Structure,Electrical Conducting and Thermal Expansion Properties of Ln0.6Sr0.4Co0.8Fe0.2O3 （Ln = La,Pr, Nd,Sm） Ceramics

Ln0.6Sr0.4Co0.2Fe0.2O3 （Ln=La, Pr, Nd, Sm） perovskite-type complex oxides were synthesized using a glycine-nitrate process, and the structure, electrical conducting and thermal expansion properties of the resulting ceramics were examined with regard to the nature of the lanthanide cations. The results indicated that the La, Pr and Nd specimens had a rhombohedral symmetry, while an orthorhombic structure was determined for the Sm specimen. The pseudo-cubic lattice constant decreased with smaller lanthanide cations. It was found that the electrical conducting properties declined with decreasing lanthanide cation size. Fortunately, all the compositions remained rather high electrical conductivities exceeding 650 Ω ^-1m·cm^-1 in the intermediate temperature range （600-800 ℃）. An appreciable thermal expansion increase at high temperatures was detected for all the compositions. Decreasing the size of the lanthanide cations resulted in an increase of thermal expansion. With respect to the high electrical conductivities, the Ln0.6Sr0.4Co0.8Fe0.2O3 oxides are considered to be acceptable as mixed conducting component in composite cathode designs together with doped ceria electrolytes.     

碱土金属双掺杂铁钴酸镧的制备和表征

柠檬酸法制备了La0.7Ba0.15E0.15Fe0.8Co0.2O3(LBEFC,E=Sr,Ca)系列阴极材料,利用XRD、SEM对LBEFC晶体结构、微观形貌进行分析,采用四探针法测试了LBEFC的电导率。实验结果表明,1 000℃煅烧2 h,LBEFC可以形成单一的畸变钙钛矿结构,LBEFC衍射峰较LaFeO3衍射峰向右偏移,晶胞参数a、b减小,c增大。La0.7Ba0.15Sr0.15Fe0.8Co0.2O3和La0.7Ba0.15Ca0.15Fe0.8Co0.2O3晶胞体积膨胀率分别为43.5%、42.7%,晶格畸变主要发生在(200)、(211)晶面方向。在300~800℃,LBEFC电导率均大于100 S/cm,满足中温固体氧化物燃料电池阴极材料的要求。LBEFC与新型电解质Ce0.8Sm0.2O2在1 200℃下烧结5 h,没有新相生成,具有良好的相容性。     

Structure and Mixed Electronic-ionic Conducting Properties of La0.6Sr0.4Co1-yFeyO3（y= 0-1.0） Ceramics Made by a Citrate Method

La0.6Sr0.4Co1-yFeyO3（y= 0-1.0） powders were synthesized by a citrate method, and the structure and mixed electronic-ionic conducting properties of the resulting ceramics were investigated. The synthesized La0.6Sr0.4Co1-yFeyO3 powders have a pure perovskite structure and consist of uniform and fine particles. A perovskite struciure with rhombohedral symmetry was certified for the La0.6Sr0.4Co1-yFeyO3 ceramics. The increase of Co/Fe ratio significantly promoted the grain growth and microstructural densification. The La0.6Sr0.4Co1-yFeyO3 compositions with relatively higher Co/Fe ratio exhibit superior mixed conducting properties. The electronic structure and microstructure of the ceramics are responsible for the variation of the mixed conducting properties with Co/Fe ratio.     

固体氧化物燃料电池阳极材料La0.8Mg0.2Cr0.8M0.2O3-δ（M=Zn,Al,Zr）的研究

采用Sm0.2Ce0.8O1.9(SDC)作为电解质材料,La0.6Sr0.4Co0.2Fe0.8O3-δ(LSCF)作为阴极材料,以溶胶—凝胶法制备的La0.8Mg0.2Cr0.8Zn0.2O3-δ,La0.8Mg0.2Cr0.8Al0.2O3-δ,La0.8Mg0.2Cr0.8Zr0.2O3-δ粉体作为阳极材料,组装硫氧固体氧化物燃料电池。分别以硫蒸汽和二氧化硫气体为燃料气,测试电池阳极材料性能。结果表明:以硫蒸汽为燃料,La0.8Mg0.2Cr0.8Zn0.2O3-δ在750℃达到最大开路电压420 mV,此时最大功率密度为23 mW/cm2;以二氧化硫为燃料,La0.8Mg0.2Cr0.8Zn0.2O3-δ在650℃获得最大开路电压162 mV,最大功率密度为2 mW/cm2。催化效果顺序为La0.8Mg0.2Cr0.8Zn0.2O3-δ>La0.8Mg0.2Cr0.8Al0.2O3-δ>La0.8Mg0.2Cr0.8Zr0.2O3-δ。     

稀土离子掺杂纳米TiO2的谱学特性研究

采用sol-gel法制备不同稀土元素(La,Ce,Pr,Nd,Sm)掺杂TiO2纳米粒子,采用荧光光谱和紫外-可见漫反射光谱对样品的谱学特性进行对比研究。结果表明,Sm掺杂引起新的发光现象,荧光谱中两个发射峰的强度随Sm掺杂浓度的改变而改变,而其余稀土元素掺杂只影响纯TiO2发射峰的位置和强度;Ce掺杂造成漫反射光谱的吸收边发生红移,且红移幅度随Ce掺杂浓度的改变而改变,其余稀土元素掺杂则造成吸收边蓝移。     

纳米钙钛矿负载型催化剂La_(0.8)Sr_(0.2)Co_(0.8)Mn_(0.2)O_3/γ-Al_2O_3的制备与评价

研制了一种替代净化机动车尾气所用贵金属催化剂的纳米钙钛矿型催化剂 .采用溶胶 -凝胶法制备了B位掺杂的纳米钙钛矿型复合氧化物La0 .8Sr0 .2 Co0 .8Mn0 .2 O3,并将其负载于自制的γ -Al2 O3上 ,于微反在线色谱装置上考察了负载后催化剂对丙烯腈合成反应释放气中的丙烷、CO和丙烯的氧化程度及工艺条件 .确定的最佳工艺条件为 :反应温度为 3 5 5℃ ,氧气体积分数为 89%～ 91% ,空速为 1.3× 10 3h- 1 ;在较宽松的反应条件下 ,丙烷、CO及丙烯的转化率均可达90 %以上 .结果表明 ,催化剂La0 .8Sr0 .2 Co0 .8Mn0 .2 O3/γ -Al2 O3被用于完全氧化反应具有很好的催化氧化活性 .     

La_(0.9)Sr_(0.1)Ga_(0.8-x)Co_xMg_(0.2)O_(3-δ)(x=0,0.05,0.08)的结构和导电性

用固相反应法合成了La0.9Sr0.1Ga0.8-xCoxMg0.2O3-δ(x=0,0.05,0.08))。XRD数据的Rietveld法精修表明其为体心正交结构,空间群Imma。掺Co量增大时,正交晶胞的晶格常数线性降低。采用直流四电极法和Hebb-Wagner极化法测定了总电导率和电子电导率。结果表明,氧离子电导率和总电导率随掺Co量增加而增大;掺Co可降低电导活化能,La0.9Sr0.1Ga0.8-xCoxMg0.2O3-δ对应x=0,0.05,0.08的活化能分别为0.978,0.739,0.489 eV。掺Co量达到0.08时,氧离子迁移数降为0.8。     

基体元素对稀土元素的光谱干扰研究

本文就基体共存元素(Fe、Si、Ba、Sr、Ti、Ca、Mg.Al、Mn、Na以及HCl、HNO_3)对稀土元素(La、Ce、Pr、Nd、Sm)的光谱干扰进行了研究,发现对Ce、Pr的光谱干扰较大,其原因是Ce,Pr具有更复杂的光谱有关。在实用分析中有必要加予注意。     

稀土氢氧化物、氧化物超微粉末的制备及性质研究

本文用醇盐法制备了La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Yb和Y的氢氧化物和氧化物的超微粉末.利用XRD、TEM等手段对其结构、形貌和粒径进行了研究,考察了超微粉末的表面光电压和差热、热重等性质.     

新型中温SOFC阴极Ba_(0.6)Sr_(0.4)Co_(0.9)Nb_(0.1)O_(3-δ)的制备与性能研究

采用固相反应法合成了中温固体氧化物燃料电池(IT-SOFCs)阴极材料Ba0.6Sr0.4Co0.9Nb0.1O3-δ(BSCN)。利用XRD对该材料的结构进行了表征。研究表明,室温下阴极材料BSCN成立方相结构(Pm-3m);将该阴极材料与电解质Ce0.9Gd0.1O1.95(GDC)混合,并在1 000℃煅烧10h后,它们之间无化学反应发生。在SOFCs的操作温度(600～800℃)下,BSCN阴极的电导率可达21～27S/cm。热膨胀测试表明,BSCN的热膨胀系数为17.0×10-6/K,明显低于SrCo0.9Nb0.1O3-δ(SCN)的热膨胀系数,这有利于提高阴极与电解质GDC间的热匹配性。以BSCN作电极,GDC作电解质,制备对称电池BSCN/GDC/BSCN,研究电极与电解质间的极化阻抗。750℃时,极化阻抗仅为0.026Ω.cm2。以BSCN作阴极,NiO-SDC(NiO-Ce0.8Sm0.2O1.9)作阳极,300μm厚的GDC作电解质,制备单电池BSCN/GDC/NiO-SDC。800℃时,单电池的最大功率密度可达782mW/cm2。以上结果表明,BSCN有望成为中温固体氧化物燃料电池阴极的候选材料。     

The conductivity of co-dopant ceria electrolyte

1　IntroductionManyresearchersaregraduallyinterestedinceriaelectrolytesfortheiroutstandingmerits ,especiallyinin termediatetemperaturesolidoxidefuelcell (IT -SOFC) .InIT -SOFCfield ,anode supportedplanarstackisbe comingthemainstream .Therefore ,mechanicalpropertiesofelectrolytesarenolongerimportantfordesiredperfor mance ,andthemainattentionfocusesonhowtoimprovetheionicconductivity .Themainaimsofimprovingtheionicconductivityaretomakethinnerfilmanddevelopnewelectrolyteseriesandco dopantsadd…     

Fe掺杂LSCCF对中低温固体氧化物燃料电池ITSOFC短期输出性能的影响

柠檬酸盐法制备La0.7Sr0.15Ca0.15Co1-xFexO3-δ(x=0.2、0.4、0.6、0.8)阴极材料。该前驱体在900℃处理2h后,XRD证实已经形成完整的钙钛矿结构衍射峰。随Fe掺杂量增加,XRD谱图衍射峰的位置向小角度发生偏移,粉体的晶粒尺寸逐渐变大。SEM观察La0.7Sr0.15Ca0.15Co1-xFexO3-δ粉体其表面活性较高并出现了一定的团聚现象,颗粒尺寸约为5μm。以La0.7Sr0.15Ca0.15Co1-xFexO3-δ为阴极,在氢气/空气中研究了模压法制备的单电池性能,Fe掺杂量对开路电压的高低不起决定性作用,而最高功率密度随Fe掺杂量增加而降低,在650℃最高功率密度由x=0.2时的351.7mW/cm2降为x=0.8时的231.1mW/cm2。     

中温SOFC复合阴极材料BSCN0.6-30%GDC的表征

通过固相反应法制备了钙钛矿氧化物Ba0.6Sr0.4Co0.9Nb0.1O3-δ(简称BSCN0.6),采用XRD对BSCN0.6与Gd0.1Ce0.9O1.95(简称GDC)电解质间的高温化学相容性进行表征。结果表明,BSCN0.6与GDC高温煅烧后存在微弱的固溶反应,但并未对阴极性能造成不利影响。将BSCN0.6与质量分数为30%的GDC复合(简称BSCN0.6-30%GDC)后作SOFC阴极,采用四电极法测电导、热膨胀测试等手段对复合阴极进行表征。结果表明,BSCN0.6与GDC复合降低了材料的电导率,同时也降低了材料的热膨胀系数,提高了阴极与GDC电解质间的热匹配性。以BSCN0.6-30%GDC复合材料作电极,700~800℃时对称电池BSCN0.6-30%GDC//GDC的极化阻抗为0.047~0.012Ω·cm2。因此,BSCN0.6-30%GDC复合材料有望作IT-SOFC的低极化阻抗的阴极材料。     

添加CaF2对烧结稀土永磁体性能的影响

用添加CaF2的方法制备了烧结Nd-Fe-B和烧结Sm-Co复合磁体,并对磁体的性能进行了分析研究.实验结果表明：在添加CaF2的烧结Nd-Fe-B复合磁体的电阻率增大,但其磁性能有一定程度的下降;而添加CaF2的烧结Sm-Co复合磁体,由于制备工艺过程中的氧化问题,导致磁体的磁性能严重下降.扫描电镜分析表明,烧结Sm-Co/CaF2复合磁体中没有形成1∶5相和2∶17R相的微观组织;在烧结Nd-Fe-B/CaF2复合磁体中,CaF2只存在于晶界富Nd相中,对磁体的微观组织没有太大的影响,烧结Nd-Fe-B磁体适合用添加CaF2的方法制备高电阻率的复合磁体.     

Growth and characterization of doped CeO2 buffers on Ni-W substrates for coated conductors using metal organic deposition method

CeO2 and Ce0.8M0.2O2-d films (M = Mn, Y, Gd, Sm, Nd and La) with (00l) preferred orientation have been prepared on biaxially textured Ni-W substrates by metal organic decomposition (MOD) method. The factors influencing the formation of cracks on the surface of these CeO2 and doped CeO2 films on Ni-W substrates were explored by X-ray diffraction (XRD), scanning electron microscopy (SEM) analysis, atomic force microscopy (AFM) and differential scanning calorimetry (DSC). The results indicate that many factors, such as the change of the ionic radii of doping cations, the transformation of crystal structure and the formation of oxygen vacancies in lattices at high annealing temperature, may be related to the formation of cracks on the surface of these films. However, the crack formation shows no dependence on the crystal lattice mismatch degree of the films with Ni-W substrates. Moreover, the suppression of surface cracks is related to the change of intrinsic elasticity of CeO2 film with doping of cations with a larger radius. SEM and AFM investigations of Ce0.8M0.2O2-d (M = Y, Gd, Sm, Nd and La) films reveal the dense, smooth and crack-free microstructure, and their lattice parameters match well with that of YBCO, illuminating that they are potentially suitable to be as buffer layer, especially as cap layer in multi-layer architecture of buffer layer for coated conductors.     

柠檬酸-硝酸盐法制备中温SOFC材料

采用燃烧合成的方法—柠檬酸-硝酸盐法合成中温固体氧化物燃料电池的电解质及电极材料的初始粉末.电池的电解质材料是Ce0.8Gd0.2O1.95(GDC),阴极材料是La0.7Sr0.3Co0.3Fe0.7O3(LSCF),还原前的阳极材料是掺Ce0.8Sm0.2O1.9(SDC)的NiO.借助XRD和TG-DTA等测试手段对材料的晶体结构和反应过程进行了分析.实验结果表明,柠檬酸-硝酸盐燃烧合成法能制备纳米级的电解质及电极材料的初始粉末,燃烧合成中pH值的大小和合成后的烧结温度能很大的影响晶粒的成长和相的生成.     

High Dielectric Constant and Low-loss Dielectric Ceramies of Sr5LnTi3Ta7O3o （Ln= La,Nd, Sm and Y）

Polycrystalline Sr5LnTi3Ta7O30 （Ln=La, Nd, Sm and Y） ceramics were prepared as single-phase materials through conventional solid-state ceramics method. The structure was characterized by X-ray diffraction method and scanning electron microscopy （SEM）. The dielectric properties were measured from room temperature to 400℃. All compounds are paraelectric phases adopting the filled tetragonal tungsten bronze （TB） structure at room temperature. At 1 MHz their dielectric constant （ετ） varied from 109 to 139, dielectric loss changed from 0.003 3 to 0.005 8, and the temperature coefficients of the dielectric constant （τε） moved from -710 to -880×10^-6℃^-1.     

La0.2Ba0．8Co0．8Fe0．2-xZrxO3-δ陶瓷的相组成与导电性能

用固相反应法制备了La0.2Ba0．8Co0．8Fe0．2-xZrxO3-δ（x≤0．10）系列陶瓷样品（简称LBCFZ）,对其相组成和电性能进行了表征。研究表明,常温下的LBCFZ为立方钙钛矿相结构,且当0≤x≤0．08时,其晶胞常数随着Zr掺杂量的增加而线性增大。LBCFZ陶瓷样品的电导率随温度的变化存在明显的转变温度（Tp）：当温度低于Tp时,样品的电导率随着温度升高而增大;当温度高于t时,样品的电导率随着温度升高而减小。另外,LBCFZ样品（x=0．02的样品例外）随着Zr含量的增加,电导率减小,转变温度Tp降低。     

电化学沉积法制备稀土掺杂氧化钇荧光薄膜的发光性能

通过改变氧化钇薄膜中掺杂稀土元素的种类,来控制发光薄膜的荧光发射波长.利用电化学沉积法制备稀土掺杂氧化钇荧光薄膜.电化学沉积法制备的薄膜结晶效果好,掺杂离子分布较均匀,且不需要高温高压或者真空条件,成本很低.所制备的Y2O3:Ln荧光发光薄膜经XRD分析具有立方晶体结构;不同稀土掺杂的氧化钇呈现出不同的表面形貌;掺杂的Ln离子均匀地分布在薄膜中,经测试所有的Y2O3:Ln荧光发光薄膜都显示出较强的发射强度,且发光波长随着掺杂离子的不同而不同:Y2O3:Er3+发绿光,Y2O3:Ce3+发黄绿光,Y2 O3:Sm3+发蓝光,Y2O3:Pr3+发橙光.因此,电化学沉积法可用于制备具有不同发光波长的氧化钇荧光薄膜.     

Crystallization kinetics of amorphous Nd_(3.6)Pr_(5.4)Fe_(83)Co_3B_5 and preparation of α-Fe/Nd_2Fe_(14)B nanocomposite magnets by controlled melt-solidification technique

1　INTRODUCTIONNanocompositeexchangecoupledmagnetsconsistingofafinemixtureofhardandsoftmagneticphaseshaveat tractedmuchattentionforpotentialpermanentmagnetde velopment,sincetheycould ,byexchangecoupling[1] ,potentiallyprovideamaximumenergyproduct [(BH) max]inexcessof 80 0kJ·m- 3[2 ] .Uptonow ,manynanocom positemagnetsystems,includingNd2 Fe14 B/Fe3B ,R2 Fe14 B/Fe,R2 Fe14 C/Fe (R =Nd ,Pr) ,Sm2 Fe17Nx/Fe ,andSm2 (Fe,Si) 17Cx/Fe[3] ,havebeenextensivelystudied .Unfortunately,inprac…