掺杂元素Co、Cr、La对尖晶石型锰酸锂电化学性能的影响

采用高温固相法合成了掺杂Co、Cr、La元素的尖晶石型锰酸锂Li1.02Co0.02M1xM2yMn1.98-x-yO4电池材料;X射线衍射（XRD）表征所合成的产物呈现出良好的尖晶石型结构材料;扫描电子显微镜（SEM）显示合成材料均具有良好的粒径分布（2～3μm）及外貌.以该活性物质作为锂离子电池正极材料,经充放电测试研究表明：掺杂的尖晶石型锰酸锂正极材料Li1.02Co0.02M1xM2yMn1.98-x-yO4能够更好地抑制尖晶石型锰酸锂材料的可逆容量在充放电过程中的衰减,循环性能有了很大改善,表现出更好的电化学可逆特性,100次循环后放电容量仍能保持初始容量的95%以上.作为锂离子电池正极材料LiCoO2的替代材料,该研究为锰酸锂尖晶石型正极材料的改性提供了一种新方法.     

尖晶石型锰酸锂的复合掺杂改性

以固相烧结法制备的尖晶石型锰酸锂为基础,对其结构中掺杂复合非金属元素B和F,合成了B、F掺杂的尖晶石。通过X射线衍射、扫描电镜、电化学分析方法对试样的晶体结构、表面形貌及电化学性能进行表征。结果表明,采用B、F包覆的锰酸锂与纯锰酸锂的X射线衍射结果相似,波峰尖锐且峰值高;随着B的掺入,尖晶石作为正极材料充放电的循环性能得到了提高,但是其初始容量较低,仅为102.3mA·h/g。随着加入复合非金属元素B和F,样品的初始容量提高到了110.9mA·h/g,50次循环后的容量保持率为83.14%。实验结果表明,复合掺杂有效提高了锰酸锂的电化学性能。     

尖晶石型锰酸锂制备及其电化学性能

锰酸锂被认为是取代商品锂离子电池正极材料的LiCoO2候选材料.以二氧化锰、醋酸锰及氢氧化锂为原料,蒸馏水为分散剂,在空气气氛下进行分段烧结,控制烧结温度和时间,制备了锂离子电池正极材料锰酸锂.用X射线衍射仪,电子扫描电镜对产物的结构特征、微观表面形貌和恒流充放电性能进行了表征.结果表明:所制得正极材料为尖晶石型锰酸锂,结晶度高,无杂质相,材料颗粒的粒径均匀,首次放电比容量为117.3 mAh/g(0.5 mA/cm2,2.8~4.4 V,vs.Li+/Li);50次循环后,放电比容量为107.9 mAh/g,不可逆容量损失为9.4 mAh/g,比容量保持率为92.0%.得到了很好的综合电化学性能.     

锂离子电池正极材料LiMn2O4掺杂及对其性能的影响

综述了近年来掺杂锂离子正极材料尖晶石LiMn2O4的元素及方法，阐述了在锂离子正极材料LiMn2O4中掺杂钴、铬、镍、铝、稀土、钒后对材料性能的影响．结果表明，掺杂均不同程度地改善材料的循环稳定性，但对容量大都产生不利影响．     

相转移法合成稀土La掺杂锰酸锂电极材料的性能

采用相转移法合成了稀土La掺杂的锰酸锂材料粉体。利用XRD、SEM等对粉体进行结构形态表征,并以其为锂离子电池正极活性材料测试其充放电性能。结果表明:按n(Li)∶n(La)∶n(Mn)=1.1∶0.01∶1.99的摩尔配比制备的前驱体,在750℃焙烧12 h合成的样品材料结构稳定且呈较好的尖晶石相,以0.1C在4.5~3.0 V范围内充放电,首次放电比容量达127.5 mAh/g,放电平台时间较长,工作电压平稳于4.1 V.     

尖晶石型正极材料LiCrxMn2-xO4的电化学特性

采用高温熔融固相浸渍法合成了掺杂铬元素的尖晶石型锰酸锂LiCrxMn2-xO4.XRD测试结果显示所合成的产品均为尖晶石结构.以该活性物质作为锂离子电池的正极材料,通过充放电测试、微分容量以及循环伏安方法的研究表明,掺铬尖晶石型LiCrxMn2-xO4材料在充放电电压区间内所发生的电化学反应经历两个阶段,同时表明铬的掺入能够有效抑制尖晶石型锰酸锂材料的可逆容量的衰减,提高了材料的稳定性.     

尖晶石型正极材料LiCrxMn2-xO4的电化学特性

采用高温熔融固相浸渍法合成了掺杂铬元素的尖晶石型锰酸锂LiCrxMn2-xO4。XRD测试结果显示所合成的产品均为尖晶石结构。以该活性物质作为锂离子电池的正极材料，通过充放电测试、微分容量以及循环伏安方法的研究表明，掺铬尖晶石型LiCrxMn2-xO4。XRD材料在充放电电压区间内所发生的电化学反应经历两个阶段，同时表明铬的掺入能够有效抑制尖晶石型锰酸锂材料的可逆容量的衰减，提高了材料的稳定性。     

尖晶石LiCoxMn2-xO4材料电化学性能研究

为了提高LiMn2O4材料的性能,采用分步加热高温固相合法,合成了尖晶石型LiCoxMn2-xO4(x=0、0.04、0.08、0.1、0.12、0.16)材料,并在562 247方形实体电池LiCoxMn2-xO4/1M LiPF6-EC DEC EMC/MCMB体系中研究Co掺杂量对材料性能的影响.通过X射线衍射仪对LiCoxMn2-xO4材料结构进行了研究,发现随着Co掺杂量的增加,LiCoxMn2-xO4材料的晶胞参数不断变小,结构稳定性增加,循环性能得到提高,但材料的起始放电比容量不断减小,Co掺杂量为0.08～0.1时,材料的起始比容量较高,循环性能也均得到较大的提高.经过1 000次循环,材料的放电容量保持率在85%左右.Co的掺杂也提高了材料的高温性能及大电流工作能力,4倍率充放电时,放电容量为1倍率时的86%.     

Preparation and Characterization of LiMn1.8Co0.2O3.95F0.05 by the Combustion-assisted Soft Route

LiMn1.8Co0.2O3.95F0.05 powder was prepared by heating the ignited LiMn1.8Co0.2O3.95F0.05 precursor gel using lithium acetate, magnesium acetate, cobalt acetate, lithium fluoride, citric acid and glycol as raw materials. The influence of the calcination temperature on the stractural and electrochemical properties of LiMn1. 8 Co0.2 O3.95 F0.05 was investigated by X-ray diffraction, scanning electron microscopy, and galvanostatic charge-discharge experiments. The powders prepared under different conditions are of good crystallinity. The discharge capacity of LiMn1. 8 Co0.2 O3.95 F0.05 powder inereased from 92 mAh/g to 105mAh/ g as the calcination temperature inereasedfrom 750 ℃ to 850 ℃ . The capacity of LiMn1. 8 Co0.2 O3.95 F0.05 heated at 750 ℃ , 800 ℃, 850 ℃ for 4 haurs remained at 95.2% , 97%, 94.2% , respectively, after being cycled 20 times, suggesting that the multiple substitution of Co and F for Mn and O results in a good cycling behavior.     

锂离子电池正极材料Li0.97Re0.01FePO4的合成及性能

采用固相反应法合成了锂离子电池正极材料Li0.97Re0.01FePO4(Re=Er,Y,Gd,Nd,La),采用X射线衍射、恒电流充放试验对掺杂试样的微观结构和电化学性能进行测试。试验结果表明:掺杂稀土金属离子对LiFePO4的晶体结构没有影响,与LiFePO4相比,掺杂Er3+,Y3+,Gd3+的试样具有优良的循环性能和倍率性能,而掺杂Nd3+,La3+的试样的循环性能和倍率性能较差。掺杂试样中,Li0.97Gd0.01FePO4的电化学性能最佳,在C/10和1C(1C=120 mA.g-1)倍率下放电容量均最大。     

Effect of sintering time on the electrochemical properties of spinel LiMn_2O_4 synthesized by solid-state reaction

LiMn_2O_4 powder as a cathode materials for rechargeable lithium-ion batteries was prepared by solid-state reaction from Li_2CO_3 and electrolytic MnO_2 at different sintering periods(2,6,18,and 32 h).X-ray diffraction(XRD)patterns of the prepared samples are identified as the spinel structure with a space group of Fd(?)m.The lattice parameters almost remain the same as the sin- tering periods increase.The sample with a sintering period of 32 h shows good cycling performance at both low and high current densities,and also elevated temperature.It is believed that the excellent electrochemical behavior of this sample results from its good crystallinity and large grain size compared with other samples.Different electrochemical measurements were conducted to investi- gate the electrochemical properties of spinel LiMn_2O_4.     

Synthesis and characterization of spinel Li_(1.05)Cr_(0.1)Mn_(1.9)O_(4-z)F_z as cathode materials for lithium-ion batteries

Samples with the nominal stoichiometry Li_(1.05)Cr_(0.1)Mn_(1.9)O_(4-z)F_z(z=0,0.05,0.1,0.15,and 0.2) were synthesized via the solid-state reaction method and characterized by X-ray powder diffraction(XRD),scanning electron microscopy(SEM),galvanostatic charge/discharge, and slow rate cyclic voltammetry(SSCV) techniques.The results show that the pure spinel phase indexed to Fd3m can be obtained when z=0, 0.05,and 0.1.The substitution of F for O with z≤0.1 contributes to the increase of initial capacity c...     

Effect of sintering time on the electrochemical properties of spinel LiMn2O4 synthesized by solid-state reaction

LiMn2O4 powder as a cathode materials for rechargeable lithium-ion batteries was prepared by solid-state reaction from LitCO3 and electrolytic MnOz at different sintering periods （2, 6, 18, and 32 h）. X-ray diffraction （XRD） patterns of the prepared samples are identified as the spinel structure with a space group of Fd3 m. The lattice parameters almost remain the same as the sintering periods increase. The sample with a sintering period of 32 h shows good cycling performance at both low and nigh current densities, and also elevated temperature. It is believed that the excellent electrochemical behavior of this sample results from its good crystallinity and large grain size compared with other samples. Different electrochemical measurements were conducted to investigate the electrochemical properties of spinel LiMn204. 2008 University of Science and Technology Beijing. All rights reserved.     

Influence on performance and structure of spinel LiMn2O4 for lithium-ion batteries by doping rare-earth Sm

The spinel LiMn2O4 used as cathode materials for lithium-ion batteries was synthesized by mechanochemistry fluid activation process, and modified by doping rare-earth Sm. Testing of X-ray diffraction, cyclic voltammograms, charge-discharge and SEM was carried out for LiMn2O4 cathode materials and the modified materials.The results show that the cathode materials doped rare earth LixMn2-ySmxO4 (0.95≤x≤1.2, 0≤y≤0.3, 0≤z≤0.2) exhibit standard spinel structure, high reversibility of electrochemistry and excellent properties of charge-discapacity is deteriorated less than 15% after 300 cycles at room temperature and less than 20% after 200 cycles at 55 C.At the same time, Crystal Field Theory was applied to explain the function and mechanism of doped rare earth element.     

固相法制备正交LiMnO2的结构与电化学性能

以Mn2O3和LiOH·H2O为原料,采用固相法制备了正交LiMnO2（简写为o-LiMnO2）,通过X射线衍射（XRD）、透射电镜（TEM）和电化学循环测试对o-LiMnO2进行了研究.结果表明,反应温度较高时,o-LiMnO2晶体生长较完整,（110）晶面的堆垛层错较少.随着温度升高,o-LiMnO2电极首次库仑效率减小,放电容量逐渐降低,但循环稳定性有所提高.o-LiMnO2的电化学性能对充放电电流密度非常敏感,当充放电电流密度增大时,o-LiMnO2的活化次数增多,放电容量减小.     

Effects of Al, F dual substitutions on the structure and electrochemical properties of lithium manganese oxide

Spinel LiMn2O4 and F, Al-doped spinel LiAl0.05Mn1.95O3.98F0.02 have been synthesized by a soft chemistry method using adipic acid as the chelating agent. The synthesized spinel materials were characterized by differential thermal analysis (DTA) and thermogravimetery (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammetry (CV), and charge-discharge testing. The results indicate that all the samples have high phase purity, and fluorine is important in controlling the morphology; the doped aluminum enhances the stability of spinel LiMn2O4. The charge-discharge tests indicate that LiAl0.05Mn1.95O4 has high capacity retention, which is 92.60% of the initial after 50 cycles. It is found that the novel compound LiAl0.05Mn1.95O3.98F0.02 with smaller particles can offer much higher capacity, whose initial discharge capacity is 126.5 mAh?g-1. The cyclic voltammetric experiments disclose the enhanced reversibility of the F, Al3 -modified spinel as compared with the undoped spinel.     

Effect of the synthesis method of SnSb anode materials on their electrochemical properties

SnSb alloy powders for the anode of Li-ion batteries were synthesized by two kinds of reduction precipitation methods: solution titration and rapid mixing. Two kinds of SnSb alloy powders showed different phase compositions and particle morpholo-gies although the same starting materials were used. The SnSb alloy electrode synthesized by titration exhibits high reversible spe-cific capacity and good cycling stability, whereas the rapid-mixing sample shows high irreversible capacity and fast capacity fade. The broad particle size distribution of SnSb powders synthesized by titration is considered to be responsible for the improvement of cycling stability. The initial charge-discharge efficiency exceeding 80/ has been obtained for the titration sample. The electro-chemical reaction process of two kinds of synthesized SnSb composite electrodes was characterized by cyclic voltammetry and AC impedance techniques.