新型氧离子导体La1.84R0.16Mo1.7W0.3O8.92（R=Ca^2＋、Sr^2＋、Ba^2＋）的制备及其电性能

以La2Mo1.7W0.3O9为本体,在La位进行碱土金属掺杂,采用溶胶-凝胶方法合成新型氧离子导体La1.84R0.16Mo1.7 W0.3O8.92(R=Ca2 、Sr2 、Ba2 ).应用示差热分析(DTA)、X射线衍射(XRD)、拉曼光谱(Raman)等手段对氧化物进行结构表征,交流阻抗谱测试电性能.结果表明:掺杂改善了本体导电性能的同时,保持了La2Mo1.7W0.3O9抑制La2Mo2O9相变的功能;碱土离子的掺杂,在体系中引入了氧空位,有利于氧离子扩散,提高氧离子导电性,773K时Ba2 掺杂体系的电导率为1.0×10-4S/cm,高于本体的电导率(5.0×10-5/cm).     

(La_(1-x)Yb_x)_2Mo_2O_9(x=0.06)陶瓷的制备及其电性能

采用XRD、SEM、电化学工作站等方法对高温固相反应法合成的(La1-xYbx)2Mo2O9(x=0.06)固体电解质材料的电性能进行了研究.粉末XRD结果表明,该样品为单一立方相La2Mo2O9结构.在测定温度范围内,不同气氛下的电导率随温度的升高基本呈线性增大,干燥氧气气氛下表现出较高的电导率,900℃时达到最大值0.066S/cm.(La1-xYbx)2Mo2O9(x=0.06)能完全抑制La2Mo2O9母体的相变.氧分压与电导率的关系表明样品在高氧分压气氛中是离子导体,在低氧分压气氛中是离子与电子的混合导体.     

NiO/La2Mo2O9介电和表面势研究

固体氧化物燃料电池(SOFC)阳极材料得失电子能力和氧扩散性能影响其催化性能。对NiO体积含量分别为20%和40%的NiO/La2Mo2O9复合材料(N/L28和N/L46)的介电行为以及得失电子能力进行了研究。N/L28和N/L46样品的介电温度谱中按照损耗峰出现的温度从低到高的顺序依次发现与NiO相和La2Mo2O9相氧短程扩散有关的损耗峰,833K处观察到的介电损耗的突变与αLa2Mo2O9-βLa2Mo2O9相变有关。N/L46样品在500~813K范围内的一个宽化的损耗峰可用一个具有弛豫性质的峰和两个非弛豫性质的峰进行拟合。表面势测量结果表明,样品失去电子所需能量由大到小的顺序为La2Mo2O9,N/L28,N/L46,NiO。     

La0.6Sr0.4Co1-yFeyO3的混合导电性研究

采用直流四探针法和两端子电子阻塞电极交流阻抗谱研究了GNP法制备La0．6Sr0．4Co1-yFeyO3陶瓷的电子-离子混合导电性能．在室温-900℃范围内，La0．6Sr0．4CoO3的电子电导率随温度的升高而单调降低，其它样品的电子电导率随温度的升高在600℃附近达到最大值．La0．6Sr0．4Co1-yFeyO3陶瓷的氧离子电导率随温度的升高而增加．在相同温度下，随着Co／Fe比例的增加，La0．6Sr0．4Co1-yFeyO3陶瓷的电子电导率和氧离子电导率增加，电子导电活化能和离子导电活化能降低．氧离子迁移数随温度的升高而增加，随Co／Fe比例的增加而降低．     

La_2Mo_(2-x)W_xO_9的氧离子扩散和相变机制研究

采用介电弛豫和内耗技术,并结合XRD技术研究了新型氧离子导体La2Mo2-xWxO9(x=0、0.25、0.5、0.75、1.0、1.2、1.4)的氧离子扩散行为和相变机制.结果表明,在La2Mo2-xWxO9的介电损耗-温度谱和内耗-温度谱上均出现了2个损耗峰,其中低温峰对应氧离子的扩散弛豫过程,高温峰对应氧离子/空位分布的静态无序态到动态无序态的转变.     

Li2O～SiO2～V2O5～SnO2体系的锂快离子导体研究

Li2O～SiO2～V2O5～SnO2四元体系固溶体是锂离子/电子混合导体,本文用均匀试验设计方法研究其电导率随组分的变化规律,寻找电导率最高的配方区域.在选取的试验点中分析了其中的离子和电子电导率的大小比例.选取试验点验证了高电导率区域的电导率变化规律.实验中获得的室温离子电导率最高的快离子导体为2.06×10-4S/cm.     

La0.8Sr0.2CoxFe1-xO3型氧扩散障层材料的制备及结构性能研究

采用共沉淀-凝胶方法制备La0.8Sr0.2CoxFe1-xO3(x=1.0、0、0.3)氧扩散障碍层材料的前驱体,分别用X射线衍射分析、透射电镜、扫描电镜和交流阻抗谱仪对三种不同粉体及其陶瓷结构和性能进行研究.结果表明:在870℃下焙烧制备的La0.8Sr0.2CoxFe1-xO3(x=1.0、0、0.3)粉末具有钙钛矿相结构,无硬团聚,颗粒大小在20～60 nm.此粉末经冷等静压250MPa成型后,在1120℃下烧结6h,La0.8Sr0.2CoO3和La0.8Sr0.2FeO3混合导体的电导率在10—1S/cm数量级,而La0.8Sr0.2Co0.3Fe0.7O3导电率最高达100 S/cm数量级.三种陶瓷都是电子电导远大于离子电导的混合导体,电导率最高值在200～300℃范围,偏向低温.     

NiO/La2Mo2O9介电和表面势研究

固体氧化物燃料电池(SOFC)阳极材料得失电子能力和氧扩散性能影响其催化性能。对NiO体积含量分别为20%和40%的NiO/La2Mo2O9复合材料(N/L28和N/L46)的介电行为以及得失电子能力进行了研究。N/L28和N/L46样品的介电温度谱中按照损耗峰出现的温度从低到高的顺序依次发现与NiO相和La2Mo2O9相氧短程扩 散有关的 损耗峰,833K处 观 察 到 的 介 电 损 耗 的 突 变 与αLa2Mo2O9-βLa2Mo2O9相变有关。N/L46样品在500~813K范围内的一个宽化的损耗峰可用一个具有弛豫性质的峰和两个非弛豫性质的峰进行拟合。表面势测量结果表明,样 品 失 去 电 子 所 需 能 量 由 大 到 小 的 顺 序 为La2Mo2O9,N/L28,N/L46,NiO。     

La2O3掺杂MoSi2的SHS合成及其性能研究

以Mo粉、Si粉和La2O3为原料,通过自蔓延高温燃烧合成(SHS)的方法制备了La2O3掺杂的MoSi2材料．研究表明,掺杂剂La2O3的加入对MoSi2燃烧合成过程的热力学和动力学具有明显的影响．并通过XRD和SEM对燃烧合成产物的物相组成和形貌进行了分析,发现La2O3的加入对合成产物的物相组成没有明显影响,但可以大大降低合成产物的晶粒尺寸．同时,力学性能研究结果表明,La2O3的加入可以提高MoSi2材料的室温断裂韧性．     

BaCe0.4Zr0.3Sn0.1Sm0.2O3-α的中温离子导电性

采用高温固相法合成了Sn4+、Sm3+双掺杂的BaCeO3-BaZrO3固溶体——BaCe0.4Zr0.3Sn0.1Sm0.2O3-α(BCZSS)固体电解质材料,并进行了XRD、SEM测试表征。采用同位素效应、浓差电池等电化学方法研究了样品在873～1073K的离子导电特性。浓差电池测试结果表明样品在湿润氧气气氛中是离子(质子+氧离子)和空穴的混合导体,样品在湿润氢气气氛下存在氧离子导电性。H2O-Ar气氛下的电导率高于相同温度下D2O-Ar气氛下的电导率,表明该样品在含水气氛中是一种优良的质子导体。     

Research status of novel La2Mo2O9-based oxide-ion conductors

La₂Mo₂O₉-based oxide-ion conductors have attracted more and more attention since the high ionic conductivity was reported in 2000 by Lacorre et al. in this kind of material. In this paper the recent investigation on the novel La2Mo2O9-based oxide-ion conductors is reviewed. It is focused on the structure and phase transition, oxide-ion conductivity, mechanism of oxygen vacancy diffusion, chemical stability and thermal expansion coefficient in the pure and doped La₂Mo₂O₉ samples. It is pointed out that the La₂Mo₂O₉-based oxide-ion conductors could be possibly applied in the fields such as solid oxide fuel cells, oxygen sensors and oxygen permeable membranes.     

Synthesis and Characterization of Fine Grained High Density La_2Mo_2O_9-based Oxide-ion Conductors

A cost-efFective technique, including nanocrystalline powder preparation using a modified Pechini method and a two-step low-temperature sintering route, was developed for the synthesis of high performance La2Mo2O9- based oxide-ion conductors. The optimum parameters of the compaction pressure, the first step and ＇the second step sintering temperatures for the synthesis of fine grained, high density and uniform La2Mo2O9- based oxide-ion conductors were determined by a series of sintering experiments. High density and uniform sintered La2Mo2O9 samples with average grain size from 0.8 to 5 μm and La1.96K0.04Mo2O8.96 sample with average grain size as small as 500 nm were synthesized by using this cost-efFective method. The impedance measurement results show that the as-fabricated La2Mo2O9-based ceramics possess much higher ionic conductivity than that obtained by solid state reaction method. It is found that in the range of 0.8-5μm the grain size of dense La2Mo2O9 samples prepared from the nanocrystalline powders has little influence on their conductivities.     

Research status of novel La2Mo2O9-based oxide-ion conductors

La2Mo2O9-based oxide-ion conductors have attracted more and more attention since the high ionic con-ductivity was reported in 2000 by Lacorre et al.in this kind of material.In this paper the recent inv...     

Study on the electrical conductivity and oxygen diffusion of oxide-ion conductors La2Mo2−xTxO9−δ (T = Al, Fe, Mn, Nb, V)

In this paper, the influence of cationic substitutions at Mo site with Al³⁺, Fe³⁺, Mn⁴⁺, Nb⁵⁺ and V⁵⁺ ions on the structure, oxygen ion diffusion and electrical properties in La₂Mo₂O₉ oxide-ion conductors have been investigated by X-ray diffraction method, dielectric relaxation technique and direct current conductivity measurement. Except for V⁵⁺ substitution all of these substitutions up to 5% cannot suppress the phase transition in La₂Mo₂O₉. In the dielectric measurement, one prominent relaxation peak is observed in temperature spectrum as well as in frequency spectrum, which is associated with the short-distance diffusion of oxygen vacancies. The activation energy for oxygen ion diffusion is deduced as in the range of 1-1.1 eV for Al, Fe, Mn and Nb doped samples and 1.4-1.5 eV for V doped samples. All substituted samples have a higher conductivity than the un-doped compound. In the Al, Fe, Mn and Nb substituted materials the phase transition is not suppressed; however, K substitution at the La site can completely suppress the transition and maintains high conductivity at low temperature.     

Relaxation peaks associated with the oxygen-ion diffusion in La2−xBixMo2O9 oxide-ion conductors

The effects of bismuth doping on the oxygen-ion diffusion in oxide-ion conductors La_2−xBi_xMo₂O₉ (x=0.05, 0.1, and 0.15) have been studied by both internal friction and dielectric relaxation techniques. Two internal friction peaks of relaxation type (P₁ and P₂ peak) were observed at a measurement frequency of 4 Hz around 380 and 430 K, respectively. As for the dielectric measurement, a prominent dielectric relaxation peak (P_d) was found in all the Bi-doped samples around 700 K at a measurement frequency of 50 kHz, which actually consists of two sub-peaks (denoted as P_d1 and P_d2 peak). With increasing Bi-doping content, two peaks shift to higher temperature and decrease in height, while the activation energy of both peaks increases. The main reason was interpreted as the introduction of the lone-pair electrons of bismuth, which tends to block the diffusion of oxygen ion.     

Growth of La2Mo2O9 films on porous Al2O3 substrates by radio frequency magnetron sputtering

Synthesis conditions of La₂Mo₂O₉ thin film by radio frequency (RF) sputtering technique on Al₂O₃ ceramic substrates are studied. It is found that the deposition temperature and oxygen partial pressure are the most important factors for obtaining pure La₂Mo₂O₉ films. Varying both parameters, Mo-rich, stoichiometric, and Mo-deficient films are obtained. With increasing the La:Mo ratio, films become denser. A crust layer is observed on top of the Mo-rich and the Mo-deficient films. The formation of the La₂Mo₂O₉ phase is discussed with respect to the sputtering mechanism.     

Al2O3基石油加氢脱硫催化剂研究现状与进展

综述了以三氧化二铝(Al_2O_3)为载体,负载Mo、Ni单一组元和Mo-Ni-W等复合组元,用于炼制石油加氢脱硫的催化剂的国内外研究现状与进展。全面总结了传统的浸渍法、混捏法、共沉淀法、离子交换法以及新型的微波-超声波法等催化剂合成方法,对Al_2O_3基催化剂的加氢脱硫性能进行了讨论,着重对催化剂合成过程中载体、活性组分、助剂(P、F、B等)和pH值对催化剂性能的影响进行了概述,在此基础上总结了Al_2O_3基加氢脱硫催化剂的不足之处,并展望了此类催化剂的发展方向与研究前景。     

La2O3在MgO-Al2O3-SiO2-TiO2微晶玻璃中的作用

在MgO-Al2O3-SiO2-TiO2玻璃中添加不同数量的氧化镧，采用差热分析，X射线衍射及电子显微镜等技术研究了氧化镧对玻璃析晶过程与力学性能的影响。氧化镧的加入使玻璃中析出α－堇青石相的温度降低，同时避免了高膨胀方石英相的析出。随着氧化镧加入量的增加，玻璃整体析晶能力下降，微晶玻璃中晶相含量减少，晶粒尺寸增大，微晶玻璃的弹性模量与硬度减小，断裂韧性增加，体现出大尺寸长柱状金红石晶粒的增韧作用。     

SnP2O7中温固体电解质的制备和导电性能

用固相反应法制备了不同P/Sn物质的量比的SnP2O7,并研究了该电解质在120～260℃范围内的导电性能。XRD分析表明SnP2O7为立方结构。热重分析了电解质在中温范围内的稳定性。用交流阻抗谱测量了电解质电导率,电导率随着HPO3在电解质中的残余量的提高而提高。测试结果表明电解质中起导电作用的主要是HPO3,而SnP2O7主要起支撑作用。最大电导率是在200℃,P/Sn物质的量比为3.0时,干空气条件下为5.1×10-2S/cm,湿空气条件下为6.6×10-2S/cm。     

Nb5+掺杂与热处理对TiO2基材料气敏特性的影响

TiO2是响应三甲胺(TMA)气体最佳的金属氧化物半导体材料，为保持TiO2基TMA旁热式气敏器件具有较高灵敏度和较低空气阻值(Ra)，相应降低器件加热功率PH，本文通过N2气氛高温退火、高价Nb^5 掺杂和长时间烧结等方法，提高TiO2基敏感材料电导率获得成功．实验与理论证明：降低氧分压可增强TiO2自身半导化程度；掺入10％左右Nb2O5，Nb^5 替代Ti^4 形成固溶体，可使TiO2得到最佳半导化效果；采用长时间的烧结处理，促使Ti^3 转化为Ti^4 ，进一步提高材料电导率和器件稳定性，从而为制造低阻、高灵敏度、高选择性动物食品测鲜传感器开辟了一条新途径。