SOFC发展的主要方向.采用丝网印刷、浆料涂敷以及两者复合的工艺制备8 mol%Y2O3稳定ZrO2(YSZ)电解质薄膜.通过在阳极基体中加入不同比例造孔剂来调整阳极收缩率,并采用三步烧结工艺降低YSZ的烧结温度,实现二者共烧.结果表明,加入10%(质量分数.下同)的造孔剂,浆料涂敷修饰的丝网印刷工艺制备的YSZ薄膜在1300～1350℃实现了共烧,YSZ层厚度在20 μm左右,微观形貌显示了良好的致密度,晶粒尺寸在0.5～3μm;阳极支撑层中连通孔较多,有利于气体扩散.     

GDC电解质粉体合成及其性能

采用甘氨酸-硝酸盐法合成了均一、单相、烧结活性高的GDC(Ce0.8Gd0.2O1.9)电解质粉体.利用交流阻抗谱法测定了350℃～700℃范围内GDC烧结体离子电导率.通过多层流延制备了GDC/YSZ/NiO-YSZ(8 mol%yttria-stabilized zirconia)3层复合生坯,共烧后在GDC面丝网印刷LSCF(La0.8Sr0 2Fe0.8Co0.2O3)阴极浆料,烧结得到了表面平整、无开裂的LSCF/GDC/YSZ/NiO-YSZ 4层PEN(Positive-Electrolyte-Negative)结构.     

NiO包覆YSZ固体氧化物燃料电池阳极材料的制备研究

采用包覆沉淀法制备NiO包覆YSZ阳极粉.用包覆沉淀法在YSZ颗粒表面均匀包覆一层氧化镍,600 ℃下煅烧得到NiO-YSZ固体氧化物燃料电池阳极粉.应用此材料制备的SOFC阳极在1400℃烧结4 h.经过SEM扫描电镜分析,高温电导测试,用这种方法制备的SOFC阳极中,NiO分布更加均匀,YSZ、NiO交替排布并有效的连接在一起,使阳极结构得到优化,电池性能提高.     

流延浸渍法制备Cu-CeO2-YSZ固体氧化物燃料电池阳极

通过流延浸渍法制备Cu-CeO2-YSZ阳极,采用淀粉做造孔剂,确定了多孔YSZ基体的制备工艺,主要包括造孔剂用量及流延浆料配比.并通过复合流延制备多孔YSZ支撑的多孔-YSZ/致密-YSZ复合基体,以Pt浆为阴极,通过电池放电考察了氢气条件下多孔YSZ孔隙率、Ce和Cu的浸渍条件等对Cu-CeO2-YSZ阳极性能影响.结果表明,原料中淀粉含量为65%(质量分数),1500℃烧结6 h得到多孔YSZ孔隙率可达到70%左右.采用真空顺次浸渍法制备20%Cu-10?O2-YSZ(质量分数)阳极,其电池800℃时的最大功率密度为113 mW/cm2.     

Fe-40Cr-2Ce合金阳极900℃氧化及电解腐蚀行为

采用真空感应熔炼法制备铝电解用Fe-40Cr-2Ce合金阳极。研究了合金阳极900℃下的氧化和电解腐蚀行为。电解测试采用900℃的NaF-AlF3低温电解质体系,阳极电流密度为0.5 A/cm2,电解时间10 h。结果表明：合金的氧化动力学曲线遵循抛物线规律;合金中高浓度的Ce形成晶界沉淀,造成Ce的＂活性元素效应＂失效。电解后的阳极表面生成连续的FeCr2O4尖晶石相氧化膜。根据热腐蚀酸-碱溶解机理,氧化物在氧化物/电解质界面上的溶解度负梯度造成了阳极表面氧化物的持续的溶解。电解质中高浓度的氧化铝有利于减缓氧化膜的酸性溶解,降低合金阳极的电解腐蚀速率。     

电脱氧法制备Ni基电池材料的研究

利用电脱氧法(FFC)从NiO-CeO2、NiO-SnO2氧化物制备CeNi5、Ni3Sn2.以不同温度烧结的混合氧化物试样作阴极,石墨碳棒作阳极,在850℃的CaCl2熔盐中,3.1 V电压下完成反应.采用SEM和XRD分析电解前后试样形貌及相组成.结果表明:烧结温度越高,试样的孔隙率越低,电解电流越小;不同温度烧结试样可电解出纯CeNi5相,低温烧结试样可电解出纯Ni3Sn2相,产物为疏松的海绵状.本实验为电池材料提供了一种新的制备方法.     

Electrodeposition of NiO/YSZ from hydroalcoholic solutions containing Chitosan

NiO-YSZ films - of thicknesses in the range ca. 1-15 μm - have been fabricated by multi-step galvanostatic deposition from acidic hydroalcoholic solutions of NiCl₂, ZrOCl₂ and YCl₃, containing Chitosan. The crystallographic structure of the electrodeposits has been studied by XRD, their chemical composition has been evaluated by EDX analysis, their morphology has been observed by SEM and optical microscopy and their adhesion has been quantified by the scratch-test method. Deposition-rate measurements have pinpointed some kinetic factors, relevant to process optimisation and bath management. As-plated samples exhibit an X-ray amorphous structure, that can be converted to crystalline fcc-NiO/cubic-fluorite YSZ by heat treatment. The YSZ composition is Y/Zr ca. 0.2 (molar ratio) and does not depend appreciably on processing conditions; the NiO content can be tuned in the range Ni/(Zr + Y) ca. 0.2-2 (molar ratio) by adjusting the electrodeposition parameters.     

氧化钇含量对氧化锆陶瓷微波介电性能的影响

研究了Y2O3含量对钇稳定氧化锆(YSZ)陶瓷微波介电性能的影响.通过热压烧结方法制备了YSZ陶瓷,对材料进行了X射线衍射分析和复介电常数测量.结果表明,当Y2O3含量从2%(摩尔分数)增加到12%时,复介电常数实部在19.49到23.39之间变化.当Y2O3含量为6%时,微波损耗达到最大值0.0789.对YSZ陶瓷的微波损耗机理进行了详细探讨,由于氧离子空位随交变电场的震动和移动而产生的漏导电流是电磁波损耗的主要原因.     

Influence of t-ZrO2 addition on mechanical property and electrical conductivity of YSZ electrolyte

8YSZ material that has high electrical conductivity is widely used as electrolytes for solid oxide fuel cells (SOFCs). But its low strength and low fracture toughness hampered the development of SOFCs. In order to find a best method to improve the capability of YSZ electrolyte, the effects of 3Y-TZP additive on the density, strength, conductivity and microstructure were studied by means of X-ray diffraction and Vicker's hardness apparatus. The strength and conductivity of YSZ electrolyte doped with different amounts of 3Y-TZP were determined. It is shown that the samples sintered at 1450 ℃ for 2 h are the best in properties. When 3Y-TZP powders are added to the YSZ system, the results demonstrate that strength of the electrolyte increases remarkably, and the fracture toughness is improved. The electrical conductivity is lowered only slightly. The results display that the flexural strength and the fracture toughness of ceramics with 30wt.% TZP reach 300 MPa and 3.7 MPa·m1/2 , respectively, and the conductivity at 1000 ℃ reaches 0.11 S·cm-1 .     

Preparation of YSZ solid electrolyte by slip casting and its properties

Fully stabilized YSZ solid electrolyte was prepared by slip casting. The density was measured according to the Archimedes principle and the linear shrinkage was calculated from measuring the sizes of samples before and after sintering. XRD analysis was conducted to verify the phase structure of both the starting YSZ powder and the prepared YSZ electrolyte. The microstructure of fracture surface and the electrical properties of the samples sintered at different temperatures were investigated via SEM and a complex impedance method, respectively. By comparison of the properties and features among the samples, a slip casting method was established to be a simple way to manufacture high-quality YSZ electrolyte at the sintering temperature of 1550℃ for 3 h, which provides a new approach for YSZ electrolyte with com-plex shapes and mass production.     

Preparation of thin film YSZ electrolyte by using electrostatic spray deposition

Yttria-stabilized zirconia (YSZ) thin film was successfully deposited onto Ni–YSZ anode disk by the electrostatic spray deposition (ESD) technique. To deposit a dense YSZ thin film onto porous Ni–YSZ substrate, the influence of process parameter variables were examined. The relationship between process parameters and morphologies of YSZ films coated by ESD was investigated by means of SEM photography and X-ray diffraction (XRD). The result showed that dense YSZ film of average 10–15 μm thickness was deposited on the porous Ni–YSZ substrate with temperature of 400 °C, the precursor solution concentration of 0.05 M, nozzle-to-substrate distance of 30 mm, applied electric field of 18 kV, and deposition time of 90 min.     

SiO2含量对YSZ陶瓷在高温时效中烧结性的影响

研究了SiO2含量对YSZ陶瓷在不同温度下时效后的烧结速率影响,同时研究了其对YSZ时效过程中的结构形貌和性能变化的影响。实验中以正硅酸乙酯(TEOS)为硅源,制备了SiO2含量不同且有约10%气孔的YSZ陶瓷块体,并在不同温度下热处理180 h。通过扫描电镜(SEM)表征了样品的微观形貌,并使用阿基米德法测试得到样品气孔率,同时表征了样品高温时效后的相组成、力学及热学性能的变化。通过交流阻抗谱法初步判断了SiO2在YSZ陶瓷晶界上的分布。研究发现,0.3%(质量分数,下同)SiO2的引入将会使YSZ晶粒尺寸变大且气孔率显著降低,同时其硬度、杨氏模量及热导率的变化率明显较未添加SiO2的要快。     

Influence of Plasma Spray Parameters on the Microstructure and Property of ZrO2-7 wt%Y2O3 Coating

The plasma sprayed ZrO2-7 wt%Y2O3(7YSZ)coating has been widely applied in aircraft engine as a thermal barrier coating.In this study,the duplex TBC system(MCrAlY+7YSZ)were deposited onto 304 stainless steel substrate by APS.Four principal spraying parameters during the deposition of 7YSZ coating were optimized by using orthogonal experimental design,including the stand-off distance,plasma power,preheating temperature and powder feeding rate.Their influences on the coating’s microstructure,adhesion and its mechanical properties were studied and the optimized parameters were finally obtained.The results showed that the dependence of the spraying parameters on the properties of 7YSZ coating is highly correlated to the melting condition of the in-flight particles.     

Research on sintering process of YSZ electrolyte

Yttria stabilized zirconia (YSZ) has widely been used as electrolyte in solid oxide fuel cell (SOFC).The microstructure of YSZ related to the fabrication process was discussed in the paper.With YSZ nano-powders about 40-100 nm as raw material, the YSZ adobe was manufactured by tape calendering process.The named three-step sintering process was performed at 1000 ℃ for 2 h, then raised the temperature with normal rate and as soon as up to 1400 ℃, the furnace was controlled at 1250-1300 ℃ for 10-20 h.The high dense YSZs with the relative density of 96%-99% were obtained; the grain size of YSZ could be reduced to 0.5-3 μm.The above result is benefited to co-fired in the electrode-supported SOFCs.     

Characterization of YSZ solid oxide fuel cells electrolyte deposited by atmospheric plasma spraying and low pressure plasma spraying

Yttria doped zirconia has been widely used as electrolyte materials for solid oxide fuel cells (SOFC). Plasma spraying is a cost-effective process to deposit YSZ electrolyte. In this study, the 8 mol% Y₂O₃ stabilized ZrO₂ (YSZ) layer was deposited by low pressure plasma spraying (LPPS) and atmospheric plasma spraying (APS) with fused-crushed and agglomerated powders to examine the effect of spray method and particle size on the electrical conductivity and gas permeability of YSZ coating. The microstructure of YSZ coating was characterized by scanning electron microscopy and x-ray diffraction analysis. The results showed that the gas permeability was significantly influenced by powder structure. The gas permeability of YSZ coating deposited by fused-crushed powder is one order lower in magnitude than that by agglomerated powder. Moreover, the gas permeability of YSZ deposited by LPPS is lower than that of APS YSZ. The electrical conductivity of the deposits through thickness direction was measured by potentiostat/galvanostat based on three-electrode assembly approach. The electrical conductivity of YSZ coating deposited by low pressure plasma spraying with fused-crushed powder of small particle size was 0.043 S cm⁻¹ at 100 °C, which is about 20% higher than that of atmospheric plasma spraying YSZ with the same powder. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

YSZ热障涂层材料时效分析

以YSZ热障涂层材料(TBCs)在长时间高温时效下发生相变老化为背景,实验利用等离子喷涂制备7YSZ热障涂层陶瓷材料,利用SEM观察其微观形貌,在1300℃对样品进行高温时效测试,利用XRD图谱定量计算样品相组成随时效热处理时间的变化,得到YSZ在1300℃时效下的相组成变化规律。