锂离子电池正极材料LiMn2O4的研究进展

具有尖晶石相的LiMn₂O₄因价格低、无毒、无环境污染、制备简单、研究较成熟,因此有着很好的应用前景,被看作最有可能成为新一代商用锂离子二次电池正极材料.由于LiMn₂O₄电化学循环稳定性能不好,表现在可逆容量衰减较大,尤其在高温下(>55℃)使用衰减更严重,从而限制了它的商业化应用.经过近十几年的研究,人们对其衰减机理有了比较清晰的了解,提出了造成容量衰减的几种可能原因如Jahn-Teller畸变效应、Mn²⁺在电解质中的溶解、出现稳定性较差的四方相以及电解质的分解等.通过掺杂、表面包覆、制备工艺的改进,人们已能制得循环稳定性能较好的尖晶相材料.本文结合我们研究小组的最新研究成果对锂离子二次电池正极材料LiMn₂O₄的最新研究进展进行综述和评论.     

S-Co复合掺杂LiMn2O4的合成与性能

为了扩大锂离子电池正极材料LixMn2O4的工作电压范围，在保证良好循环性能的基础上提高材料的容量，本文对S-Co复合掺杂LiMn2O4的合成工艺和电化学性能进行了研究．溶胶-凝胶法合成的各试样均为纯的立方尖晶石相，且结晶状态良好．S—Co复合掺杂综合了S掺杂效应和Co掺杂效应，改善了LiMn2O4的电化学性能，在2．4—4．3V充放电压范围内，初始容量较高，达到170mAh／g，30次循环后容量不但没有衰减而且有一定增加．     

钛掺杂尖晶石LiMn2O4的制备及电化学性能

为解决锂离子电池正极材料LiMn2O4的容量衰减的问题,以TiO2为掺杂体采用固相法制备了LiMn2-xTixO4,并与未掺杂的LiMn2O4进行性能比较.X射线衍射(XRD)和扫描电子显微镜(SEM)分析表明:制备的LiMn2-xTixO4(x≤0.1)具有与LiMn2O4同样的尖晶石结构,并且颗粒形貌随钛的引入得到改善.电化学测试结果显示:钛掺杂能使LiMn2O4的循环性能提高,电化学容量衰减得到抑制.其中LiMn1.995Ti0.005O4具有较好的初始比容量和高温循环性能.     

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。     

阴、阳离子共掺杂合成Li-Mn-O尖晶石锂离子电池正极材料

用传统的高温固相法合成了锂离子电池正极材料LiMn2 O4,LiMn2-x MxO4及LiMn2-xMxO4-yFy(x,y=0.05,M=Al,Mg).充放电结果表明,LiMn2-xMxO04及LiMn2-xMxO4-yFy的循环性能优于LiMn2O4,LiMn2-xMxO4-y,Fy的循环性能优于LiMn2-xMxO4.合成的Al、F共掺杂的材料在循环过程中电化学循环性能良好,首次放电容量为120.6mAh/g,40次循环后,放电容量为114.3mAh/g,容量保持率为94.8%;循环性能相当好,而且放电容量也高,所以有望作为优良的锂离子电池正极材料     

S掺杂LiMn2O4尖晶石的合成与性能

分别用溶胶-凝胶法和固相法合成了锂离子电池正极材料LiMn2O4-xSx,在掺S量x＞0.04时,两种方法都不能获得纯的立方尖晶石相.LiMn2O4-xSx电化学性能测试结果表明,S掺杂对LiMn2O4的4V区性能没有明显的改善,但是在3V区具有良好的循环性能,30次循环后容量不但没有衰减而且有一定的增加.S掺杂对LiMn2O4在3V区的改善作用为扩大材料的工作电压范围、提高材料的初始容量提供了一条可能的途径.     

锂离子电池正极材料LiMn2O4研究现状

作为锂离子电池正极材料的锂锰氧化物体系因其价格便宜、安全、无污染,被认为是锂离子电池中最有发展前景的正极材料,但由于其在高温下的循环性能不好,容量衰减较快,大大影响了其商业化的进程.本文对引起LiMn2O4循环稳定性衰减的原因进行了分析,并综述了当前抑制循环容量衰减、提高电性能的方法.     

锌掺杂正极材料尖晶石LiMn_2O_4的制备及电化学性能

为改善锂离子电池正极材料LiMn2O4的电化学循环性能,以乙酸锂、乙酸锰和乙酸锌为原料,采用固相法制备了LiMn2-xZnxO4(x=0.02、0.04、0.06),并与未掺杂的LiMn2O4进行性能比较。X射线衍射(XRD)和扫描电子显微镜(SEM)分析表明所制备的LiMn2-xZnxO4具有与LiMn2O4同样的尖晶石结构,锌的掺入细化了尖晶石颗粒,增强了Li+在固相中的扩散能力。电化学测试结果显示锌掺杂能抑制LiMn2O4的电化学容量衰减现象,使其循环性能得到显著提高。其中LiMn1.96Zn0.04O4表现出最佳的循环性能,循环20次后放电容量可保持在106.6mAh/g。     

尖晶石LiMn2O4容量衰减的原因及解决方法

尖晶石LiMn2O4被认为是最具发展前景的锂离子电池正极材料,但其容量衰减快和循环性能差是制约其商品化的主要原因.分析了尖晶石LiMn2O4容量衰减快和循环性能差的原因,将其归结为内因和外因;在此基础上,从离子掺杂、表面修饰、电解液改性、合成工艺优化几个方面讨论了改善尖晶石LiMn2O4性能的解决方法.     

镍铬复合掺杂尖晶石锰酸锂的合成与性能研究

采用高温固相合成法制备了LiMn2O4、Ni和Cr以及Ni-Cr复合掺杂的锂离子电池用锰酸锂正极材料.采用扫描电子显微镜、X射线粉末衍射和充放电性能测试等手段研究了材料的形貌、物相和电化学行为.结果表明:掺杂改善了材料的形貌,稳定了材料的结构.样品LiMn1.85Ni0.075Cr0.075O4的表面光滑,粒度分布范围小,为单一的尖晶石结构的物相.其首次放电容量为81.2mAh/g,300次循环后容量保持率为首次的91%,表现出优异的循环性能.     

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.     

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.     

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.     

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.     

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.     

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.     

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.