EDTA络合溶胶凝胶法制备La_(0.8)Sr_(0.2)FeO_3纳米粉体

以金属硝酸盐和乙二胺四乙酸 (EDTA)为原料 ,用EDTA络合溶胶 凝胶法合成了La0 .8Sr0 .2 FeO3 复合氧化物纳米粉体 ,并对过程参数进行了优化。用TG DTA、IR、SEM、XRD等手段对制备过程、热分解机理及粉体的性质进行了研究。硝酸根离子可以加速EDTA 凝胶的热分解 ,仅在 35 0℃就有La0 .8Sr0 .2 FeO3 相生成 ,但此温度下有SrCO3 相出现 ,需经 75 0℃焙烧 2h才能彻底除去 ,得La0 .8Sr0 .2 FeO3 纯相的纳米粉。颗粒呈球形 ,分散性较好 ,平均粒径在 70nm左右。与传统的固相反应相比 ,该法制得的La0 .8Sr0 .2 FeO3 组分均匀 ,化学计量比易于控制 ,烧成温度低。而且 ,由于EDTA可以和元素周期表中绝大多数金属元素络合 ,因此该技术可广泛应用于复杂氧化物体系纳米材料的制备及研究。     

Preparation and performance of Pr-doped Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ) cathode for IT-SOFCs

(Ba0.5Sr0.5)1-xPrxCo0.8Fe0.2O3-δ(BSPCFx;x=0.00-0.30) oxides were synthesized by a sol-gel thermolysis process using combination of PVA and urea,and were also investigated as cathode material for intermediate temperature solid oxide fuel cells(IT-SOFCs).X-ray diffraction(XRD) results showed that all the samples formed a single phase cubic pervoskite-type structure after being calcined at 950 oC for 5 h and the lattice constant decreased with the Pr content increasing.The electrical conductivity of Ba0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) was greatly enhanced by Pr-doping.The thermal expansion coefficient(TEC) of BSPCFx was increased with the content of Pr increasing,and all the thermal expansion curves had an inflection at about 250-400 oC due to the thermal-induced lattice oxygen loss and the reaction of Co and Fe ion.Ac impedance analysis indicated that BSPCFx possessed better electrochemical performance.The polarization resistance of the sample with x=0.2 was only ～0.948 Ω cm2 at 500 oC,significantly lower than that of BSCF(～2.488 Ω cm2).     

La_(0.4)Ca_(0.6)Mn_(1-x)Ga_xO_3体系的电荷有序相

用固相反应法制备La0.4Ca0.6Mn1-xGaxO3(x=0,0.08,0.10,0.12,0.15)系列多晶样品。通过X射线衍射(XRD)图谱、电阻率-温度(ρ-T)曲线、磁化强度-温度(M-T)曲线和电子自旋共振(ESR)图谱,研究Ga3+替代Mn3+对La0.4Ca0.6Mn1-xGaxO3体系电荷有序相的影响。结果表明,当Ga掺杂量高达15%时电荷有序相仍然没有被破坏。这是因为Ga3+是非磁性离子,而La0.4Ca0.6MnO3是CE型反铁磁电荷有序相结构,Ga3+替代Mn3+只是仅仅起到把体系中的长程自旋序破坏为短程自旋序的作用,同时随Ga替代量增大,Mn3+与Mn4+的比远离双交换的最佳摩尔配比(Mn3+∶Mn4+=2∶1),不利于双交换,因而非磁性的Ga3+替代Mn3+难以破坏La0.4Ca0.6MnO3的电荷有序相。     

Synthesis and characterization of Ce_(0.6)Sr_(0.4)Fe_(0.8)Co_(0.2)O_(3–δ) perovskite material:Potential cathode material for low temperature SOFCs

A sol-gel method and a modified chemical vapour deposition technique were used to produce nanostructured Ce_(0.6)Sr_(0.4)Fe_(0.8)Co_(0.2)O_(3–δ) materials at temperatures as low as 400 °C. Powders were characterized using Fourier transform infrared spectroscopy(FTIR), Raman spectroscopy, thermo gravimetric analysis, powder X-ray diffraction(XRD), scanning electron microscopy(SEM) with energy dispersive X-ray spectroscopy, high resolution transmission electron microscopy(HRTEM), and nitrogen sorption at 77 K. FTIR spectra showed that the sol-gel method resulted in residual carbon groups on the materials after calcination, while the Raman and XRD analysis confirmed that both synthesis methods resulted in cubic perovskite structure. However, the chemical vapour deposition(CVD) method resulted in materials with a smaller crystallite size when compared to those prepared via the sol-gel route. The overall morphology of the powders was irregularly shaped aggregated particles as observed by SEM and HRTEM. In addition, HRTEM analysis showed that the materials were highly crystalline. Textural analysis revealed the powders had some mesoporosity, and the surface areas were 76.69 and 65.90 m~2/g for materials synthesized using the CVD and sol-gel methods, respectively. The synthesized perovskite powders were used to fabricate button cells employing samarium doped ceria(SDC) as the electrolyte and NiO/SDC as the anode materials. As cathode materials, the maximum power density observed was 308.4 mW/cm~2 at 500 oC.     

锂离子电池材料LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2的制备与性能研究

以Ni_(0.6)Co_(0.2)Mn_(0.2)(OH)_2与碳酸锂为原料,采用高温固相法制备得锂离子电池正极材料LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2。用X射线衍射、扫描电镜以及充放电测试对样品进行表征,研究了烧结温度对材料电化学性能的影响。结果表明,当烧结温度为880℃时,合成的LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2材料物相单一无杂项,具有标准的的ɑ-Na FeO_2晶型。SEM测试表明,产物为球形且球形度较好,颗粒粒度均一,平均粒度均在10μm。880℃烧结的材料在3.0~4.3 V、0.1 C的倍率下放电比容量可达188 m A·h/g,在1.0 C的倍率下循环10次后电池容量保持率为95.46%,表现出较好的电化学性能。     

Pr0.6 Sr0.4FeO3-δ钙钛矿结构材料的制备与表征

用甘氨酸．硝酸盐（GNP），Pechini，柠檬酸-硝酸盐（CNP）以及尿素-硝酸盐法（UNP）制备了Pr0.6Sr0.4FeO3-δ复合氧化物粉体，通过电感耦合等离子发射光谱（ICP），比表面积测试（BET），粒度分布、热重-差热分析（TG-DTA），傅立叶变换红外光谱（FT-IR）和X射线衍射（XRD）等手段对产物进行了分析和表征。结果表明：4种方法合成的粉体组成与Pr0.6Sr0.4FeO3-δ化学计量比一致；比表面积在9～27m^2·g^-1之间，粒度范围35～110nm，CNP法所得粉体的比表面积最大，UNP法最小；XRD结果证实，Pechini法制备的干凝胶粉在600℃下焙烧即可形成立方结构的钙钛矿相产物；PT-IR结果表明，GNP，CNP及UNP工艺合成的初级粉体中产物物相已基本形成；热分析结果预示，初级产物在1000℃下煅烧，均形成钙钛矿结构的单相固溶体。     

钙钛矿型稀土复合氧化物整体式催化剂的研究进展

概述了钙钛矿型稀土复合氧化物用于燃烧催化剂的发展动态 ,综述了钙钛矿型稀土复合氧化物整体式催化剂的研究进展 ,并分析和归纳了相关的影响因素及其中钙钛矿型稀土复合氧化物粉体的制备技术     

锂离子电池正极材料LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2的制备与性能研究

以自制Ni0.4Co0.2Mn0.4(OH)2前驱体和Li_2CO_3为原料,在空气气氛下采用固相烧结工艺制备了LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2锂离子电池正极材料。通过SEM和XRD等手段对材料烧结前后形貌与结构进行表征,并测试了烧结后锂离子电池正极材料的电化学性能。结果表明,Ni0.4Co0.2Mn0.4(OH)2前驱体具有良好的片状嵌入结构,且烧结制备的LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2正极材料混排因子c/a=4.967 3,阳离子混排因子I(003)/I(104)=1.25、I(006+102)/I(101)=0.333、I(018)/I(110)=0.87,表明LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2具有良好的层状结构。在2.5~4.6V、0.2C和0.5C下,LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2正极材料的首次放电比容量分别为166和154mAh/g,循环80次后容量分别保持为111和100mAh/g,具有良好的电化学性能。     

溶胶-冷冻干燥法制备La1-xCaxCo0.8Ni0.2O3及其性能研究

采用溶胶-冷冻干燥法制备了La1-xCaxCo0.8Ni0.2O3(x=0.1、0.2、0.3、0.4、0.5)催化剂.用X射线衍射(XRD)、比表面测定仪(BET)和扫描电子显微镜(SEM)等分析手段对催化剂的结构和形貌进行了表征,并探讨Ca2+掺杂对催化剂结构和催化活性的影响.结果表明,溶胶-冷冻干燥法可制得单一的钙钛矿型氧化物,最佳焙烧温度为600℃.Ca2+掺杂取代La3+后,当x≤0.3时,催化剂可形成单一的钙钛矿结构,x=0.4、0.5时,催化剂以钙钛矿相和CaO相共存. x=0.2、0.3时,催化剂对CO的催化活性最高(T100%=160℃).     

La_(0.8)Zn_(0.2)MnO_3固体电解质的制备及导电性能

以Mn(NO3)2、La(NO3)3.6H2O和Zn(NO3)2.6H2O为原料,通过溶胶-凝胶法制备单一钙钛矿结构La0.8Zn0.2MnO3(LZMO)。对合成后的LZMO凝胶进行自蔓延燃烧。XRD分析表明,高于873K煅烧后得到的LZMO,粉体形成了钙钛矿结构且没其他杂相。在673~973 K条件下,空气气氛中,用两端阻塞的交流阻抗方法研究了由1 073 K煅烧所得的钙钛矿材料LZMO离子导电性能,表明了该材料在中高温条件下已经具有了非常好的离子导电性能,673~973 K固体电解质的导电率为1.3×10-3~7.4×10-2Ω-1.m-1。应用Arrhenius公式对离子导电的活化能进行计算,求得离子导电活化能为70.17 kJ/mol。     

Influence of calcination temperature for LaTi_(0.2)Fe_(0.8)O_3 on catalytic pyrolysis of bagasse lignin

LaTi_(0.2)Fe_(0.8)O_3(LTF)was prepared by the sol-gel method,and the effects of calcination temperature on the structure and properties were investigated,A new method of preparing aryl oxygen-containing compounds from bagasse lignin(BL)by the catalytic pyrolysis over LTF was proposed.The results show that LTF has cubic crystal phase and porous structure and its optimal calcination temperature is 800 ℃(LTF-800).In the test for catalytic pyrolysis of BL,with the addition of LTF-800,the yield of liquid product reaches the maximum; the contents of phenolics,guaiacols,syringols,phenylates and furans increase obviously,while those of benzenes,esters and carboxylic acid decrease.The total content of aryl oxygencompounds(including phenolics,guaiacols,syringols and phenylates)in liquid product is more than 74 wt%with the addition of LTF-800,larger than that obtained by single BL pyrolysis(62 wt%).LTF could avoid oxygen-containing functional groups from being excessively destroyed.It has nice regeneration performance by controlled combustion of char even after 5 cycles.     

载体对La0.8Sr0.2CoO3燃烧催化剂性能的影响

用浸渍法制备负载型La0.8Sr0.2CoO3燃烧催化剂,比较了γ-Al2O3和堇青石(Cordierite,2MgO·2Al2O3·5SiO2)载体的负载效果和这两种催化剂二甲苯完全氧化的催化活性。利用TPR和XPS等手段对两种催化剂的结构性质进行了表征。     

Production of aryl oxygen-containing compounds by catalytic pyrolysis of bagasse lignin over LaTi_(0.2)Fe_(0.8)O_3 prepared by different methods

To realize the resource and high-value utilization,a new approach,named bagasse lignin(BL) used to produce aryl oxygen-containing compounds by catalytic pyrolysis over perovskite,was proposed,LaTi_(0.2)Fe_(0.8)O_3(LTF) samples prepared by the sol-gel method(SG) and the solid-state reaction method(SS)were characterized.The catalytic action on BL pyrolysis was performed by the test of TG-DTG and the evaluation of the fixed bed micro-reactor,the components and contents of the products were determined.The results show that LTF samples have cubic perovskite phase,LTF prepared by SG(LTF-SG) is porous with larger specific surface area than LTF prepared by SS(LTF-SS).During the pyrolysis of BL,the addition of LTF lowers the pyrolysis temperature and the activation energy,the contents of CO_2 and CO in gaseous products reduce by 4.6%-8.0% and 30.7%-34.3%,respectively,the total content of aryl oxygencontaining compounds(including phenolics,guaiacols,syringols and phenylates) in liquid products increases from 62 wt% to more than 72 wt%,and LTF-SG shows better catalytic performance.LTF samples have nice phase and catalytic stabilities for BL pyrolysis after five successive redox cycles.     

Preparation and Physicochemical Characterization of La1-xCexCoO3+δ Perovskite Catalyst and Its Methane Catalytic Combustion

Perovskite oxide LaCoO3 methane catalytic material was synthesized with citric acid complexation and bubbling method.The effect of doped cerium was studied on the series of La1-xCexCoO3 δ materials by means of BET,XRD and SEM techniques.Their catalytic behaviors were studied with methane catalytic complete combustion as probe reaction.The results show that doped cerium has great effect on crystal phase formation.When doped cerium is less than 0.3 (molar ratio),the crystal phase of oxide has little changed.When doped cerium is up to 0.5,Co3O4 phase is obviously discovered and the perfectibility of LaCoO3 perovskite crystal phase is deteriorated.When x is over 0.7,perovskite crystal phase is weakened or completely disappeared.Considering the crystal phase of oxides,the optimum doped cerium is about 0.3.The perovskite oxides can be formed at a low calcinations temperature of 700 ℃.When x is 0.3,the highest catalytic activity of T10% (390 ℃) and T90% (603 ℃) is obtained on the series of La1-xCexCoO3 δ materials calcined at 800 ℃.     

La_(0.5)Sm_(0.2)Sr_(0.3)MnO_3/Ag_x二相复合体的结构及磁电阻

用固相反应法制备La0.5Sm0.2Sr0.3MnO3/(Ag2O)x/2(x=0.00,0.04,0.08,0.25,0.30)样品,通过X射线衍射谱线(XRD),扫描电子显微镜(SEM)照片及SEM能谱(EDS),ρ-T曲线,研究样品的输运行为及磁电阻效应。结果表明:少量掺杂时Ag全部挥发。掺杂量较多时,挥发后多余的Ag主要以金属态包覆在母体颗粒的表面,使体系形成两相复合体。掺Ag为30%摩尔比时,样品的电阻率较低掺杂样品的电阻率降低一个数量级,在300K、0.5T磁场下,磁电阻明显增强,达到9.4%,这与颗粒母体界面结构的改善有关,也与材料电阻率的降低有关。     

酒石酸-硝酸盐低热固相反应制备Ni_(0.18)Cu_(0.2)Zn_(0.62)O(Fe_2O_3)_(0.98)铁氧体

以酒石酸和金属硝酸盐为原料,采用低热固相反应方法合成了Ni0.18Cu0.2Zn0.62O(Fe2O3)0.98尖晶石型铁氧体,并应用FT-IR,DSC-TG,XRD,TEM以及SEM等技术对低热固相反应过程和样品进行了研究和表征。FT-IR研究表明,酒石酸和金属硝酸盐在研磨30min后发生了低热固相反应,生成金属酒石酸盐前驱体。FT-IR和XRD分析表明,前驱体经不同温度焙烧后得到单一尖晶石相的NiCuZn铁氧体粉。依据谢乐公式计算和TEM表征,证明干凝胶在350℃分解1h后的粒径约为20～30nm,将此粉体在750℃下焙烧2h后,粒径增大到100～150nm。铁氧体于900℃烧结为陶瓷体后,晶粒约为2～4μm,烧结致密。随着烧结温度由850℃提高到900℃,NiCuZn铁氧体的矫顽力Hc有所下降,但饱和磁化强度Ms有所升高。磁谱测量表明,900℃烧结样品的磁导率为170,截止频率为32MHz,样品的磁性主要来源于畴壁位移的贡献。     

Effects of Support on Catalytic Behavior of Combustion Catalyst La0.8Sr0.2CoO3/γ-Al2O3

Combustion catalyst La0.8Sr0.2CoO3 (LSC) is expected to possess relatively high activity for the oxidation of carbon monoxide and many hydrocarbons. If γ-Al2O3 is used as its support, cobalt ions can easily react with γ-Al2O3 at not very high temperature to form spinel CoAl2O4 or spinel-like, which decreases the activity of the combustion catalyst. In this paper, MgAl2O4 and CaAl2O4 were pre-coated on γ-Al2O3 by impregnation respectively, which formed compound support for LSC. It is shown that, when MgAl2O4 layer is covered on the surface of MgAl2O4 by impregnation, the entering of cobalt ions into γ-Al2O3 lattice is restrained, then LSC formed on the surface of MgAl2O4, which leads to a good catalytic activity of xylene complete oxidation. But the layer of MgAl2O4 should be thick enough to reach 30% (mass fraction) MgO in the support due to large size particle of MgAl2O4 crystalline. If polyvinyl alcohol (PVA) is added into the impregnation solution adequately, MgAl2O4 particles formed on the surface of γ-Al2O3 are getting smaller, and less amount of MgAl2O4 is needed to cover up the surface of γ-Al2O3. If CaAl2O4 layer substituted for MgAl2O4, more closed cover is obtained in virtue of fine particles of CaAl2O4. The activity examination shows that smaller particles of MgAl2O4 or CaAl2O4 can be more effective to hinder cobalt ions entering the lattice of γ-Al2O3, and better activities will be obtained.     

Microstructure and electrochemical properties of melt-spun Nd_(0.8)Mg_(0.2)(Ni_(0.8)Co_(0.2))_(3.8) hydrogen storage alloy

The effects of rapid solidification on the microstructure and electrochemical properties of Nd0.8Mg0.2(Ni0.8Co0.2)3.8 alloy were systematically investigated.The microstructure of alloys was characterized by scanning electron microscopy(SEM),X-ray diffractometer(XRD) and transmission electron microscopy(TEM).It was found that the melt-spun Nd0.8Mg0.2(Ni0.8Co0.2)3.8 ribbons became thinner and the average grain size of the ribbons became smaller with increasing wheel speed.A fraction of amorphous phase was observed for the ribbons melt-spun at high wheel speed(≥20 m/s).Microstructural characterization revealed that two phases:(Nd,Mg)2(Ni,Co)7 main phase(Ce2Ni7 type structure) and NdNi5 second phase(CaCu5 type structure),existed in the samples in cast state and melt-spun.The cycle stability of the melt-spun alloys was significantly enhanced as compared with cast alloy,and the sample prepared at wheel speed of 20 m/s exhibited good comprehensive electrochemical properties.