锰掺杂对锂离子电池正极材料Li3V2（PO4）3/C性能的影响（英文）

采用溶胶-凝胶法合成Li3V2-2/3xMnx(PO4)3(0≤x≤0.12)。采用XRD、SEM、XPS、恒流充放电和电化学阻抗谱(EIS)研究Mn掺杂对Li3V2(PO4)3/C结构和电化学性能的影响。XRD研究表明:掺杂少量的Mn2+不会影响材料的结构,所有样品均具有单一相态的单斜结构(P21/n空间群)。XPS分析表明:在Li3V1.94Mn0.09(PO4)3/C中,V和Mn的化合价分别为+3和+2,原料中的柠檬酸在煅烧过程中分解成C而残留在Li3V1.94Mn0.09(PO4)3/C中。电化学测试表明:掺杂Mn改善了电极材料的循环性能和倍率性能,正极材料Li3V1.94Mn0.09(PO4)3/C表现出最好的循环稳定性和倍率性能。在40mA/g的放电电流密度下,循环100次后,Li3V1.94Mn0.09(PO4)3/C的放电容量从158.8mA·h/g衰减到120.5mA·h/g,容量保持率为75.9%,而未掺杂样品的放电容量从164.2mA·h/g衰减到72.6mA·h/g,容量保持率为44.2%。当放电电流密度增加到1C时,Li3V1.94Mn0.09(PO4)3/C的初始放电容量仍能达到146.4mA·h/g,循环100次后,放电容量保持为107.5mA·h/g。EIS测试表明,掺杂适量的Mn2+减小了电荷转移阻抗,这有利于Li+的脱嵌。     

Li3V2(PO4)3/C复合结构正极材料的制备和电化学性能

以柠檬酸为螯合剂和碳源,采用溶胶凝胶法在强弱不同条件下制备锂离子正极材料Li3V2(PO4)3/C.利用XRD、SEM和恒电流充放电等进行测试和表征.结果表明,所有样品为纯相的单斜Li3V2(PO4)3,制备条件的不同不会影响Li3V2(PO4)3正极材料的晶型结构和晶胞参数,但对材料颗粒尺寸有较大影响,加入蔗糖可以抑制颗粒的长大和团聚,从而影响电化学性能;在3.0～4.3 V电压,由于Li3V2(PO4)3结构的稳定性,在低倍率下表现出优异的循环性能;随着颗粒的变大和团聚,材料的倍率性变差,在高倍率下充放电容量衰减快.     

Ni2+掺杂对Li3V2（PO4）3电化学性能的影响

采用X射线衍射(XRD)、透射电镜(TEM)和电化学方法,研究Ni2+掺杂对正极材料Li3V2(PO4)3的结构、形貌和电化学性能的影响。结果表明:掺杂适量的Ni2+不会改变Li3V2(PO4)3的单斜晶系结构,但可提高材料的电导率,抑制电池在充放电过程的极化。在室温下,Li3(Ni0.05V0.95)2(PO4)3以0.1C倍率放电的初始比容量为115mA.h/g,放电倍率从0.1C增加到0.4C循环60次后,比容量衰减率仅为2.7%,而未掺杂原样Li3V2(PO4)3的初始比容量为129 mA.h/g,60次循环后比容量衰减率约为30.3%;当放电倍率增至1C时,80次循环后,Li3(Ni0.05V0.95)2(PO4)3比容量为99.8 mA.h/g,而原样的比容量为84.1 mA.h/g;当放电倍率增至5C时,循环120次后,Li3(Ni0.05V0.95)2(PO4)3比容量为67.7 mA.h/g,而原样的比容量降为0。循环伏安和交流阻抗测试表明,Li3(Ni0.05V0.95)2(PO4)3的可逆性明显优于Li3V2(PO4)3的可逆性。     

影响锂离子电池正极材料LiMn2O4性能的因素

介绍了锂离子电池正极材料LiMn2O4的制备方法，并以柠檬酸体系溶胶一凝胶法合成LiMn2O4为例，从溶液pH值及含水量、Li的含量及酸与金属离子摩尔比、合成温度及时间、冷却速度及粒度等方面阐述了影响LiMn2O4性能的因素。实验表明，体系溶液最好为饱和溶液，pH值应控制在6．5左右；锂盐略为过量，柠檬酸与金属离子摩尔比为1：1。最佳烧结温度为750℃。8000℃，并合理控制冷却速率，合理控制烧结时间及烧结温度，从而控制粒子半径。     

锂离子电池正极材料LiχMn2O4电子结构的量子化学DV-Xα研究

采用原子基表示的第一原理赝势DV-α方法，计算了锂离子电池正极材料LiχMn2O4 (χ=0，1，2)各种模型的电子结构。结果表明：电极材料LiχMn2O4具有较好的电子导电性，锂离子嵌入正极材料后发生Jahn-Tell-er效应引起材料结构改变；锂离子的净电荷变为 0．7(χ=1)、 0．9或 0．5(χ=2)，说明锂离子过度嵌入LiχMn2O4中，导致部分锂离子和氧离子的相互作用增强，锂离子脱出较为困难，从而容量降低。最高占有轨道(HOMO)到最低空轨道(LUMO)的跃迁能很小，电子较易进行嵌入和脱出。     

锂离子电池正极材料 LixMn2O4电子结构的量子化学DV-Xα研究

采用原子基表示的第一原理赝势DV-Xa方法,计算了锂离子电池正极材料LixMn2O4(x=0,l,2)各种模型的电子结构.结果表明:电极材料L.xMn2O4具有较好的电子导电性,锂离子嵌入正极材料后发生Jahn-Tell-er效应引起材料结构改变;锂离子的净电荷变为 0.7(x=1)、 0.9或 0.5(x=2),说明锂离子过度嵌入LixMn2O4中,导致部分锂离子和氧离子的相互作用增强,锂离子脱出较为困难,从而容量降低.最高占有轨道(HOMO)到最低空轨道(LUMO)的跃迁能很小,电子较易进行嵌入和脱出.     

新型锂离子电池负极材料Li1.1V0.9O2的制备及其电化学性能

通过固相合法制备了新型锂离子电池负极材料Li1.1V0.9O2,考察不同合成工艺对其结构、形貌及电化学性能的影响。采用X射线衍射、扫描电子显微镜和恒电流充放电法研究了试样的结构、形貌和电化学性能。实验结果表明:采用两段烧结法合成的试样结构更完整、粒径分布更均匀、电化学性能更优良。在1 C倍率下,充电容量高达275 mAh/g,经过50次循环后,充电容量保持率高达96.73%。     

锂离子电池锡基负极材料研究进展

锡基负极材料容量高,安全性好,是目前动力锂离子电池用新型负极材料研究的热点。本文综述了近年来国内外在锂离子电池锡基各类负极材料方面的研究进展。重点介绍了它们的电极反应机理,材料合成方法及电化学性能,分析阐述了它们各自存在的优势和不足,总结了现有材料的改性手段。提出制备炭包覆锡基纳米颗粒的复合材料或者核壳、多孔等特殊结构的纳米级锡基材料,并在负极极片中预先引入金属锂,将是解决问题的最佳手段。指出锡基材料作为锂离子电池负极材料具有良好的商业化发展前景。     

Li3Ni0.1V1.9（PO4）3的电化学性能研究

采用X射线衍射和电化学方法,研究了正极材料Li3Ni0.1V1.9(PO43)的结构和电化学性能。结果表明:Li3Ni0.1V1.9(PO43)具有单斜晶系结构。在室温下,以0.1C倍率放电时Li3Ni0.1V1.9(PO4)3的初始比容量为115mAh/g,从0.1C增加到0.4C经过60次循环后,比容量保持率为97.3%,而未掺杂镍的Li3V2(PO4)3,初始比容量为129mAh/g,60次循环后,比容量保持率仅为69.7%。循环伏安和交流阻抗测试表明,Li3Ni0.1V1.9(PO4)3有较低的极化电阻和较好的可逆性。     

EuVO4-V2O5复合物作为高性能锂离子电池电极材料

本文采用水热法、阳离子交换法和煅烧处理,制备了相似于梅花结构的EuVO4-V2O5纳米线复合物。分别在300和500 oC温度条件煅烧制备的EuVO4-V2O5纳米线,实验发现随着温度不断增加,EuVO4-V2O5纳米线表面上的纳米颗粒发生了一定的团聚,当温度升高至500 oC时,纳米线出现了融化。通过实验测试比较发现,其中,300 oC煅烧制备的EuVO4-V2O5纳米线复合物的电化学储锂性能较好,在电流密度为30 mA g-1下经过50次循环后的放电比容量仍保持有376 mAh g-1,表现出良好的循环稳定性,且本文开发了一种新的稀土钒酸盐合成路径。     

Electrochemical performance of Al-substituted Li_3V_2(PO_4)_3 cathode materials synthesized by sol-gel method

The effect of Al-substitution on the electrochemical performances of Li3V2(PO4)3 cathode materials was studied.Samples with stoichiometric proportion of Li3AlxV2-x(PO4)3(x=0,0.05,0.10)were prepared by adding Al(NO3)3 in the raw materials of Li3V2(PO4)3.The XRD analysis shows that the Al-substituted Li3V2(PO4)3 has the same monoclinic structure as the un-substituted Li3V2(PO4)3.The SEM images show that Al-substituted Li3V2(PO4)3 has regular and uniform particles.The electrochemical measurements show that Al-substitution can improve the rate capability of cathode materials.The Li3Al0.05V1.95(PO4)3 sample shows the best high-rate performance.The discharge capacity at 1C rate is 119 mA·h/g with 30th capacity retention rate about 92.97%.The electrode reaction reversibility and electronic conductivity are enhanced,and the charge transfer resistance decreases through Al-substitution.The improved electrochemical performances of Al-substituted Li3V2(PO4)3 cathode materials offer some favorable properties for their commercial application.     

新型锂离子电池正极材料Li3V2(PO4)3的合成及其性能

以LiOH·H2O、V2O5和NH4H2PO4为原料,C为还原剂,采用高温固相法合成了锂离子电池正极材料磷酸钒锂(Li3V2(PO4)3).考察了合成温度等条件对产物组成和晶相的影响.结果表明:随着焙烧温度的升高,杂相的衍射峰相对强度逐渐减弱,当煅烧温度达到800℃时,杂相衍射峰消失,所得样品为纯相的Li3V2(PO4)3样品;按Li、V、P的摩尔比为3:2:3将原料在800℃下焙烧24 h,合成得到正极材料.该材料在0.1 C充放电制度下,首次充电比容量达到135 mA·h/g,首次放电比容量130 mA·h/g,充放电效率达96.3%;经过20次循环后,放电容量仍然高达110 mA·h/g.对经过20次循环后的样品进行了X射线衍射分析,结果发现,经过20次循环后样品仍然具有单斜晶体结构,样品各主要衍射峰强度都急剧减弱,说明样品在充放电过程中晶体结构发生了变化;采用最小二乘法对样品充放电前后的晶胞参数进行了计算,发现样品在经过充放电循环后晶胞参数都有不同程度的增加,晶胞体积增大0.6%左右.     

Electrochemical properties of high-power lithium ion batteries made from modified spinel LiMn2O4

A prismatic 204056-type high power lithium-ion battery was developed. Modified LiMn₂O₄ and carbonaceous mesophase sphere (CMS) were adopted as the cathode and anode, respectively. The effects of proportion of conductive carbon black in cathode and the rest time after discharge on the electrochemical properties of batteries were investigated. The electrochemical tests show that the proportion of conductive carbon black in cathodes affects the high rate capability and discharge voltage plateau distinctly. The battery with 3.0% of conductive carbon black in cathode shows excellent electrochemical performances when being charged/discharged within 2.5?4.2 V at room temperature. The discharge capacity at 20C rate is 94.4% of that at 1C rate, and the capacity retention ratio charged at 1C and discharged at 5C is 86.6% after 390 cycles at room temperature. The test result of impulse discharge at 50C for 5 s shows that the battery has outstanding high rate discharge performance when the battery is in the depth of charge of 90%, 75%, 60%, 45%, 30% and 15%. The battery also shows good charge performance. When the battery is charged at 0.5C, 1C, 2C and 4C, the ratios of capacity for constant current charge are 98.4%, 96.4%, 91.0% and 72.9% of the whole charge capacity, respectively. In addition, the rest time after discharge affects the cycle performance distinctly when the battery is discharged at high rate.     

Synthesis and electrochemical performance of Li3V2(PO4)3 by optimized sol-gel synthesis routine

Li₃V₂(PO₄)₃ samples were synthesized by sol-gel route and high temperature solid-state reaction. The influence of Li₃V₂(PO₄)₃ as cathode materials for lithium-ion batteries on electrochemical performances was investigated. The structure of Li₃V₂(PO₄)₃ as cathode materials for lithium-ion batteries and morphology of Li₃V₂(PO₄)₃ were characterized by X-ray diffractometry (XRD) and scanning electron microscopy (SEM). Electrochemical performances were characterized by charge/discharge and AC impedance measurements. Li₃V₂(PO₄)₃ with smaller grain size shows better performances in terms of the discharge capacity and cycle stability. The improved electrochemical properties of Li₃V₂(PO₄)₃ are attributed to the refined grains and enhanced electrical conductivity. AC impedance measurements also show that the Li₃V₂(PO₄)₃ synthesized by sol-gel route exhibits significantly decreased charge-transfer resistance and shortened migration distance of lithium ions.     

Electrochemical Study of Monoclinic Li3V2(PO4)3 in the Voltage Range of 1.5~3.0 V

采用液相法合成了Li3V2(PO4)3(空间群P21/n)电活性材料。用XRD和恒流充放电对样品的微观结构和电化学性能进行了表征。结果表明,在1.5~4.3V电压范围内,样品在平均电压为1.81和3.77V时均发生了可逆的锂嵌入反应;锂嵌出和嵌入过程中均出现一系列复杂的相变。在1.5~3.0V电压范围内,以C/5倍率循环50周后,样品的容量衰减极小,表明锂脱嵌反应具有优良的循环稳定性。因此,Li3V2(PO4)3可以同时作为正极和负极而组成对称电池。另外,1.5~4.3V电压范围内进行的嵌锂反应可以充当一种内置的过充电安全阀。     

动力锂离子电池正极材料的研究评述

通过衡量锂离子电池正极材料的安全性,认为LiMn2O4和LiMPO4可以作为动力电池的正极材料,综述LiMn2O4和LiMPO4正极材料的研究现状,重点对各种材料的合成、结构和性能进行总结和探讨.从目前来看,LiMn2O4仍然是主流的动力电池正极材料,但从长远来看,LiMPO4特别是Li3V2(PO4)3是动力锂电池正极材料的发展趋势.     

锂离子电池正极材料Li3V2(PO4)3的研究进展

Li3V2(PO4)3具有较高的能量密度、更好的电化学性能和热力学稳定性而成为潜在的、最有前途的锂离子电池正极材料。本文对Li3V2(PO4)3研究现状进行了全面介绍,综述了其电化学性能、微观结构、制备方法、改性研究以及其他研究,提出了目前研究中存在的问题,并就Li3V2(PO4)3作为锂离子电池正极材料的研究前景进行了展望。     

Li_3V_2(PO_4)_3溶胶-凝胶-微波合成工艺优化及性能研究

用溶胶-凝胶-微波法制备了锂离子电池正极材料Li3V2(PO4)3样品,用正交试验法考察了影响样品性能的因素,分析并优化了工艺。XRD、SEM和电化学测试表明:该方法所制备的样品为单斜结构,粒径尺寸0.2～1μm,颗粒分布比较均匀。锂源为Li2CO3、反应物摩尔比为Li∶V=3.0∶2.0、微波时间为25 min时,为最佳合成工艺条件。在此优化条件下,3.0～4.3 V区间内0.2 C放电比容量达到106 mAh/g,交换电流密度高达6.17×10-6 A/cm2。     

Synthesis and electrochemical performance of Co3O4/C composite anode for lithium ion batteries

The Co3O4/acetylene black composite anodes were successfully prepared by combination of oxalate precipitation and pyrolysis of the precipitate. The composite and its precursor were characterized by thermo-gravimetric analysis(TGA), differential thermal analysis(DTA), X-ray diffractometry(XRD), scanning electronic microscopy(SEM) and electrochemical measurements. The effects of carbon content and calcination temperature on properties of the composite were investigated in detail. The cycling performance of the Co3O4 anode is improved remarkably by the addition of carbon. As the calcination temperature rises in the range of 300-450 ℃, the crystallinity of the composites increases, but their reversible capacity and cycling stability decrease. Being charged/discharged at a current density of 0.1C rate, the optimized Co3O4/C composite anode shows a large initial reversible capacity of 757 mA-h/g, and a capacity of 743 mA-h/g is observed after 10 cycles.