以Mn_3O_4为前驱体的LiMn_2O_4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．     

温度对燃烧包覆LiMn2O4/ZnO及其电性能的影响

通过葡萄糖辅助低温燃烧制备ZnO包覆型LiMn2O4,利用X射线衍射仪、扫描电子显微镜、循环伏安、交流阻抗以及恒流充放电测试等手段,研究了温度对产物晶体结构、微观形貌及电化学性能的影响。XRD结果表明所有产物均为单相尖晶石型LiMn2O4结构。SEM结果表明产物的颗粒尺寸随温度的升高而增大。电化学性能测试表明400℃和500℃制备的LiMn2O4/ZnO具有相对优异的电化学性能,室温1C条件下首次放电比容量分别为119.3mAh/g、116.3mAh/g,循环100次后容量保持率分别85.6%、87.8%。尖晶石LiMn2O4电极的阻抗谱特征与温度有关,电池的电化学性能主要受电荷转移电阻(Rct)影响。     

Co^3＋—modified Surface of LiMn2O4 Spinel for its Improvementof Electrochemical Properties

Cobalt was used to modify the surface of spinel LiMn2O4 by a solution technique to produce Co^3 -modified surface material (COMSM). Cobalt was only doped into the surface of LiMn2O4 spinel. XPS(X-ray photoelectron spectroscopy) analysis confirms the valence state of Co^3 . COMSM has stable spinel structure and can prevent active materials from the corrosion of electrolyte. The ICP(inductively coupled plasma) determination of the spinel dissolution in electrolyte showed the content of Mn dissolved from COMSM was smaller than that from the pure spinel. AC impedance patterns show that the charge-transfer resistance (Rct) for COMSM is smaller than that for pure spinel. The particles of COMSM are bigger in size than those of pure spinel according to the micrographs of SEM(scanning electron microscopy). The determinations of the electrochemical characterization show that COMSM has both good cycling performance and high initial capacity of 124.1 mA/h at an average capacity loss of 0.19 mAh/g per cycle.     

柠檬酸络合无焰燃烧法制备尖晶石型LiMn2O4

采用柠檬酸络合无焰燃烧法制备锂离子电池正极材料尖晶石型LiMn2O4，颗粒大小只有10－100nm，晶型完整，电化学性能与国内外商品化的同种材料相当。直流电阻实验显示该材料在低于室温处存在一个相变。采用柠檬酸络合无焰燃烧法可以简化柠檬酸络合反应法的制备工艺，降低其成本。     

Influences of Sintering Process of Sprayed Precursors on the Structure and Electrochemical Properties of LiMn2O4 Cathode Material

Well-defined spinel LiMn2O4 powders were synthesized via sintering a precursor, which was prepared by spraydrying method. The effects of sintering process on the structure and electrochemical properties of LiMn2O4 were discussed. It was found that a single sintering could not synthesize a pure LiMn2O4 compound, while two-step sintering procedure consisting of decomposing sprayed precursors at 350℃ and further sintering at an elevated temperature leads to the formation of a single-phased LiMn2O4 with homogeneous particle size distribution. As compared to that sintered in air, the two-step sintered LiMn2O4 in oxygen shows tighter structure and more uniform particle size, as well as better electrochemical properties. It delivers an initial discharge capacity of 131 mAh·g^-1 （1/10C）, and still has excellent cycling stability at higher rate （1/5C）.     

Synthesis and Structure Transformation of Orthorhombic LiMnO2 Cathode Materials by Sol-gel Method

Orthorhombic LiMnO2 cathode materials were synthesized successfully at lower temperature by sol-gel method. When LiMnO2 precursor prepared by sol-gel method was fired in air, the product was a mixture of spinel structure LiMn2O4 and rock-salt structure Li2MnO3, whereas in argon single-phase orthorhombic LiMnO2 could obtain at the range of 750℃ to 920℃. The substitution of Mn by Zn2+ or Co3+ in LiMnO2 led to the structure of LiMnO2 transiting to Qα-LiFeO2. The results of electrochemical cycles indicated that the discharged capacity of orthorhombic-LiMnO2 was smaller at the initial stages, then gradually increased with the increasing of cycle number, finally the capacity stabilized to certain value after about 10th cycles. This phenomenon reveals that there is an activation process for orthorhombic LiMnO2 cathode materials during electrochemical cycles, which is a phase transition process from orthorhombic LiMnO2 to tetragonal spinel Li2Mn2O4. The capacity of orthorhombic LiMnO2 synthesized at lower te     

锂离子电池正极材料LiMn_2O_4制备新工艺

采用球磨湿混和旋转合成相结合的新工艺来制备锂离子电池正极材料ＬｉＭｎ２Ｏ４,并对制备的材料进行了粒度、化学成分以及电化学性能测试．制备的ＬｉＭｎ２Ｏ４为正尖晶石结构,而且物质纯净．同一批次制备的材料化学成分均匀,粉末粒度分布范围窄,中粒径为１０．６７μｍ,首次充电容量为１２４ｍＡｈ／ｇ,放电容量为１１５ｍＡｈ／ｇ．循环次数达３０次时,放电容量还大于１００ｍＡｈ／ｇ,循环稳定性良好．球磨湿混工艺能将原料混合均匀,并能有效地使原料粒度细化而且粒度均匀．旋转合成工艺能使反应物和反应产物的温度均匀、粒度均匀、晶型结构与成分均匀．球磨湿混和旋转合成相结合的固相合成新工艺能制备出电化学性能性能良好的ＬｉＭｎ２Ｏ４     

溶胶-凝胶法制备尖晶石型LiMn_2O_4正极材料

采用溶胶-凝胶法制备了锂离子电池正极材料锂锰氧化物。以Mn(NO3)2(50%)、LiOH·2H2O为原料,以柠檬酸为螯合剂制得前驱体,400℃预烧6h,再经750、850℃分别焙烧并保温6h得到粉体产物。XRD分析表明,所合成的产物为尖晶石型LiMn2O4;SEM观察结果表明,合成产物颗粒均匀,形貌规则。用其组装的电池经恒电流充放电测试,表明其初始比容量可达118.76mAh/g,具有良好的循环性能。     

Physical Properties and Electrochemical Performance of LiNixMn2-xO4 Cathode Materials Preparedusing a Precipitation Method

To improve the cycle performance of spinel LiMn204 as the cathode material of 4 V class Li secondary batteries, LiNixMn2-xO4 （x=0-0.3） samples were prepared using a simple precipitation method, and the effects of Ni doping on the physical properties and electrochemical performance of the samples were investigated using various methods. All LiNixMn2-xO4 （x=0-0.3） compounds show a single spinel phase, and the lattice parameter （a）, the unit cell volume （v） and particle size decrease with increasing Ni content. The results of the electrochemical experiments showed that the initial charge-discharge capacity of LiNixMn2-xO4 samples in the 3.0-4.4 V range decreases with increasing Ni content except for pure LiMn2O4; however, the capacity in the 4.4-4.9 V range increases with the increasing Ni content. For spinel samples Ni substitution can contribute to the improvement of their cycle performance due to the formation of the stronger Ni-O bond, homogeneous morphology, and sub-micron sized particles, and the sample with x=0.05 has larger peak currents, higher initial capacity and better cycling capability due to its lower electrochemical and diffusion polarization than those of other samples.     

稀土掺杂锂锰氧化物LiMn2-xNdxO4(X=0.005～0.1)的结构和电性能研究

采用微波与传统加热相结合的方法首次合成了稀土掺杂基锂锰氧化物LiMn2-xNdxO4(x=0.005-0.1)材料，电化学性能测试结果表明材料在掺杂量为x=0.01时表现出最大放电比容量，同时具有很好的循环稳定性，经过100次循环其容量衰减仅为14.9%；XRD测试结果表明在LiMn2O4尖晶石晶格中掺入合适量的Nd对稳定尖晶石骨架结构起重要作用；FTIR分析技术揭示了容量少量衰减的原因。     

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。     

Li1.02CoxCryMn2-x-yO4的固相合成及性能表征

采用固相法合成锂离子正极材料尖晶石相Li1.02CoxCryMn2-x-yO4，研究元素Co、Cr不同掺杂量对产物的结构、晶胞常数、电化学性能和电池内阻的影响．分析表明，掺杂少量的Co、Cr的LiMn2O4依然保持着尖晶石结构；晶胞常数随掺杂量的增加而减小，从而使尖晶石的比表面积增大，有利于提高电池的初始容量；并有效地抑制了充放电过程中的Jahn-Teller效应和Mn^3＋的歧化反应．掺杂Co、Cr后Li1.02MnO4初始容量有所下降，且随掺杂量增加而减小，但能明显改善材料的循环性能．     

溶胶凝胶法制备尖晶石型LiMn2O4的研究现状及展望

综述了用溶胶凝胶法制备锂离子电池正极活性材料尖晶石型LiMn2O4的方法及其发展方向。溶胶凝胶法制备材料具有贩优越性,研究工作取得了很大进展,但还不够系统深入,工业化尚有较大困难,认为这一领域的研究方向为：溶胶凝胶过程的基础性研究;尖晶石型LiMn2O4正析材料的掺杂改性、低温合成、纳米化和薄膜化;优化工艺过程,降低制备成本,实现工业化。     

钴镍掺杂锰酸锂的电化学性能研究

采用固相烧结法分别制备了钴掺杂和镍掺杂锰酸锂锂离子电池正极材料,同时制备了纯相锰酸锂进行比较.用电感耦合等离子发射光谱仪、X射线衍射仪、电子扫描电镜和电池性能测试系统对产物的组成、结构特征、微观表面形貌和恒流充放电性能进行了表征.结果表明:所制备的掺杂锰酸锂LiMn0.9 Ni0.1O2、LiMn0.9 Co0.1O2的结晶度高,无杂质相,材料颗粒的粒径均匀、表面光滑;首次放电比容量分别为114.7mAh/g和110.8mAh/g(0.5mA/cm,2.8~4.4V,vs.Li+/Li);50次循环后,放电比容量为107.2mAh/g和103.3mAh/g,50次循环比容量保持率分别达到94.1%和95.4%.     

锂离子电池正极材料LiMn2O4的改性研究

分别采用过渡元素掺杂和不同聚合物(聚丙烯晴和聚噻吩)包覆的方法对锂离子电池用正极材料LiMn2O4进行改性,研究了改性前后LiMn2O4的电化学性能.结果表明采用掺杂改性和聚合物包覆改性都可以提高LiMn2O4的电化学性能,减缓容量衰减.但单纯用一种方法改性效果都不理想,而将两种方法结合起来使用则不仅能有效地阻止电池在室温下的容量衰减(在前60个循环中,改性前电池的放电容量从119.1mAh/g下降到99.6mAh/g,平均每个循环的容量衰减率为0.27%,经Cr元素掺杂再用聚丙烯腈包覆后电池的放电容量从94.6mAh/g下降到91.8mAh/g,平均每个循环的容量衰减率为0.05%),而且使电池在高温下(60oC)也有很好的循环性能.     

尖晶石LiMn2O4的容量衰减及掺杂改性研究

分析了锂离子电池正极材料尖晶石LiMnO4在应用中容量衰减的难点,并对主要的影响因素如Mn溶解,Jahn-Teller效应,电解液的分解等,从机理上作出探讨,对尖晶石LiMn2O4的掺杂能够从改变d电子结构,缩小晶胞参数,减小从表面,改变Mn的平均氧化态等方面改变其结构,从而抑制其容量衰减,改善循环性能。     

不同锰源对尖晶石型锰酸锂性能影响的研究

分别以自制锰源和工业用电解二氧化锰为原料,采用固相合成法,将锰源和碳酸锂的混合物合成尖晶石型锰酸锂.通过扫描电子显微镜、X射线衍射的方法研究了不同锰源合成的尖晶石型锰酸锂之间形貌和结构的区别,通过电性能测试研究了不同锰酸锂对锂离子电池电性能的影响.结果表明：合成的锰酸锂都有良好的尖晶石型立方结构,以碳酸锰为原料的自制三...     

锂离子二次电池正极材料氧化锰锂的研究进展

综述了最近几年对于锂离子二次电池正极材料氧化锰锂的研究。研究的氧化锰锂材料主要有尖晶石结构的ＬｉＭＮ２Ｏ４、Ｌｉ４Ｍｎ５Ｏ９和Ｌｉ４Ｍｎ５Ｏ１２以及层状结构的ＬｉＭｎＯ２。对于ＬｉＭＮ２Ｏ４,通过引入适当的杂原子和采用新的溶胶－凝胶法制备复相 可以有效地克服Ｊａｈｎ－Ｔｅｌｌｅｒ效应所造成的容量衰减现象。Ｌｉ４Ｍｎ５Ｏ９display structure     

Characterization of nanoparticles of LiMn2O4 synthesized by a one-step intermediate-temperature solid-state reaction

Nanoparticles of lithium manganese oxide (LiMn2O4) with a spinel structure have been synthesized by a one-step intermediate temperature solid-state reaction. The influence of the molar ratio of citric acid to the metal ions on the physicochemical properties of LiMn2O4 powders in air has been analyzed by means of X-ray diffraction and electron microscope techniques. The electrochemical behavior of the material has been examined by charge/discharge tests and cyclic voltammetry. Test results reveal that LiMn2O4 particles with lower molar ratios of citric acid to metal ions (1:2) are highly crystalline and highly electrochemically reversible, with better cycle capabilities when compared with a sample with a higher molar ratio (2:1). The LiMn2O4 powders obtained by this method have a uniform morphology with a narrow size distribution.     

溶胶—凝胶—酯化法制备LiMn2O4超细粉及其电化学性质的研究

溶胶－凝胶－酯化方法是通过金属离子与多元有机酯的均一的螯合物。在较低的温度（〈２５０℃）下形成尖晶石型ＬｉＭＮ２Ｏ４正极材料。雇轩的ＬｉＭｎ２Ｏ４具有很好的电化学活性。Ｌｉ＝ＬｉＭｎ２Ｏ４二次电池首次充放电容量超过１３０ｍＡｈ／ｇ,循环１０次以后容量仍然保持在１２０ｍＡｈ／ｇ的较高水平。