尖晶石型 Li4Ti5O12电极材料的合成与电化学性能研究

分别采用三种方法合成了尖晶石型Li4Ti5O12电极材料.考察了不同的工艺条件对目标材料性能的影响.应用XRD、SEM、LSD、CV、AC impedance以及恒流充放电测试等手段对目标材料进行了结构表征和性能测试.结果表明,利用溶剂分散湿磨可以在较短的时间内得到纯相的Li4Ti5O12.葡萄糖的加入能够提高Li4Ti5O12导电性,使材料具有良好的嵌锂性能.在0.2C倍率下进行充放电测试,其可逆比容量超过160mAh·g-1,44次循环后,容量没有明显衰减.Li4Ti5O12/LiFePO4实验电池测试表明Li4Ti5O12是可选的锂离子负极材料.     

改进固相法制备Li4Ti4.95Nb0.05O12及其性能研究

为提高Li4Ti5O12的导电性和倍率性能,应用二步固相法制备了Nb掺杂的Li4Ti4.95Nb0.05O12负极材料,X射线衍射、扫描电镜、激光粒度分布仪、充放电测试、循环伏安和交流阻抗等测试结果表明,合成的样品具有单一的尖晶石结构和平稳的充放电平台,粒径分布均匀,Nb掺杂改性的Li4Ti5O12具有优良的电化学性能,0.1、0.5、1和10C首次放电比容量分别为174.1、159.7、147和123.3mAh/g。10C下,循环20次后容量保持为118.1mAh/g。     

Si/Li4Ti5O12复合锂离子电池负极材料的制备、结构和电化学性能

本文以纳米Si为原料,通过溶胶-凝胶法,采用不同的煅烧温度,合成了在Si颗粒表面包覆Li4Ti5O12的复合结构材料作为锂离子电池负极材料。结合采用XRD、SEM、TEM、HRTEM和EDS等材料结构分析方法和对合成材料的首次库仑效率、循环稳定性及CV曲线的测试分析,研究了凝胶煅烧温度对合成材料的结构和电化学性能的影响,探讨了Li4Ti5O12的引入对改善Si负极材料循环性能的作用。研究结果表明,在600-800℃的煅烧温度下,溶胶-凝胶过程的产物主要为Li4Ti5O12,产物中Si保持其初始的晶体结构和颗粒特征。提高煅烧温度至1000℃,产物中出现相当量的杂相,大大降低了材料的容量。Si/Li4Ti5O12材料的首次充放电容量随煅烧温度的升高呈现先升高后又下降的变化,并在700℃获得最大值。Li4Ti5O12的引入较明显地改善了Si负极材料的循环稳定性。     

Li_4Ti_5O_(12)的溶胶-凝胶合成及性能研究

研究了一种制备锂离子电池负极材料的Li4Ti5O12新工艺.以醋酸锂和钛酸丁酯为原料,异丙醇为溶剂,采用溶胶-凝胶法制备前驱体,再通过一定的热处理后制备了锂离子电池负极材料Li4Ti5O12采用XRD、SEM及电化学性能测试等分析手段考察了不同热处理温度对产品性能的影响.结果发现,经过850℃热处理24h后得到的产品粒径分布均匀、结晶度好;并且表现出较好的电化学性能,在1～2.5V之间充放电,0.1、1.0和2.0C首次放电比容量分别达到174.5、154.9和124.38mAh/g,并且大电流充放电时具有较好的循环性能.研究表明该方法是适合制备高活性的Li4Ti5O12工艺方法.     

尖晶石钛酸锂的三乙醇胺辅助溶胶-凝胶法合成及其性能

以三乙醇胺为配位剂,Ti(OC4H9)4和LiAc·2H2O为原料,通过溶胶-凝胶法制备锂离子电池负极材料尖晶石Li4Ti5O12。通过X射线衍射、扫描电子显微镜、循环伏安、电化学阻抗和恒流充放电分析检测产物的结构、形貌及电化学性能。结果表明:配位剂的用量对Li4Ti5O12结构及电化学性能有显著影响,其中三乙醇胺与Ti摩尔比为0.8时,Li4Ti5O12具有良好的的电化学性能。1.0C下,其首次放电容量为153.0mAh·g-1,35次循环后放电容量仍为139.9mAh·g-1,容量保持率为91.5%。     

锂离子电池负极材料球形Li4Ti5O12的合成及性能研究

研究了一种制备锂离子电池负极材料Li4Ti5O12的新工艺．以TiCl4为原料,水解制备出Ti4 溶液,通过“外凝胶”法制备出球形前驱体,与Li2CO3按计量比混合均匀,再通过一定的热处理后制备了锂离子电池负极材料球形Li4Ti5O12．采用XRD、SEM及电化学性能测试等分析手段考察了不同热处理温度对产品性能的影响．结果发现,经过800℃热处理16h后得到的产品颗粒呈球形、流动性好、粒径分布均匀、结晶度好;产品具有较高的振实密度,达到1．8g／cm3;并且还表现出较好的电化学性能,在1-3V之间充放电,其首次放电比容量高达160．7mAh·g-1,经过20次充放电循环后,其放电比容量仍有150．2mAh·g-1．研究表明该方法是一种适合制备高密度高活性Li4Ti5O12材料的工艺方法．     

复合熔盐法合成Li4Ti5O12及其电化学性能研究

采用LiOH-LiNO3复合熔盐合成锂离子电池负极材料尖晶石结构Li4Ti5O12,应用XRD、SEM、CV以及恒流充放电测试等手段对所合成材料进行了结构表征和性能测试.结果表明,当反应物中n(Li):n(Ti)=4时合成的样品为纯的尖晶石相Li4Ti5O12,合成所需时间短、熔盐比例低.以电流密度15mA/g进行恒流充放电测试,其首次放电比容量为164.4mAh/g,电压平台宽,平台电压为1.55V.循环15周后放电比容量为156.7mAh/g,容量保持率为95.3%,循环性能优良.     

锂离子电池Li_4Ti_5O_(12)负极材料的尿素掺杂氮化修饰

Li4Ti5O12是最具前景的混合电动汽车用锂离子动力电池负极材料之一.为了提高其倍率性能,以尿素为氮源对Li4Ti5O12进行掺杂热处理,以在Li4Ti5O12颗粒表面自生长一层高电导TiN修饰膜,利用X射线衍射仪、扫描电镜、透射电镜、X射线能谱仪、Raman光谱仪和半电池充放电测试仪研究了材料的物相、结构、形貌、成分以及电化学性能.结果表明:氮化修饰Li4Ti5O12样品与未修饰样品具有相同的尖晶石Li4Ti5O12的衍射峰,氮化修饰后Li4Ti5O12颗粒表面自生长了一层均匀的薄膜,该薄膜不仅含有N元素,而且还具有TiN的Raman光谱特征振动峰;氮化修饰Li4Ti5O12样品的0.1C首次放电比容量比未修饰Li4Ti5O12样品有所降低,但是却展示了优异的电化学倍率性能和循环性能,3C倍率充放电比容量是未修饰Li4Ti5O12样品的2.6倍,0.1C充放电循环100次后其容量损失仅3%.     

Li4Ti5O12合成及电化学性质研究

报道一种合成Li4Ti5O12的新颖方法。XRD结果表明该方法合成的Li4Ti5O12化合物为尖晶石结构。用扫描透射显微镜对该化合物的粒径和形貌进行了分析．并对Li4Ti5O12的电化学性能进行测试。结果表明，通过该法合成的尖晶石材料在3．2-0．8V电压范围，采用一定电流密度下进行充放电，具有较高的放电容量（235mAh／g）和较好的循环性能。该法合成的具有良好电化学性能的Li4Ti5O12,使得其成为很有潜力的锂离子电池负极材料。     

石墨掺杂钛酸锂负极材料的合成及性能研究

以钛酸锂,二氧化钛,石墨为原料采用固相烧结法制备了Li4Ti5O12/graphite复合材料。采用X-射线衍射、扫描电镜和电化学测试等对合成产物进行了表征。结果表明制得的Li4Ti5O12/graphite复合材料的首次可逆容量达到152mAh/g;在0.2C倍率下,经160次循环后,容量仍能保持111.5mAh/g。与纯Li4Ti5O12相比,Li4Ti5O12/graphite复合材料具有更高的可逆容量,表现出较好的循环性能,是一种优良的锂离子电池负极材料。     

Magnetic coupling in La0.67Ca0.33MnO3/La0.67Sr0.33CoO3/La0.67Ca0.33MnO3 sandwiches

La_0.67Ca_0.33MnO₃ (LCMO)/La_0.67Sr_0.33CoO₃ (LSCO)/LCMO trilayer films are fabricated on single-crystal substrates NdGaO₃ (110) and the interlayer coupling are investigated. Compared with LCMO single layer, sandwiches showed the enhanced metal-insulator transition temperature of LCMO layers. The magnetoresistance is dependent on spacer thickness and the peak value dramatically decreases when LSCO layer is thick enough because of shorting by the LSCO layer. The magnetic coercivity H_C shows a nonmonotonic behavior with changing spacer layer thickness and the waist-like hysteresis indicates that there is an indirect exchange coupling between the top and bottom LCMO layers across the spacer layer.     

Varistor properties of ZnO-Pr6O11-CoO-Cr2O3-Y2O3-In2O3 ceramics

The varistor properties of the ZnO-Pr₆O₁₁-CoO-Cr₂O₃-Y₂O₃-In₂O₃ ceramics were investigated for different concentrations of In₂O₃. The increase of In₂O₃ concentration slightly increased the sintered density (5.60-5.63 g/cm³) and slightly decreased the average grain size (3.4-2.9 μm). The breakdown field increased from 6023 to 14822 V/cm with increasing concentration of In₂O₃. The nonlinear coefficient increased from 17.6 to 44.6 for up to 0.005 mol%, whereas the further doping caused it to decrease to 36.8. In₂O₃ acted as an acceptor due to the donor concentration, which decreases in the range of 1.02 × 10¹⁷ to 0.24 × 10¹⁷/cm³ with increasing concentration of In₂O₃.     

Nanocrystallization of SrBi2Nb2O9 from glasses in the system Li2B4O7---SrO---Bi2O3---Nb2O5

Transparent glasses in the system (100−x)Li₂B₄O₇–x(SrO---Bi₂O₃---Nb₂O₅) (10≤x≤60) (in molar ratio) were fabricated by a conventional melt-quenching technique. Amorphous and glassy characteristics of the as-quenched samples were established via X-ray powder diffraction (XRD) and differential thermal analyses (DTA) respectively. Glass–ceramics embedded with strontium bismuth niobate, SrBi₂Nb₂O₉ (SBN) nanocrystals were produced by heat-treating the as-quenched glasses at temperatures higher than 500 °C. Perovskite SBN phase formation through an intermediate fluorite phase in the glass matrix was confirmed by XRD and transmission electron microscopy (TEM). Infrared and Raman spectroscopic studies corroborate the observation of fluorite phase formation. The dielectric constant (_r) and the loss factor (D) for the lithium borate, Li₂B₄O₇ (LBO) glass comprising randomly oriented SBN nanocrystals were determined and compared with those predicted based on the various dielectric mixture rule formalism. The dielectric constant was found to increase with increasing SBN content in LBO glass matrix.     

Syntheses of hollandite type Rb2Cr8O16, K2Cr2V6O16 and K2V8O16

Hollandite-type compounds, Rb₂Cr₈O₁₆, K₂Cr₂V₆O₁₆ and K₂V₈O₁₆, were synthesized under high P-T conditions up to 1200°C and 7GPa. The structural refinement using a single crystal of Rb₂Cr₈O₁₆ confirms that the structure is similar to that of K₂Cr₈O₁₆. Magnetic measurements indicate that Rb₂Cr₈O₁₆ is ferromagnetic below 295K, K₂Cr₂V₆O₁₆ paramagnetic down to 77K and K₂V₈O₁₆ has susceptibility anomaly at 175K. These compounds are all semiconductive and show discontinuities in temperature-resistivity curves at points corresponding to magnetic anomalies.     

PbSbBiS4-Sb2S3 and PbSbBiS4-Bi2S3 joins in the PbS-Sb2S3-Bi2S3 system

Phase equilibria along the PbSbBiS₄-Sb₂S₃ and PbSbBiS₄-Bi₂S₃ joins of the PbS-Sb₂S₃-Bi₂S₃ system have been studied for the first time using differential thermal analysis, X-ray diffraction, microstructural analysis, microhardness tests, and density measurements, and the phase diagrams of the joins have been mapped out. The joins are shown to be pseudobinary with limited series of terminal solid solutions. The solid solutions are p-type semiconductors.     

Microstructures of YBa2Cu3O7/La0.7Ca0.3MnO3 and La0.7Ca0.3MnO3/YBa2Cu3O7 bi-layers grown on (001)LaAlO3

Epitaxial YBa₂Cu₃O₇/La_0.7Ca_0.3MnO₃ (YBCO/LCMO) bi-layers and La_0.7Ca_0.3MnO₃/YBa₂Cu₃O₇ (LCMO/YBCO) bi-layers were grown on (001)LaAlO₃ by pulsed laser deposition, and their microstructures were compared by transmission electron microscopy investigation. In the YBCO(100 nm)/LCMO(150 nm) bi-layers, the LCMO layer consists of columnar grains of ~ 17 nm in diameter and contains mixed orientation domains of [100]_c, [010]_c and [001]_c. The YBCO layer is totally c-axis oriented and the YBCO lattices are tilted − 2.5° to + 2.5° as they grew on the rough surfaces of LCMO columnar grains. For the LCMO(140 nm)/YBCO(140 nm) bi-layers, the LCMO/YBCO interface is sharp and flat. The initial 12-nm thickness of the YBCO layer is composed of c-axis oriented domains, and the upper part of YBCO layer is [100] oriented. The LCMO layer was predominantly [001]_c oriented while [100]_c-oriented domains were occasionally observed.     

Vapour-liquid equilibria in the ternary mixtures N2---CH4---C2H6 and N2---C2H6---C3H8

A systematic study was performed with mixtures consisting of N₂, CH₄, C₂H₆ and C₃H₈, to investigate experimentally phase equilibria and caloric properties and to test the accuracy of thermodynamic correlations. The first part of this Paper reports results of T---p---x---y measurements on ternary systems in the range 20 < p < 120 bar and 140 < T < 220 K. The results are compared with data calculated by generalized equations of state.     

Characterization of YBa2Cu3O7/PrBa2Cu3O7 superlattices

We investigated the structural and superconducting properties ofc-axis oriented (YBa₂Cu₃O₇) _nY /(PrBa₂Cu₃O₇) _npr superlattices with thicknesses of the individual layers down to one unit cell (10nY1; 18>nPr 1). By transmission electron microscopy and X-ray diffraction we find an excellent structural quality of the samples, though the quantitative analysis shows the existence of defects. In superlattices with decoupled YBa₂Cu₃O₇ layers of two unit cell thickness we find a highT _c value of 75 K. We probed the flux line structure in the superlattices by measurements of the critical current density in magnetic fields. The experiments show that the flux-line dynamics is dominated by the movement of pancake vortices.     

Structural study of Sr0.3Ba0.7Nb2O6 and La0.030Sr0.255Ba0.700Nb2O6 ceramic systems

Sr_0.3Ba_0.7Nb₂O₆ (SBN) and La_0.030Sr_0.255Ba_0.700Nb₂O₆ (LSBN) ceramic compounds have been prepared using the traditional ceramic method at two different calcination temperatures (900 and 1000 °C) and later sintered both at 1400 °C. A study of the effects of the calcination temperatures and La substitution on the morphological, compositional, and structural properties of SBN and LSBN is presented using scanning electronic microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD) analysis. From Rietveld refinement processes, the XRD patterns were interpreted to evaluate such effects in the structural parameters and the site occupation factors of the heavy metals and oxygen atoms. The effect of the incorporation of La resulted in a 0.25% cell contraction and turned out to be higher than the 0.08% dilation effect produced by the increase of calcination temperature. The La ion with similar effective ionic radius and higher electronegativity is incorporated into the structure occupying the A₁ site just like the Sr ions in the SBN compound. Differences in the site occupation factors between the SBN and LSBN samples lead to substantial changes in the physical properties such as temperature of relative dielectric constant maximum, relative dielectric constant, and dielectric loss, correlated with the distortion and the relative orientation of the oxygen octahedra.     

The effect of Bi1.5Zn0.5Nb0.5Ti1.5O7 cover layer on the dielectric and tunable properties of Ba0.6Sr0.4TiO3/Bi1.5Zn0.5Nb0.5Ti1.5O7 bilayered thin films

Bi_1.5Zn_0.5Nb_0.5Ti_1.5O₇ (BZNT) thin films with different thicknesses as cover layers were deposited on the Ba_0.6Sr_0.4TiO₃ (BST) thin films on the Pt/Ti/SiO₂/Si substrates by radio frequency magnetron sputtering method. The microstructure, surface morphology, dielectric and tunable properties of BST/BZNT heterogeneous bilayered films were investigated as a function of the thickness of BZNT films and the effect of BZNT films on the asymmetric electrical properties of BST/BZNT bilayered films was discussed. It was found that BZNT cover layer significantly improved the leakage current and the dielectric loss, and the dielectric constant and tunability of BST/BZNT bilayered thin films simultaneously decreased with the increasing thickness of BZNT films. The BST/BZNT bilayered thin film with a 50 nm BZNT cover layer gave the largest figure of merit (FOM) of 33.48 with the upper tunability of 55.38%. The asymmetric electrical behavior of BST/BZNT bilayered films is probably related to an internal electric field caused by built-in voltages at Pt/BST and BZNT/Au interfaces.