LiNi0.9Co0.1O2正极材料的EDTA络合法合成及其性能研究

采用络合法制备了锂离子电池的活性正极材料LiNi0．9Co0．1O2粉体，实验表明合成的LiNi0．9Co0．1O2粉体结晶良好，层状结构发育完善．电池充放电测试结果表明，其容量及循环性能与LiNi0．9Co0．1O2粉体的合成温度有关，其中900℃合成得到的LiNi0．9Co0．1O2材料具有最好的电化学性能，首次放电比容量高达120．5mAh／g，循环30次后可逆放电比容量仍高达118．8mAh／g，容量损失仅为1．4％．文中对容量退化的原因进行了分析．     

锂离子电池正极材料LiV3O8的低温合成研究

以ＬｉＮＯ_３和ＮＨ_４ＶＯ_３为原料,通过溶胶－凝胶法制备了层状锂钒氧化物ＬｉＶ_３Ｏ_８锂离子电池正极材料,通过ＴＧ－ＤＴＧ、ＸＲＤ等考察了合成条件对产物首次放电比容量的影响．实验结果表明,在４５０℃左右热分解２０ｈ可得到单一相产物ＬｉＶ_３Ｏ_８,其层状结构较为完整,电化学性能好,首次放电比容量可达３５０ｍＡｈ·ｇ－１,作为高能锂离子电池正极材料较为理想．     

以球形α-Ni0.8Co0.2(OH)2制备锂离子电池正极材料LiNi0.8Co0.2O2

LiNio.8Co0.2O2是很有希望取代LiCoO2的新一代锂离子电池正极材料.采用控制结晶法合成球形α-Nio.8Coo.2(OH)2为前驱体,与LiOH@H2O混合,在700℃通O2热处理4h合成锂离子电池正极材料LiNio.8Coo.2O2粉末.X光衍射分析表明合成的LiNio.8Coo.2O2粉末结晶良好,具有规整的α-NaFeO2层状结构.扫描电镜分析表明粉末颗粒呈球形,粒径约8μm.粉末的流动性好,堆积密度高.充放电测试表明,合成的LiNio.8Coo2O2正极材料具有优良的电化学性能首次充电比容量为197mAh.g-1,放电比容量为174mAh.g-1,10次充放电循环后保持初始放电比容量的96.6%.     

锂离子电池正极材料LiNi0.8Co0.15Mo0.05O2的制备与性能

利用具有低共熔组成的LiOH-LiNO3混合锂盐体系,与高密度前驱体混合,经3阶段恒温烧结制备出高密度锂离子电池正极材料LiNi0.8Co0.15Mo0.05O2。X射线衍射分析表明合成的材料具有规整的层状α-NaFeO2结构。SEM显示材料的颗粒均匀。电性能测试表明,在0.2C放电倍率和3.0～4.3V的电压范围内,LiNi0.8Co0.15-Mo0.05O2首次放电比容量达175mAh/g,且具有良好的循环性能。     

锂离子电池正极材料Li1+xV3O8的合成及性能研究

研究了一种新型制备锂离子电池正极材料Li_(1+x)V_3O_8的工艺方法.以NH_4VO_3为原料,通过淬火法制备出V_2O_5溶胶,加入LiOH溶液后,通过喷雾干燥法制备球形前驱体,再通过一定的热处理即制得锂离子电池正极材料Li_(1+x)V_3O_8.试验中,进行了前驱体的DTA/TGA分析;对产物进行了XRD、SEM及电化学性能测试研究.结果表明,经过350℃热处理24h后得到的样品颗粒细小、呈球形、粒径分布均匀、结晶度好,并且还表现出很好的电化学性能,其首次放电比容量高达378mAh·g~(-1),经过10次充放电循环后,其放电比容量为312mAh·g~(-1).     

以Mn3O4为前驱体的LiMn2O4及其电化学性能

对传统的固相反应进行了改进,以控制结晶法合成出来的Mn3O4为前驱体,和LiOH混合煅烧,制备出锂离子电池正极活性材料尖晶石LiMn2O4。对由此方法得到的尖晶石LiMn2O4的结构和电化学性能进行了研究。通过X线光衍射和扫描电镜分析表明,该材料为纯相尖晶石LiMn2O4,不含其它杂质相,而且晶粒大小比较均匀;通过电化学性能测试表明,该尖晶石LiMn2O4具有良好的电化学性能：其首次放电比容量为128mAh/g,经过10次充放电循环后,其放电比容量仍有124mAh/g。     

溶胶-凝胶法制备LiCr0.03Mn1.97O3.95F0.05及其电化学性能

采用溶胶-凝胶法合成了锂离子电池正极材料LiCr0.03Mn1.97O3.95F0.05.使用X射线衍射、扫描电子显微镜对合成材料的结构及物理性能进行了表征.将合成材料作为锂离子电池正极活性材料,考察烧结温度对其结构及电化学性能的影响.随着烧结温度的升高,尖晶石型结构越来越完整,初始放电比容量增大,但循环性能却逐渐变差.在750℃下烧结温度12h得到了性能较好的LiCr0.03Mn1.97O3.95F0.05,首次放电比容量为120.9mAh/g,35次循环后,其放电比容量仍保持在111.8mAh/g,适合作为锂离子电池的正极材料.     

不同沉淀剂对所制备的LiNi0.8Co0.1Mn0.1O2正极材料性能影响的研究

采用共沉淀-高温固相烧结法,控制合成条件,以不同的沉淀剂(Na2CO3、NaOH)制备出正极材料。通过XRD、SEM及电池测试系统对不同沉淀剂制备的正极材料进行结构、形貌和电化学性能的表征,对比两者存在的优缺点。研究结果表明,以NaOH为沉淀剂制备的正极材料有更好的层状结构,形貌也更好,充放电性能和倍率性能也较好。其首次放电比容量达到了187.9mAh/g,最高可达196.2mAh/g,50次充放电循环后,容量保持率为81.6%;以Na2CO3为沉淀剂制备的正极材料的放电比容量较低,但容量保持率较高,为85.3%。     

高致密球形LiNi0.8Co0.1Mn0.1O2颗粒的合成及性能研究

以氨水为络合剂,NaOH为沉淀剂,通过共沉淀制备了高致密、粒度均匀的球形前驱体Ni0.8Co0.1Mn0.1(OH)2.通过焙烧该前驱体和LiOH.H2O的混合物制备出球形锂离子电池正极材料LiNi0.8Co0.1Mn0.1O2.采用XRD、SEM、TEM、TGA/DSC以及恒流充放电测试对材料的结构、形貌和电化学性能进行表征.结果表明,球形前驱体是由纳米级一次颗粒团聚形成,而不是晶粒的长大,且反应时间对前驱体的形貌、粒径分布及振实密度有显著影响.750℃焙烧16 h后的正极材料,保持了完好的球形形貌,具有最佳的层状结构和电化学性能,振实密度最大(2.98 g/cm3),首次放电容量为202.4 mAh/g,倍率性能佳,在3C的放电电流下容量为174.1 mAh/g,且循环性能优良,在40次循环以后,放电容量保持率为92.3%.     

锂离子电池正极材料LiCo1/3Ni1/3Mn1/3O2的研究进展

综述了近几年锂离子电池正极材料层状三元过渡金属氧化物LiCoxNiyMn1-x-yO2的研究进展，重点讨论了综合性能优异的LiCo1/3Ni1/3Mn1/3O2的电化学性能、结构、制备方法以及存在的不足，LiCo1/3Ni1/3Mn1/3O2与其它商业化正极材料相比具有高容量、热稳定性好、高倍率放电等诸多优异的性能，若能解决循环、存放等问题，将有望成为新一代锂离子电池正极材料。     

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.     

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.     

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.     

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.