尖晶石型LiNixMn2-xO4锂离子正极材料的电化学性能

采用Pechini法在800℃空气中焙烧6h制备LiNixMn2-xO4试样(x＝0，0．05，0．1，0.2，0．3，0．4，0．5)。经XRD测试表明除LiNi0.5Mnl．5O4以外，其它的试样均为纯净的尖晶石结构。尖晶石LiNixMn2-xO4试样电极在3．3—4．5V以及4．5—4．8V范围内的电化学性能测试表明：在3．3—4．5V范围内，试样初始充放电容量随Ni元素掺杂比例的增加而降低；在4．5—4．8V范围内，试样初始充放电容量随Ni元素掺杂比例的增加而增大；在3．3—4．8V范围内，试样总的初始容量基本不变；在3．3—4．5V范围内，试样的循环性能随Ni元素掺杂比例的增加而提高。     

锂离子电池正极材料LiNixMn2-xO4的制备和电化学性能研究

采用固相反应和湿化学两种方法合成了材料LiNixMn2-xO4含Ni量影响材料在4．7V高电压区间的容量，用固相反应法制备的LiNi0.5Mn1.5O4中含有杂相物质，首次放电容量可以达到118mAh／g，其中高电压区的容量为100mAh／g，循环50次的容量保持率为97％。用湿化学法可以得到纯相的LiNi0.5Mn1.5O4，首次放电容量为140mAh／g，其中高电压区的容量为125mAh／g，循环50次后，容量仍能达到133mAh／g，容量保持率为95％。XPS检测结果表明，湿化学法制备的LiNi0.5Mn1.5O4中Mn为＋4价，Ni为＋2价。     

5V锂离子电池尖晶石正极材料LiM0.5Mn1.5O4的研究评述

评述了锂离子电池锰酸锂正极材料的重要性，介绍了3d．过渡金属离子（Cr^3＋，Ni^2＋，Cu^2＋，Fe^3＋）掺杂在锰酸锂正极材料中的应用。研究了3d-过渡金属离子掺杂对锰酸锂正极材料结构和电化学性能的影响，并提出了其影响锂离子电池充放电和循环性能的机制。展望了3d-过渡金属离子掺杂在锂离子电池锰酸锂正极材料中的发展前景，并指出LiM0.5Mn1.5O4是非常有应用前景的5V锂离子电池正极材料。     

锂离子二次电池正极材料晶体结构与电化学性能

对比分析了锂离子电池的正极材料锂钻氧系、锂锰氧系、锂镍氧系材料以及目前颇具潜力的正极替代材料：含铁的聚阴离子化合物和高分子聚合物的微观晶体结构特征，讨论了由于材料晶体结构的差异产生的不同电化学性能提出了锂离子二次电池正极材料在结构上所必须具备的特征。     

锂离子电池正极材料LiNi_(0.5)Co_(0.5)O_2制备与电化学性能

采用球磨湿混和旋转合成相结合的新工艺制备了锂离子电池正极材料LiNi0.5Co0.5O2,并对材料进行了粒度、化学成分以及电化学性能测试。球磨湿混工艺能将原料混合均匀,并能有效地使粒度细化。旋转合成工艺能使混合料在均匀的温度场中进行反应,并使反应产物粒度均匀和成分均匀。制备的LiNi0.5Co0.5O2为单一的α-NaFeO2层状结构,粉末粒度分布范围窄,平均粒径约为8μm-10μm。电化学性能测试结果表明,在0．2mA/cm^2充放电流密度和3．0V－4．2V电压范围内,首次充电容量为173mAh/g,放电容量为148mAh/g。循环次数达30次时, 放电容量还有129mAh/g,循环稳定性良好。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良好的LiNi0.5Co0.5O2正极材料。     

锂离子电池LiLa_(0.02)Mn_(1.98)O_4正极材料的合成及电化学性能EI北大核心CSCD

采用液相无焰燃烧法制备单晶多面体LiLa_(0.02)Mn_(1.98)O_4材料,通过X射线衍射(XRD)、场发射扫描电子显微镜(FESEM)和透射电子显微镜(TEM)等表征手段对材料的结构和形貌进行分析,并通过恒电流充放电、循环伏安(CV)、交流阻抗(EIS)等测试分析材料的电化学性能。结果表明:掺杂La^(3+)没有改变LiMn_(2)O_(4)的尖晶石结构。在25℃、1C和5C倍率条件下,LiLa_(0.02)Mn_(1.98)O_4初始放电比容量分别为112.7和94.5mA·h/g,循环500次后,LiLa_(0.02)Mn_(1.98)O_4的容量保持率为64.42%和81.45%,而LiMn_(2)O_(4)样品的容量保持率分别为53.69%和56.9%;特别是在10C高倍率下,LiMn_(2)O_(4)样品的初始放电比容量仅有44.7mA·h/g,同样条件下,LiLa_(0.02)Mn_(1.98)O_4首次放电比容量达73.5mA·h/g,循环500次后,容量保持率为81.09%。CV和EIS测试发现,掺杂后的材料有较好的循环可逆性,较大的锂离子扩散系数1.04×10^(-16)cm^(2)/s,对循环2000次后的极片进行分析,材料的晶体结构和颗粒形貌基本没有变化,适量的La掺杂能够稳定材料的晶体结构,有效抑制Jahn-Teller,提高材料的循环性能。     

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。     

高倍率锂离子电池正极材料LiCo_(0.9)Ni_(0.05)Mn_(0.05)O_2的合成及电化学性能

以碳酸氢铵为沉淀剂采用共沉淀法合成球形Co0.9Ni0.05Mn0.05CO3前驱体,以碳酸盐前驱体和Li2CO3为原料,在空气中通过固相反应制备出LiCo0.9Ni0.05Mn0.05O2正极材料,研究烧结温度对产物结构及电化学性能的影响。采用扫描电镜(SEM)、X射线衍射(XRD)和光电子能谱(XRS)分别表征样品的形貌、结构和元素价态。结果表明:不同烧结温度下合成产物的性能差别很大,较适合的合成温度为900℃;在3.0~4.5 V电压范围内,LiCo0.9Ni0.05Mn0.05O2显示出较好的倍率性能;在25℃测试条件下,材料在0.2C、0.5C、1C、5C和10C时的放电比容量分别为181.6、178.3、173.9、167.8和157.1 mA·h/g。     

Al掺杂Li_2MnSiO_4锂离子电池正极材料的合成和电化学性能

以Li2SiO3、Mn(CH3COO)2.4H2O和Al(OH)3为原料,用传统高温固相合成法成功制备出Li2Al0.1Mn0.9SiO4锂离子电池正极材料。采用XRD、FESEM分析了正极材料的相组成、结构和形貌,利用电池测试仪测试了正极材料的电化学性能。研究结果表明,固相合成的产物主相为Li2Al0.1Mn0.9SiO4,同时存在少量的杂质,产物表面形貌为非球形颗粒,颗粒尺寸为100～500 nm。实验结果表明,Al掺杂后,正极材料的可逆容量和循环寿命都得到提高。正极材料电化学性能提高的机理在于Al掺杂稳定了Li2MnSiO4正极材料的结构。     

LiFePO4/C锂离子电池正极材料的电化学性能

以碳凝胶作为碳添加剂,采用固相法制备了复合型LiFePO4/C锂离子电池正极材料.研究了不同掺碳量对样品性能的影响.利用X射线衍射仪、扫描电镜和碳硫(质量分数)分析方法对所得样品的晶体结构、表面形貌、含碳量进行分析研究.结果表明:样品中的碳含量(质量分数)分别为0%、5%、10%、22%,所得样品均为单一的橄榄石型晶体结构,碳的加入使LiFePO4颗粒粒径减小.另外,碳分散于晶体颗粒之间,增强了颗粒之间的导电性.合成样品的电化学性能测试结果表明,掺碳后的LiFePO4放电比容量和循环性能都得到显著改善.其中,含碳量为22%的LiFePO4/C在0.1 C倍率下放电,首次放电容量达143.4 mA·h/g,充放电循环6次后电容量为142.7 mA·h/g,容量仅衰减0.7%.     

Effects of sodium substitution on properties of LiMn2O4 cathode for lithium ion batteries

Na-doped Li1.05Mn2O4 cathodes were synthesized using a sol-gel process.The samples were characterized by X-ray diffractometry(XRD),cyclic voltammetry(CV),electrochemical impedance spectroscopy(EIS)and charge-discharge measurements. The results show that all the samples exhibit the same cubic spinel phase structure without impurity.The lattice constant and unit cell volume decrease with increasing the sodium dopant amount.As the molar ratio of sodium to manganese(x=n(Na)/n(Mn))increases from 0 to 0.03,the initial discharge capacity of the Li1.05Mn2O4 cathodes decreases from 119.2 to 107.9 mA·h/g,and the discharge capability at large current rate and the storage performance decline dramatically,while cycling performance at room temperature and 55℃are improved.The CV and EIS studies indicate that reversibility of Li1.05Mn2O4 cathodes decreases and the electrochemical impedance increases with increasing the sodium dopant amount.     

锂离子电池正极材料LiNi0.5Mn0.5O2的循环性能

采用共沉淀法可以制备出首次放电容量高达210 mA.h/g的LiNi0.5Mn0.5O2材料(2.8~4.5 V,电流密度30 mA/g),但材料循环性能受制备过程中的处理工艺影响很大,处理不严格将导致材料循环性能严重下降。围绕材料的循环性问题,对其机理进行了分析并在此基础上对制备工艺进行了进一步改善:分别从配锂方式,烧结过程中的升降温速率以及烧结的保温制度进行了系统研究。结果表明:采用改进配锂方式,缓慢升温速率(2℃/min),高低温结合的烧结制度和快速风冷工艺所制备的材料首次放电容量达到188 mA.h/g,30个循环后仍保持在174 mA.h/g,循环效率有了明显的提高。     

Synthesis and characterization of LiNi0.45Co0.10Mn0.45O2 cathode for lithium ion batteries

1INTRODUCTIONAdvanced rechargeable lithium ion batteriesare attractive for use in consumer electronic andelectric vehicle(EV)application because of a fa-vorable combination of voltage,energy density,cycling performance,and have been developed rap-idly worldwide during the past decade[1,2].LiCoO2has been widely used as a cathode material in com-mercial lithiumion battery because it is reasonableeasy to synthesize and shows a stable discharge ca-pacity[3].But due to its high cost and toxic…     

以Mn3O4为前驱体制备尖晶石型LiMn2O4及其性能

采用改进的固相反应法合成了高性能的锂离子电池正极材料LiMn2O4。首先,以廉价的MnSO4为原料,通过水解氧化法制备纳米级Mn3O4前驱体;然后,将Mn3O4和Li2CO3混合均匀,在750℃固相反应20 h,得到尖晶石型LiMn2O4。用X射线衍射(XRD)和扫描电镜(SEM)对Mn3O4前驱体和LiMn2O4样品进行表征,用充放电测试和循环伏安技术对LiMn2O4样品进行电化学性能研究。结果表明:所制备的LiMn2O4具有完整的尖晶石型结构,且晶体粒子分布均匀。所制备的LiMn2O4材料在3.0~4.4 V之间,室温(25℃)下,在0.2C倍率下首次放电比容量为130.6 mA.h/g;在0.5C倍率下首次放电比容量为127.1 mA.h/g,30次循环后,容量仍有109.5 mA.h/g,且样品具有较好的高温性能。     

Preparation and characteristics of Li2FeSiO4/C composite for cathode of lithium ion batteries

A Li2FeSiO4/C composite cathode for lithium ion batteries was synthesized at 650 ℃ by solid-state reaction. The effects of carbon sources and carbon content on the properties of the Li2FeSiO4/C composites were investigated. The crystalline structure, morphology, carbon content and charge/discharge performance of Li2FeSiO4/C composites were determined by X-ray diffraction(XRD), scanning electron microscopy(SEM), carbon/sulfur analyzer and electrochemical measurements. As carbon content increases in the range of 5%-20%, the amount of Fe3O4 impurity phase decreases. The SEM micrographs show that the addition of the carbon is favorable for reducing the Li2FeSiO4 grain size. Using sucrose as carbon source, the Li2FeSiO4/C composite with 14.5% carbon synthesized at 650 ℃ shows good electrochemical performance with an initial discharge capacity of 144.8 mA-h/g and a capacity retention ratio of 94.27% after 13 cycles.     

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.     

Electrochemical properties of the carbon-coated lithium vanadium oxide anode for lithium ion batteries

Carbon-coated Li_1.1V_0.9O₂ powder was prepared by dissolving pure crystalline Li_1.1V_0.9O₂ powder in an ethanol solution containing 10 wt% sucrose and sintering it under an argon atmosphere. The structures of the bare and carbon-coated Li_1.1V_0.9O₂ powders were analyzed using X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy. These powders were used as anode active materials for lithium ion batteries in order to determine the electrochemical properties via cyclic voltammetry (CV) and constant current methods. CV revealed the carbon-coated Li_1.1V_0.9O₂ anode to have better reversibility during cycling than the bare Li_1.1V_0.9O₂ anode. Carbon-coated Li_1.1V_0.9O₂ also showed a higher specific discharge and charge capacities, as well as lower electrolyte and interfacial resistance properties. The observed specific discharge and charge capacities of the carbon-coated Li_1.1V_0.9O₂ anode were 330 mAh/g and 250 mAh/g, respectively, in the first cycle. In addition, the cyclic efficiency of this cell was 75.8% in the first cycle. After 20 cycles, the specific capacity of the Li_1.1V_0.9O₂ anode was reduced to approximately 50% of its initial capacity, irrespective of the presence of a carbon coating.     

高密度锂离子电池正极复合材料LiFePO4/C

以FeC2O4-2H2O、NH4H2PO4、Li2CO3和乙炔黑为原料,采用两步固相反应法制备了高密度LiFePO4/C正极复合材料.利用差热(DSC),热重(TGA)和X射线衍射(XRD)等分析手段具体探讨了第一步固相反应中可能存在的反应过程和中间产物.利用扫描电镜表征了复合材料LiFePO4/C中LiFePO4微粒形貌和接触状态.结果表明,乙炔黑的含量是影响LiFePO4微粒尺寸和微粒间接触界面的重要因素.在一次热处理的基础上,二次球磨和烧结有利于第二次固相反应过程中反应物质的接触和传质,较一步固相法提高了生成的LiFePO4的振实密度.当乙炔黑的含量(质量分数)为0.1%～1.5%时,两步固相法所制正极材料LiFePO4/C的振实密度可达到1.7 g/cm3,初次放电容量达到105 mA.h/g.