锂离子蓄电池正极材料Li_(1+δ)M_xV_(3-x)O_8的合成与电化学性能研究

锂钒氧化物Li1+δV3O8具有比容量高、循环寿命长、价格低等优点,因此它是一种非常有应用前景的锂离子蓄电池正极材料。作者采用传统的高温固相反应法合成了Ti、Fe、Ni、Co4种过渡金属元素部分取代Li1+δV3O8中钒的掺杂产物Li1+δMxV3-xO8,研究了不同掺杂元素及其掺杂量对材料电化学性能的影响。结果表明,掺杂Ti元素且掺杂量x≤0.1时,掺杂对材料的性能有一定的改善。掺杂没有提高其放电电压平台,降低了其比容量。但掺杂对其循环性能没有明显影响。综合考虑电化学性能,掺杂少量Ti比较适宜。     

过渡金属掺杂BaTiO3的晶格结构和相变特性

采用溶胶-凝胶法制备纯净BaTiO3,将1.0mol%的Cr、Fe、Mn、Co掺杂BaTiO3和浓度分别为1.25mol%、1.5mol%、1.75mol%、2.0mol%的Fe掺杂BaTiO3前驱粉体,经热压烧结,并在1350℃下烧结成多晶陶瓷样品。对样品进行XRD和DSC表征的研究。分析了掺杂离子种类和浓度对样品的晶格四方性、相变温度(居里点)和相变潜热的影响。分析结果表明,掺杂BaTiO3的四方性、居里点和相变潜热低于纯净BaTiO3且随Cr、Fe、Mn、Co的掺杂顺序以及Fe掺杂浓度的增加而减少。过渡元素掺杂BaTiO3的居里点和相变潜热随晶格四方性的降低逐渐减小。     

过渡金属掺杂BaTiO3的晶格结构和相变特性

采用溶胶一凝胶法制备纯净BaTiO3,将1．0mol％的Cr、Fe、Mn、Co掺杂BaTiO2和浓度分别为1．25mol％、1．5mol％、1．75mol％、2．0mol％的Fe掺杂BaTiO2前驱粉体,经热压烧结,并在1350℃下烧结成多晶陶瓷样品。对样品进行XRD和DSC表征的研究。分析了掺杂离子种类和浓度对样品的晶格四方性、相变温度（居里点）和相变潜热的影响。分析结果表明,掺杂BaTiO2的四方性、居里点和相变潜热低于纯净BaTiO。且随Cr、Fe、Mn、Co的掺杂顺序以及Fe掺杂浓度的增加而减少。过渡元素掺杂BaTiO2的居里点和相变潜热髓晶格四方性的降低逐渐减小。     

Cr3+离子在硅酸三钙中的固溶行为

通过制备纯C3S和掺杂Cr2O3的C3S样品,采用ICP、XRD、IR、SEM等测试方法研究了掺杂Cr3+离子对C3S晶体结构及性能的影响,Cr3+离子在C3S矿物中的最大固溶量.结果表明:原料中掺杂2％ Cr3+离子,使得C3S的晶型发生改变;掺量超过4％时,将造成C3S矿物分解.Cr3+离子的掺杂将提高C3S晶体结构对称性,加速早期水化速率.     

锂离子蓄电池正极材料Li1+δMxV3-xO8 的合成与电化学性能研究

锂钒氧化物Li1 δV3O8具有比容量高、循环寿命长、价格低等优点,因此它是一种非常有应用前景的锂离子蓄电池正极材料。作者采用传统的高温固相反应法合成了Ti、Fe、Ni、Co4种过渡金属元素部分取代Li1 δV3O8中钒的掺杂产物Li1 δMxV3-xO8,研究了不同掺杂元素及其掺杂量对材料电化学性能的影响。结果表明,掺杂Ti元素且掺杂量X≤0．1时,掺杂对材料的性能有一定的改善。掺杂没有提高其放电电压平台,降低了其比容量。但掺杂对其循环性能没有明显影响。综合考虑电化学性能。掺杂少量Ti比较适宜。     

过渡金属离子对渗花黑釉砖呈色的影响

本文运用正交法法,探讨了过渡金属Ni2 、Cu2 、Co2 、Fe3 、Cr6 离子用于呈黑色渗花釉的影响。     

核桃青皮醇提取物对棉织物染色性能的研究

为解决天然染料核桃青皮染色色调单一的问题,以颜色特征值和染色牢度为指标,通过单因素和正交实验优化了影响染色效果的温度、时间、p H值及核桃青皮色素染液的质量浓度等条件,比较了单金属盐的不同媒染方法、复合金属盐复配的不同配方对纯棉织物染色性能的影响。结果表明:核桃青皮色素染色的优化条件为温度90℃、质量浓度71.40 g/L、染浴p H=4.0、时间140 min。核桃青皮提取液染色棉织物色谱范围广,染色深度(k/s值)分布范围从2.55到16.09,耐摩擦牢度均在4级以上;单金属盐媒染的耐皂洗牢度后媒预媒同浴直接染色,复合金属盐复配及Fe3+、Fe2+、Cu2+、Al3+、Cr6+等单金属盐媒染的耐皂洗色牢度均能达到3级以上。X-射线衍射及紫外透过率测试结果表明:棉织物内部结构未受影响,Fe3+、Fe2+、Cr6+、Sr2+、Na+和K+等单金属盐和Fe2+/Cu2+、Fe2+/Ti4+、Cu2+/Ti4+、Cu2+/Sn2+、Al3+/Cr6+、Cr6+/Ti4+和Cr6+/Sn2+等复合金属盐媒染后的棉织物紫外线防护能力增强。     

水杨醛型Schiff碱配合物的合成、表征与磁性研究

以乙醇为溶剂、水杨醛缩邻氨基苯酚(L)与过渡金属(M)硝酸盐或醋酸盐作用,制得了6个LM及6个L2M配合物(合成过程中须将反应混合液蒸馏至干才能得到Cr、Fe、Ni的配合物)。对所制备的配合物进行了摩尔电导、磁化率、DTA、SEM、UV、IR等表征。结果表明:LM(M=Cr3+、Mn2+、Fe3+、Co2+)为平面正方形场低自旋型;LNi、LCu及L2M(M=Mn2+,Co2+,Cu2+)为四面体场高自旋型;其余经蒸馏得到的L2M(M=Cr3+,Fe3+,Ni2+)则为八面体场配合物。配合物均为顺磁性,除LCr、LFe、LCu及L2Cu也有电子轨道运动的贡献外,磁性主要是电子自旋运动的贡献,LM分子中有水参与配位,并有分子内氢键形成。     

核桃青皮醇提物对棉织物染色性能的研究

为解决天然染料核桃青皮染色色调单一的问题,以颜色特征值和染色牢度为指标,通过单因素和正交实验优化了影响染色效果的温度、时间、pH值及核桃青皮色素染液的质量浓度等因素,比较了单金属盐的不同媒染方法和双金属盐复配对纯棉织物染色性能的影响。结果表明,核桃青皮色素染色的优化条件为：温度90oC、质量浓度71.40 g/L、染浴pH=4.0、时间140 min。核桃青皮提取液染色棉织物色谱的范围广,耐摩擦牢度好;耐皂洗牢度上单金属盐媒染是后媒＞前媒＞同浴＞直接染色,双金属盐复配及Fe3+、Fe2+、Cu2+、Al3+、Cr6+等单金属盐媒染的耐皂洗色牢度均能达到3级以上。X-射线衍射分析表明棉织物内部结构未受影响,Fe3+、Fe2+、Cr6+、Sr2+、Na+和K+等单金属盐和Fe2+/Cu2+、Fe2+/Ti4+、Cu2+/Ti4+、Cu2+/Sn2+、Al3+/Cr6+、Cr6+/Ti4+和Cr6+/Sn2+等双金属盐媒染后的棉织物紫外线防护能力增强。     

四氧化三锰制备掺杂LiMn_2O_4及其性质研究

以Mn3O4、Li2CO3、Co3O4、Al2O3和NiCO_3为原料,固相法合成Co、Al、Ni掺杂LiMn_2O_4。采用X-射线衍射、扫描电子显微镜、恒电流充放电和电化学阻抗等技术研究合成材料的结构、形貌及电化学性能。结果表明:Co、Al、Ni掺杂没有改变LiMn_2O_4的晶体结构,但晶格常数略有减小。掺杂后LiMn_2O_4晶粒规整,表面光滑,晶粒形貌差别不大。掺杂后LiMn_2O_4的比容量有所下降,循环性能得到改善,容量保持率是Li Co0.05Mn1.95O4Li Ni0.05Mn1.95O4Li Al0.05Mn1.95O4LiMn_2O_4。Li Co0.05Mn1.95O4的循环性能最好。掺杂后LiMn_2O_4锂离子扩散系数有所提升,其中Li Co0.05Mn1.95O4的锂离子扩散系最大。     

Alkoxide-Hydroxide Route to Syntheltize BaTiO3-Based Powders

When preparing homogeneous, fine barium titanate powders, the major difficulty is to avoid the spontaneous self-condensation between the Ti-OH groups. In the usual way of preparing fine barium titanate powders, chelating agents (citrate, oxalate) or simply unidentate ligands (alkoxy or carboxyl groups) are used to complex titanium atoms. Another way is to mix barium and titanium precursors in a strongly basic medium. The condensation between the Ti(OH)^2-₆Ba²⁺ species directly gives the perovskite compound. Using an alkoxide-hydroxide route, a homogeneous Ba-Ti solution was prepared that completely advanced by condensation between the Ti(OH)^2-₆Ba²⁺ species and led to a controlled-stoichiometry powder. Concerning pure barium titanate, dried powders exhibited the cubic perovskite structure, and a direct sintering at 1150°C, without calcination, led to highly dense BaTiO₃ bodies with fine-grained uniform microstructure (1 μm) that exhibited a high permittivity value at room temperature ( K = 5400). The alkoxide-hydroxide method was also used to prepare dense alkaline-earth perovskite ceramics with complex compositions.     

Density functional theory investigation of site predilection of Fe substitution in barium titanate

The site predilection and effects of the impurity in the form of Fe (II) and Fe (III) in the tetragonal barium titanate lattice were systematically determined by density function theory calculations. All electron calculation was carried out in the local density approximation (LDA). It is shown that both Fe (II) and Fe (III) prefer to substitute at the titanium site with oxygen vacancy compensation as a result of lowest substitution energy. Effect of Fe dopant both in form of Fe (II) and Fe (III) at titanium site with oxygen vacancy compensation lead to change in electrical property in terms of energy band structure of the tetragonal barium titanate lattice.     

Vanadium doping effects on microstructure and dielectric properties of barium titanate ceramics

V-doped barium titante ceramics were prepared by conventional solid state reaction method. XRD patterns show that V⁵⁺ ions have entered into the tetragonal perovskite structure of solid solution to substitute for Ti⁴⁺ ions on the B sites. Addition of vanadium accelerates grain growth of BTO ceramics and there is abnormal grain growth of barium titanate ceramics with higher vanadium concentration. Vanadium doping can increase the Curie temperature and decrease the dielectric loss of barium titanate ceramics. As vanadium concentration increases, the remnant polarization of V-doped BTO ceramics begins to increase and reaches the maximum and then decreases. The coercive electric field for V-doped barium titanate ceramics decreases with the increasing of vanadium concentration. As temperature rises, the remnant polarization and the coercive electric field of V-doped barium titanate ceramics decrease simultaneously.     

超声化学法制备高纯钛酸钡的工艺研究

以氯化钡和钛酸丁酯为原料,采用超声化学法制备高纯钛酸钡（BaTiO3）粉体。利用X衍射分析、扫描探针、激光粒度仪等检测方法对样品进行表征。研究超声化学法制备高纯钛酸钡的方法和影响因素,对比研究了超声化学法与传统化学沉淀法制备对粉体粒度的影响。结果表明,将反应的pH控制在3左右,反应物的n（钡）/n（钛）控制在1∶（1～1.02）时,超声化学法制备的钛酸钡为立方相,且为均匀的球形,粒度为100 nm,纯度为99.82%。     

Antimonates as Additives to Barium Titanate Dielectric Bodies

Antimonates of a number of the alkalis and alkaline earths and of several other metals were prepared and their ceramic and dielectric properties were determined. Only porous bodies could be produced from the individual anti-monates. Dielectric measurements on these bodies showed that they all had relatively low dielectric constants. The properties of dielectric bodies in the binary systems composed of the an-timonates of sodium, lithium, barium, strontium, magnesium, and lead plus barium titanate were determined. Additions of all the antimonates except that of magnesium had a depressing effect on the Curie peak of barium titanate, resulting in bodies with dielectric constants of 2000 or less, which showed relatively little variation with temperature. The addition of magnesium orthoantimonate to barium titanate produced a very rapid downward shift in the temperature of the Curie peak. X-ray studies showed that the antimonates of barium, strontium, sodium, and magnesium, when added to barium titanate in small amounts, formed solid solutions with slightly expanded lattice structures.     

Peroxo-oxalate Preparation of Doped Barium Titanate

The peroxo-oxalate complexation method is a method that can be used for the preparation of doped barium titanate. In this paper we focus on BaTi_0.91Zr_0.09O₃, which can be used for discharge capacitors in lamp starters. The preparation method described here is based on the complexation and subsequent precipitation in basic environment of Ba, Ti, and Zr ions with hydrogen peroxide and oxalate. The influence of several process parameters, like precipitation temperature and pH, on powder properties is described. A single-phase perovskite crystal structure is obtained after calcination starting from a chloride precursor solution using a precipitation temperature of 40°C and a pH of 9. Because the peroxo-oxalate process starts with inexpensive chlorides and is performed in air, the peroxo-oxalate process is suitable for the commercial production of doped barium titanate.     

Optical Absorption in Sol-Gel-Derived Crystalline Barium Titanium Fine Particles

Pure, translucent, and highly crystallized barium titanate (BaTiO₃) monolithic gels were synthesized via a sol-gel technique at temperatures down to 90°C by using a high-concentration solution of barium alkoxide and titanium alkoxide. The gels consisted of fine particles with an average diameter of ~10 nm and showed the X-ray diffraction patterns of a pseudo-cubic BaTiO₃ system at room temperature; however, in bulk crystal, the tetragonal structure was more stable. The optical transmission spectra of the polycrystalline gels were similar to those for single-crystalline BaTiO₃. From the excitation energy dependence of the absorption-edge structures, the optical-gap energies for the gels were estimated to have values that were ~0.1 eV higher than those for the single crystal; these higher optical-gap energies may be attributed to size effects.     

Effects of Excess Barium Ions on Aqueous Barium Titanate Tape Properties

The effects of excess free barium ions in aqueous barium titanate slip on the resulting BaTiO₃ tape properties were investigated in terms of the slip behavior, green/sintered tape density and morphology, and dielectric properties. The excess free barium ions expressed by means of the Ba/Ti ratio adversely affected most tape properties. Increase in the slip viscosity, green porosity, and agglomeration along with a decrease in mechanical properties and green/sintered density were found with the increase in the Ba/Ti ratio. However, dielectric permittivity was increased with increase in the Ba/Ti ratio. An effort was made to correlate these phenomena with Ba²⁺ leaching in water for realistic multilayer ceramic capacitor applications.     

Crystallographic Properties of Hydrothermal Barium Titanate Crystallites

The crystallographic properties and defects of hydrothermally grown barium titanate crystallites are reported. When a precursor with a Ba:Ti molar ratio of 1.0 was used, cubic barium titanate crystallites were formed. However, when the precursor Ba:Ti molar ratio was 3.0, the product was tetragonal. The defect concentration (including OH defects and barium vacancies) was higher in cubic crystallites than in tetragonal crystallites. Because of the defects in the crystallites, the displacement of Ba²⁺ cations and the deformation of the Ti-O₆ octahedrons was suppressed; thus, no phase transition from cubic to tetragonal occurred at the Curie point. When the defects were eliminated by thermal treatment, the normal crystallographic properties were obtained. A high reaction temperature and a high Ba:Ti molar ratio in the precursor were beneficial to limiting defect dormation in the crystallites; thus, tetragonal crystallites were obtained.     

BaO过量的钛酸钡中施主Sb的取代位置

Sb仅在低浓度掺杂时,才能使BaTiO_3半导化。对该现象的解释,先需弄清楚Sb在BaTiO_3晶格中的位置。本文运用缺陷化学理论,分析了Sb掺杂BaTiO_3电导率和氧分压之间的关系,提出BaO过量时,Sb位于BaTiO_3晶格中的Ti位,形成电子补偿,导致BaTiO_3半导化的机理。