添加剂四氟硼酸四乙基铵对石墨负极界面性能的影响

采用恒流充放电、循环伏安(CV)和交流阻抗(EIS)测试方法研究四氟硼酸四乙基铵(Et4NBF4)作为锂离子电池电解液添加剂对石墨负极材料界面性质的影响,通过傅里叶变换红外光谱(FTIR)对固体电解质界面膜(SEI)的成分变化进行分析。结果表明:添加剂Et4NBF4参与了SEI膜的形成,提高了人造石墨(AG)/Li半电池充电容量和后续的循环效率,但是降低了首次充放电效率;首次放电过程中1.0～0.5 V是SEI膜形成和生长的电位区间,而0.5 V以下SEI膜进行不断的修复;添加少量Et4NBF4降低了SEI膜阻抗,提高了电解液与石墨负极的相容性。     

碳酸亚乙烯酯添加剂对LiFePO_4/石墨电池高温循环性能的影响（英文）

研究成膜添加剂对材料结构稳定性及LiFePO4/石墨电池高温循环性能的影响。分别测试添加和未添加碳酸亚乙烯酯(VC)的18650电池的高温循环性能,并通过充放电测试、交流阻抗、扫描电镜、X射线能量色散光谱以及拉曼光谱等方法研究VC对电池正、负材料结构的影响。结果表明:VC添加剂在提高石墨结构稳定性的同时显著抑制LiFePO4材料中的溶铁行为;此外,VC添加剂阻止电解液在负极表面还原分解及负极表面SEI膜的增厚,也阻止电解液在LiFePO4电极表面的分解;含有VC添加剂的电解液可以有效改善LiFePO4/石墨电池在高温下的循环稳定性。     

Al离子掺杂正极材料LiMn2O4的高温循环性能

采用固相反应法分别合成正极材料LiMn2O4和LiAlxMn2-xO4(x=0.05,0.1,0.3).对它们进行XRD和SEM测试,并对比了高温下的循环性能.结果显示:除Al掺杂量x=0.3时,合成物出现了LiAlO2杂质相外,其余皆具有单一的尖晶石相结构.掺杂后的晶体颗粒比较圆润.LiMn2O4在高温下经过20次循环后,其比容量降低29%,衰减很快.造成衰减的主要原因是Mn3+歧化反应生成的Mn2+在电解液中的溶解,以及Jahn-Teller效应.通过阳离子Al3+的掺杂,有效的提高了尖晶石LiMn2O4的高温循环性能.     

复合锰源前驱体制备的尖晶石锰酸锂的结构与性能

以复合锰氧化物为锰源前驱体,采用多段高温热处理工艺合成了尖晶石锰酸锂(LiMn2O4),采用X射线衍射(XRD)、扫描电镜(SEM)、电化学阻抗谱(EIS)和充放电测试等研究了其晶体结构、微观形貌和电化学性能.结果表明:随着类球形Mn3O4组分在复合锰源前驱体中的占比提高,合成的尖晶石锰酸锂的晶格常数增大,晶胞体积变大...     

碳酸亚乙烯酯添加剂对LiFeP04／石墨电池高温循环性能的影响

研究成膜添加剂对材料结构稳定性及LiFePO4/石墨电池高温循环性能的影响。分别测试添加和未添加碳酸亚乙烯酯（VC）的18650电池的高温循环性能,并通过充放电测试、交流阻抗、扫描电镜、X射线能量色散光谱以及拉曼光谱等方法研究 VC 对电池正、负材料结构的影响。结果表明：VC 添加剂在提高石墨结构稳定性的同时显著抑制LiFePO4材料中的溶铁行为;此外,VC添加剂阻止电解液在负极表面还原分解及负极表面SEI膜的增厚,也阻止电解液在LiFePO4电极表面的分解;含有VC添加剂的电解液可以有效改善LiFePO4/石墨电池在高温下的循环稳定性。     

尖晶石LiMn2O4和LiCoO2与电解液的相容性

研究锂离子电池正极活性材料尖晶石LiMn2O4和LiCoO2与6种电解液充、放电时的相容性。用X射线衍射检测自制的LiCoO2试样和尖晶石LiMn2O4试样的结构；用粉末微电极循环伏安法测定6种电解液在导电剂乙炔黑表面的氧化电位；将制得的尖晶石LiMn2O4试样和LiCoO2试样在上述电解液中进行恒电流充放电实验。结果表明：充电至高电位3．3～4．3V（vs Li／Li^＋）时，如果正极活性材料表面与电解液发生不可逆反应并在其上覆盖一薄层电子不可导的钝化膜，则将导致活性材料的充、放电效率降低，放电容量减少，即正极活性材料与电解液的相容性差；反之，则相容性好；尖晶石LiMn2O4与上述6种电解液的相容性都很好，普适性强；LiCoO2与上述6种电解液的相容性差别较大，呈选择性。     

高温下锂离子电池电解液与电极的反应

采用DSC和XRD方法研究了1 mol.L-1 LiPF6电解液的热行为,发现EMC和H2O降低了1 mol.L-1 LiPF6电解液(溶剂为EC\DML,质量比为1:1)的热稳定性。电解液热分解反应是EMC分解生成DEC和DMC,而DEC和DMC与LiPF6的分解产物PF5发生系列化学反应,释放大量反应热与气体。由于可燃性电解液与Li0.5CoO2的热分解产物O2之间发生燃烧反应,使Li0.5CoO2发生复杂的热分解反应。高温下电解液与LiC6电极的热反应主要是:固体电解质膜(SEI膜)的碎裂反应,LiC6与粘结剂和电解液之间的反应。热反应主要发生在石墨的表面,而石墨的晶形结构在160℃热反应前后没有变化。     

耐久型高倍率性能锰酸锂微球的合成(英文)

以Mn2+和NH4HCO3为原料,通过控制结晶法合成球形MnCO3前驱体模板。以LiNO3和MnCO3为原料,按照一定的摩尔比机械混合,在700°C下煅烧8h,合成高倍率性能和长循环性能的球形尖晶石LiMn2O4材料。分别考查原料的摩尔比、反应时间以及反应温度对前驱体MnCO3形貌和产率的影响。采用X射线粉末衍射和扫描电镜对合成的MnCO3和LiMn2O4进行表征,对LiMn2O4样品进行室温条件下的充放电性能测试。电化学测试结果表明:尖晶石锰酸锂微球在10C的放电倍率下的首次放电容量达90mA·h/g(1C放电容量为148mA/g),800次循环后容量保持率达到75%。该方法合成的LiMn2O4微球作为高功率型锂离子电池的正极材料有着较好的应用前景。     

Al离子掺杂正极材料LiMn2O4的高温循环性能

采用固相反应法分别合成正极材料LiMn2O4和LiAl，Mn2-xO4（x=0．05，0．1，0.3）。对它们进行XRD和SEM测试，并对比了高温下的循环性能。结果显示：除Al掺杂量x=0．3时，合成物出现了LiAlO2杂质相外，其余皆具有单一的尖晶石相结构。掺杂后的晶体颗粒比较圆润。LiMn2O4在高温下经过20次循环后，其比容量降低29％，衰减很快。造成衰减的主要原因是Mn^3＋歧化反应生成的Mn^2＋在电解液中的溶解，以及Jahn—Teller效应。通过阳离子Al^3＋的掺杂，有效的提高了尖晶石LiMn2O4的高温循环性能。     

锂离子电池正极材料LiMnO_2的表面修饰及电化学性能

运用热处理技术分别制备B2O3、CuO和FePO4包覆的LiMnO2锂离子电池正极材料。采用X射线衍射(XRD)和扫描电镜(SEM)对材料的晶体结构和表观形貌进行分析,通过恒电流充放电以及电化学阻抗技术(EIS)分析其电化学性能。结果表明:包覆后材料的电化学阻抗与Warburge阻抗值有所增大,但包覆能有效抑制正极材料LiMnO2在电化学过程中锰的溶解,改善和提高材料的充放电循环性能和结构的稳定性。     

Performance and capacity fading reason of LiMn2O4/graphite batteries after storing at high temperature

Spinel LiMn2O4 was synthesized by a solid-state method. A 204468-size battery was fabricated and stored at 55℃. The structure and mor-phology of the LiMn2O4 cathode were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (gEM) technique. Energy dispersive spectroscopy (EDS) was used to analyze the surface component of the carbon anode. The discharge capacities of LiMn2O4 stored for 0, 24, 48, and 96 h are 106, 98, 96, and 92 mAh-g-1, respectively. The cyclic performance is improved after storage. The capacity reten-tions of LiMn2O4 stored for 0, 24, 48, and 96 h are 83.8%, 85.8%, 86.9%, and 88.6% after 180 cycles. The intensity of all the LiMn2O4 dif-fraction peaks is weakened. Mn is detected from the carbon electrode when the battery is stored for 96 h. Cyclic voltammograms and elec-trochemical impedance spectroscopy (EIS) were used to examine the surface state of the electrode after storage. The results show that the re-sistance and polarization of LiMn2O4/electrolyte is increased after storage, which is responsible for the fading of capacity.     

稀土元素对LiMn_2O_4电极材料相结构及性能的影响

采用X射线衍射仪、扫描电子显微镜、电池测试系统等研究了不同稀土掺杂元素La、Ce、Nd等对Pechini法合成的LiMn2O4材料的相结构、形貌及电化学性能的影响规律.结果表明,合成的LiMn2O4、LiLa0.03Mn1.97O4、LiLa0.01Ce0.01Nd0.01Mn1.97O4样品具有纯尖晶石型LiMn2O4结构,LiLa0.015Ce0.015Mn1.97O4样品由LiMn:O.相及微量杂质相CeO2组成;样品呈规则的近球形或球形,其粒径范围为0.5～2.5μm.稀土元素取代使LiMn2O4材料的初始容量略有降低、循环稳定性能有较大增加,LiMn2O4、LiLa0.03Mn1.97O4、LiLa0.015Ce0.015Mn1.97O4、LiLa0.01Ce0.01Nd0.01Mn1.97O42样品的初始容量分别为126.0、120.0、117.3、124.0 mA·h/g,经30次循环充放电后的容量分别为88.9、102.7、101.6、109.1 mA·h/g.     

Improving the electrochemical performance of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/graphite batteries using LiF additive during fabrication

LiMn2O4/graphite batteries using LiF additive were fabricated and their electrochemical performance including discharge,cycling and storage performances were tested and compared with LiF-free LiMn2O4/graphite batteries.The LiMn2O4/graphite battery with LiF added shows better capacity (107.5 mAh/g),cycling performance (capacity retention ratio of 93% after 100 cycles),and capacity recovery ratio (98.1%) than the LiF-free battery.The improvement in electrochemical performance of the LiF-added LiMn2O4/graphite...     

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.     

合成温度对LiMn1.95Mg0．05O4结构与性能的影响

用柠檬酸辅助溶胶一凝胶法在不同温度下合成了LiMn1.95Mg0．05O4正极材料。用X射线衍射、充放电测试以及电化学阻抗谱分析技术研究了不同合成温度对LiMn1.95Mg0．05O4结构和电化学性能的影响。结果表明：合成温度对LiMn1.95Mg0．05O4正极材料的晶相结构、电化学性能有显著影响,LiMn1.95Mg0．05O4尖晶石相的生成和长大与其合成的温度有密切的关系,合成的最佳温度为750℃;在750℃条件下合成的LiMn1.95Mg0．05O4具有较高的电化学活性和较好的晶相结构;高温合成有利于提高LiMn1.95Mg0．05O4正极材料的放电容量,低温合成有利于提高其循环性能。     

Structure and electrochemical properties of LiMn2O4

LiMn2O4, a cathode material of lithium ion battery, was prepared by the citric acid complexing method using lithium acetate and manganese acetate as raw materials. The type of atom location confused degree, the confused degree and judgement method in LiMn2O4 were analyzed. The effect of sintering temperature on structure and electrochemical properties of LiMn2O4 was also investigated. The results show that the atom location confused degree increases with the decrease of the X-ray diffraction peak intensity ratio of LiMn2O4, Ⅰ111/Ⅰ311. The type of atom location confused degree depends on the variation tendency of Ⅰ111/Ⅰ311 and Ⅰ311/Ⅰ400 value. If the variation tendency is the same, it belongs to the 16c type location confusion, however, if the variation tendency is contrary, it belongs to the anti-spinel type location confusion. When the sintering temperature is low, it is apt to produce the anti-spinel location confusion in LiMn2O4. With the increase of sintering temperature, the confused degree with the anti-spinel type gradually reduces, however, the confused degree with 16c type increases to some extent. When the atom location confusion with the anti-spinel type appears in LiMn2O4, both the initial discharging capacity and cycling properties of LiMn2O4 reduce. However, the atom location confusion with 16c type does not affect the charge and discharge properties of LiMn2O4.     

Electrochemical performances and structure characteristic of LiMn2O4-xYx（Y=F, Cl, Br） compounds

Spinel LiMn2 O4-x Yx (Y=F, Cl, Br) compounds were prepared by solid-state reaction and the electrochemically galvanostatic charge-discharge cycles were performed using as-prepared compounds as cathode material. The influence of halogens on their lattice constants and the relation of electrochemical properties and their lattice constants were investigated. It is concluded that when the lattice constants are smaller than that of LiMn2O4, the reversible capacity fade is suppressed and the initial capacity sacrifice is observed. When the content of fluorine is 0.05, the lattice constant of LiMn2O3.95 F0.05 is larger than that of LiMn2O4, the initial capacity is improved. An efficient method was found to control the lattice constants of LiMn2O4 through the addition of halogen, and to improve the electrochemical performance of LiMn2O4. The LiMn2O3.95 F0.05 shows excellent electrochemical charge-discharge performance, with high initial capacity of 143 mAh/g and nearly no capacity loss after 116 cycles.     

掺杂元素La、F对尖晶石LiMn2O4材料结构及性能的影响

采用X-射线衍射仪(XRK)、扫描电子显微镜(SEM)、电池测试系统等研究了掺杂元素La、F对高温固相合成尖晶石型LiMn2O4材料的相结构、貌、活化性能、循环稳定性能的影响.结果表明:掺杂元素La、F可有效地提高LiMn2O4样品的充放电效率、循环稳定性能:随着掺杂元素F含量的增加,LiMn2O4-xFx样品的初始容量降低、循环稳定性能呈现出先增后减的变化规律;当掺杂元素La、F的含量较少时,LiLay,Mn2-yO4-xFx样品具有纯的尖晶石LMn2O4结构,样品呈球形或近球形,粒径范围为0.5～2.5 μm,LiLa0.02Mn1.98O3.95F0.05样品的初始放电容量为123.6mAh/g,经30次循环充放电后的容量为114.6mAh/g,容量保持率为92.7%,具有较好的活化性能和循环稳定性能.     

Effects of Mn-Precursor on Performances of LiMn2O4 Cathode Material for Lithium Ion Battery

通过固相烧结工艺,制备了铝掺杂的Li Mn2O4锂离子电池正极材料。其中球型化及鳞块状的Li Mn2O4分别由Al共沉积的锰氧化物(CMO)前驱体及电解二氧化锰(EMD)前驱体制备。通过X射线衍射仪、扫描电子显微镜、电感耦合等离子光谱仪及方型铝壳全电池充放电测试等手段对试样的物化指标进行了测试。结果表明两组试样都为纯相,同时以CMO为前驱体制备的Li Mn2O4材料具备较好的球型度,更高的振实密度以及更优异的电化学性能。     

Powder electrochemical properties with different particle sizes of spinel LiAl0.05Mn1.95O4 synthesized by sol-gel method

An Al-doped spinel lithium manganese oxide was prepared by the adipic acid-assisted sol-gel method at 800℃, and the cathode materials （Liml0.05Mnl.9504） with different particle sizes were obtained through ball milling. The effects of particle size on the electrochemical performance of LiAl0.05Mnl.9504 samples were investigated by differential thermal analysis and thermogravimetry, X-ray diffraction, galvanostatic charge-discharge test, cyclic voltammetry, and electrochemical impedance spectroscopy. The results indicate that all samples with different particle sizes show the same pure spinel phase and good crystal structure; LiAlo.osMnl.9504 with Dso = 17.3 μm shows better capacity retention; LiAlo.osMnl.gsO4 cathode materials with small particle size have a bigger resistance of charge transfer than the large one, and the particle size has significant effects on the electrochemical performance of Al-doped spinel LiMn2O4 cathode materials.