球形LiNi1/3Co1/3Mn1/3O2的合成及其电化学性能

以化学共沉淀法制备的球形Ni1/3Co1/3Mn1/3CO3为前驱体合成了球形LiNi1/3Co1/3Mn1/3O2,研究LiNi1/3Co1/3Mn1/3O2合成工艺对产物形貌的影响.结果表明直接以前驱体Ni1/3Co1/3Mn1/3CO3与Li2CO3反应合成的LiNi1/3Co1/3Mn1/3O2的一次颗粒较大,以前驱体分解后的氧化物与Li2CO3反应合成的LiNi1/3Co1/3Mn1/3O2的一次颗粒相对细小;合成的LiNi1/3Co1/3Mn1/3O2均为具有层状结构的纯相物质;球形正极材料LiNi1/3Co1/3Mn1/3O2充放电过程中存在一个材料活化的过程,在前10周期充放电时,电池容量处于增加的状态;在2.7～4.3 V的电压范围内1 C倍率下电池的放电比容量达到149 mA·h/g,0.2 C倍率下为158 mA·h/g,经50次循环后容量无衰减.     

不同金属离子价态的前驱体制备球形LiNi1/3Mn1/3Co1/3O2的性能比较

利用共沉淀法和控制结晶氧化法在不同条件下分别制备出低价态球形Ni1/3Co1/3Mn1/3(OH)2和高价态球形Ni1/3Co1/3Mn1/3OOH前驱体,并分别和LiOH·H2O在不同温度烧结合成出球形锂离子正极材料Li(Ni1/3Co1/3Mn1/3)O2.XPS分析表明,制备的高价态球形Ni1/3Co1/3Mn1/3OOH前驱体其过渡金属Ni、Co和Mn的价态分别是2+,3+,4+,XRD分析表明,高价态球形Ni1/3Co1/3Mn1/3OOH前驱体比低价态球形Ni1/3Co1/3Mn1/3(OH)2前驱体具有较高的活性,能够在低温下合成出Li(Ni1/3Co1/3Mn1/3)O2,而且制备的产物结晶度高,阳离子混排程度小,具有规整的层状a-NaFeO2结构.充放电实验表明,由高价态球形Ni1/3Co1/3Mn1/3OOH前驱体制备的Li(Ni1/3Col/3Mn1/3)O2具有优良的充放电性能和循环性能.     

Synthesis of LiNi1/3CO1/3Mn1/3O2 cathode material via oxalate precursor

Using oxalic acid and stoichiometrically mixed solution of NiCl2, CoCl2, and MnCl2 as starting materials, the triple oxalate precursor of nickel, cobalt, and manganese was synthesized by liquid-phase co-precipitation method. And then the LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion battery were prepared from the precursor and LiOH-H2O by solid-state reaction. The precursor and LiNi1/3Co1/3Mn1/3O2 were characterized by chemical analysis, XRD, EDX, SEM and TG-DTA. The results show that the composition of precursor is Ni1/3Co1/3Mn1/3C2O4·2H2O. The product LiNi1/3Co1/3Mn1/3O2, in which nickel, cobalt and manganese are uniformly distributed, is well crystallized with a-NaFeO2 layered structure. Sintering temperature has a remarkable influence on the electrochemical performance of obtained samples. LiNi1/3Co1/3Mn1/3O2 synthesized at 900 ℃ has the best electrochemical properties. At 0.1C rate, its first specific discharge capacity is 159.7 mA·h/g in the voltage range of 2.75-4.30 V and 196.9 mA·h/g in the voltage range of 2.75-4.50 V; at 2C rate, its specific discharge capacity is 121.8 mA·h/g and still 119.7 mA·h/g after 40 cycles. The capacity retention ratio is 98.27%.     

Surface modification of spherical LiNi1/3Co 1/3 Mn1/3O2 with Al2O3 using heterogeneous nucleation process

To improve the cycle stability at high voltage and high charge/discharge rate, spherical LiNi1/3Co1/3Mn1/3O2 was coated with Al2O3 by using heterogeneous nucleation process, and the physical and electrochemical properties were studied. The SEM images show that there is a uniform coating on the modified spherical LiNi1/3Co1/3Mn1/3O2. The electrochemical tests indicate that the properties of LiNi1/3Co1/3Mn1/3O2 coated with 0.5% aluminum oxide are the best. The initial capacities are 150 and 173 mA.h/g at the rate of I C in the voltage range of 2.7-4.3 V and 2.7-4.6 V, respectively, and the discharge capacities maintain about 99% and 85% after 30 cycles, respectively. While those of the bare LiNi1/3Co1/3Mn1/3O2 are only 90% and 75%, respectively. The CV tests of LiNi1/3Co1/3Mn1/3O2 show that Al203-coating can restrain the oxide-reduction peak currents fading during the charge/discharge course.     

锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的制备及性能研究

采用溶胶-凝胶法制备了锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2,并考察了烧结温度对材料结构、表面形貌和电化学性能的影响.XRD和SEM测试结果表明,900℃下烧结得到的样品是粒径在0.3～0.5 μm范围的球形粒子,具有最佳的阳离子有序度;充放电测试结果表明,其在0.1C倍率下首次放电容量达到148.8...     

Effect of calcination temperature on characteristics of LiNi1/3Co1/3Mn1/3O2 cathode for lithium ion batteries

LiNi1/3Co1/3Mn1/3O2 was synthesized by sol-gel method and effect of calcination temperature on characteristics of LiNi1/3Co1/3Mn1/3O2 cathode was investigated. The structure and characteristics of LiNi1/3Co1/3Mn1/3O2 were determined by XRD, SEM and electrochemical measurements. The results show that the compound LiNi1/3Co1/3Mn1/3O2 has layered structure with hexagonal lattice. With the increase of calcination temperature, the basicity of the material decreases, and the size of primary particle rises. The LiNi1/3Co1/3Mn1/3O2 calcined at 900 ℃ for 12 h shows excellent electrochemical performances with large reversible specific capacity of 157.5 mA-h/g in the voltage range of 2.75-4.30 V and good capacity retention of 94.03% after 20 charge/discharge cycles. Capacity of LiNi1/3Co1/3Mn1/3O2 increases with enhancement of charge voltage limit, and specific discharge capacities of 179.4 mA.h/g, 203.1 mA.h/g are observed when the charge voltages limit are fixed at 4.50 V and 4.70 V, respectively.     

正极材料Li（Ni1／3Co1／3-xMn1／3）MxO2（M=Ti，Mg）的合成及性能

采用草酸盐前驱体合成Ti4+、Mg2+掺杂正极材料Li(Ni1/3Co1/3-xMn1/3)MxO2(M=Ti, Mg).利用XRD和SEM对其结构和形貌进行表征,并采用循环伏安、交流阻抗、恒流/恒压充放电测试其电化学性能.结果表明:Ti4+、Mg2+掺杂后晶胞体积增大,大倍率充放电时LiNi1/3Co1/3Mn1/3O2的电化学反应阻抗Rct降低,其大倍率充放电性能得到改善,Ti4+掺杂效果更好;当掺杂量x＝0.025时,材料晶型完整,具有单一的a-NaFeO2层状结构;1C倍率时Li(Ni1/3Co1/3-0.025Mn1/3)Ti0.025O2的第二循环放电容量为143.2 mA-h/g,2C时为128.0 mA-h/g,经100次循环后容量分别为132.5和115.8 mA-h/g,容量保持率为92.53%和90.47%.     

锂离子电池正极材料LiNi_1/3Co_1/3Mn_1/3O_2的研究进展

介绍了一种新型的锂离子电池正极材料LiNi1/3Co1／3Mn1／3O2的最新研究状况,描述了材料的晶体及电子结构,以及电化学性能;重点总结了现今国内外制备此材料的几种主要合成方法及研究进展;同时,介绍了不同掺杂元素（Fe、B、Al、Ti）对材料的改性作用。     

Li(Mn1/3Ni1/3Co1/3)1-yMyO2(M=Al,Mg,Ti)正极材料的制备及性能

采用液相共沉淀合成锰镍钴氢氧化物前驱体, 在前驱体中掺入元素M(M=Al, Mg, Ti), 与锂结合生成Li(Mn1/3Ni1/3Co1/3)0.98M0.02O2材料, 结果表明掺杂可有效提高材料的循环性能. X射线衍射结果表明 随掺钛量增大(0≤y≤0.15), 晶格畸变增大, 半高宽变大, 晶粒粒径增大; 其中掺钛量y=0.1的材料电化学性能表现最好, 以20 mA/g电流充放电, 在2.5～4.6 V电压区首次放电容量可达215 mA·h/g.     

Synthesis and characterization of LiCo1/3Ni1/3Mn1/3O2 prepared by Pechini process

Layered cathode material LiCo1/3Ni1/3Mn1/3O2 was synthesized by Pechini process, and investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and galvanostatic charge/discharge cycling. The sample is well-crystallized and has a phase-pure a-NaFeO2 structure. The particle sizes are uniform, and distributed in the range of 20-200 nm. The initial discharge capacity of the Li/LiCo1/3Ni1/3Mn1/3O2 cell was about 149 mAh·g -1 when it was cycled at a voltage range of 4.5-2.3 V with a specific current of 0.25 mA. The result is better in comparison with solid-state solution method. The synthetic procedure was discussed. Three major reactions: chelation, esterification, and polymerization successively occurred.     

Uniform AlF3 thin layer to improve rate capability of LiNi1/3Co1/3 Mn1/3O2 material for Li-ion batteries

LiNi1/3Co1/3Mn1/3O2 was coated with uniform nano-sized AlF3 layer by chemical precipitation method to improve its rate capability. The samples were characterized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), charge-discharge cycling, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). Uniform coated layer with a thickness of about 3 nm was observed on the surface of LiNi1/3Co1/3Mn1/3O2 particle by TEM. At 0.5C and 2C rates, 1.5% (mass fraction) AlF3-coated LiNi1/3Co1/3Mn1/3O2/Li in 2.8-4.3 V versus Li/Li+ after 80 cycles showed less than 3% of capacity fading, while those of the bare one were 16.5% and 45.9%, respectively. At 5C rate, the capacity retention of the coated sample after 50 cycles maintained 91.4% of the initial discharge capacity, while that of the bare one decreased to 52.6%. EIS result showed that a little change of charge transfer resistance of the coated sample resulting from uniform thin AlF3 layer was proposed as the main reason why its rate capability was improved obviously. CV result further indicated a greater reversibility for the electrode processes and better electrochemical performance of AlF3-coated layer.     

Zn掺杂对LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2结构与电化学性能的影响

用溶胶凝胶法制备了Li Ni1/3Co1/3-x Mn1/3Znx O2(x=0,1/24,2/24,4/24)锂离子电池正极材料。由X射线衍射和扫描电镜对其分析结果表明,Zn掺杂不改变Li Ni1/3Co1/3Mn1/3O2的α-Na Fe O2层状结构,当掺杂量达到4/24时,杂相产生。电化学研究表明,当Zn掺杂量为2/24时,Li Ni1/3Co1/3Mn1/3O2首次放电容量由未掺杂的169.2 m Ah·g-1降低为160.1m Ah·g-1,但循环性能明显提高,30次循环后的容量保持率由未掺杂的89.2%升至97%。并且在20、40、60和80 m A·g-1不同的电流密度下继续循环20次后,当再次恢复到20 m A·g-1的电流密度时,放电容量可恢复到150.3 m Ah·g-1。     

Structure and transport properties of （La1-x-yYy）2/3Cal/3MnO3 with La-site vacancies

Several samples of manganese oxides La（1-x）2/3Cal/3MnO3 （V-LCMO） and （La0.7-xY0.3）2/3Cal/3MnO3 （x〈0.15） （V-LYCMO） with vacancies at La-site （La-vacancy） were prepared by solid-state reaction method. The X-ray diffraction（XRD） patterns refined by Rietveld confirm that these compounds exhibit single phase structure with orthorhombic symmetry （Pnma）. The lattice parameters, Mn-O bond length and Mn—O—Mn bond angle vary with La-vacancy concentration, as an indication of the occurrence of the local Jahn-Teller effect. The measurement result of V-LCMO compounds shows that the maximum magnetoresistance（MR） is about 220% at TIM=268 K and La-vacancy content x=0.04. For V-LYCMO compounds, there exists metal-insulator transition at about 50 K, and a very large MR （over 106%） is observed at the temperature ranging from 40 K to 50 K.     

La1/3Sr2/3Mn1-xFexO3(x=0,0.05)中电荷有序现象的超声研究

系统研究了La1／3Sr2／3Mn1-xFexO3(x=0，0．05)单相多晶样品在20--300K温区内的电荷输运性质和超声特性，结果表明，La1／3Sr2／3MnO3样品在235K存在明显的电荷有序现象，但是极少量的Fe取代Mn就会有效地抑制电荷有序现象的发生，伴随电荷有序现象的发生声速出现极大的软化，其相对变化超过5％，这表明La1／3Sr2／3Mn1-xFexO3中存在剧烈的电-声子相互作用，分析指出该电-声子耦合主要起源于Jahn-Teller效应。     

颗粒尺寸对多晶La2／3Ca1／3Mn1-xCuxO3低场磁电阻的影响

采用溶胶-凝胶法制备了不同颗粒尺寸的La2/3Ca1/33Mn1-xCuxO3(x=0.04)系列试样。X射线衍射实验说明Cu掺杂和不同温度烧结没有改变晶体的结构。电阻-温度实验曲线表明，随颗粒尺寸的减少，半导体-金属转变温度（Tp）向低温方向移动。磁电阻曲线显示，随颗粒尺寸的减少，与颗粒晶界有关的磁电阻在25K恒温、0.4T低场下由25%增加到了51%。实验结果表明，在La2/3Ca1/3MnO3中少量Cu掺杂和小颗粒尺寸可以实质性地提高与颗粒晶界有关的低场磁电阻效应。     

LiOH-Li_2CO_3低共熔混合锂盐体系合成LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2

利用低共熔组成的0.24LiCO3-0.76LiOH混合锂盐体系,与钴、镍、锰的球形氢氧化物按1.1:1混合,无需前期球磨,直接经二段控温程序制备出锂离子正极材料LiNi1/3Co1/3Mn1/3O2。X射线衍射分析表明合成的Li(Ni1/3Co1/3Mn1/3)O2结晶度高,具有规整的层状α-NaFeO2结构,扫描电镜显示产物颗粒均匀,振实密度高达2.89g·cm-3,显著高于用单一锂盐制备的同样产品(2.4g·cm-3)。充放电测试表明,材料具有良好的电性能,首次充放电容量为176和166mhA·g-1,循环50次后,材料的电性能没有明显的衰减。     

Si4+和F-掺杂对LiNi1/3Co1/3Mn1/3O2结构和电化学性能的影响

以Li2CO3、NiO、Co2O3、MnO2、LiF和SiO2为原料,采用机械力活化固相法制备了Si4+和F-掺杂的锂离子电池正极材料LiNi1/3Co 1/3Mn1/3O2.通过X射线衍射(XRD)、扫描电镜(SEM)和电化学性能测试等技术研究了LiNi1/3Co1/3Mn1/3O2的结构特征、形貌及电化学性能等.结...     

Synthesis and characterization of layered Li（Ni1/3Mn1/3CO1/3）O2 cathode materials by spray-drying method

Spherical Li(Ni_(1/3)Mn_(1/3)Co_(1/3))O_2 was prepared via the homogenous precursors produced by solution spray-drying method. The precursors were sintered at different temperatures between 600 and 1 000 ℃ for 10 h. The impacts of different sintering temperatures on the structure and electrochemical performances of Li(Ni_(1/3)Mn_(1/3)Co_(1/3))O_2 were compared by means of X-ray diffractometry(XRD), scanning electron microscopy(SEM), and charge/discharge test as cathode materials for lithium ion batteries. The experimental results show that the spherical morphology of the spray-dried powers maintains during the subsequent heat treatment and the specific capacity increases with rising sintering temperature. When the sintering temperature rises up to 900 ℃ , Li(Ni_(1/3)Mn_(1/3)Co_(1/3))O_2 attains a reversible capacity of 153 mA·h/g between 3.00 and 4.35 V at 0.2C rate with excellent cyclability.     

稀土空位锰氧化物(La(1-x-y)Yy)2/3Ca1/3MnO3的结构和输运性质

用固相反应法制备了La(1-x)2/3Cai/3MnO3(V-LCMO)和(La(0.7-x)Y0.3)2/3Cai/3MnO3)(V-LYCMO)(x=0,0.02,0.04,0.08,0.10)系列La空位锰氧化物样品.X射线衍射(XRD)分析表明:所有的样品均为单相,具有正交对称性(Pnma).La(1-x)2/3Cai/3MnO3系统和(La(0.7-x)Y0.3)2/3Cai/3MnO3系统的晶格参数以及Mn-O键长和Mn-O-Mn键角随La空位浓度不同而改变,说明在室温系统中存在Jahn-Teller效应.对于V-LYCMO系统,其晶格参数、Mn-O键长和Mn-O-Mn键角都比V-LCMO相应的值更小,这可能与离子半径小的Y3 部分替代La3 导致更大的晶格畸变有关.V-LCMO系统随着空位浓度的增大,绝缘体-金属的转变温度TMI几乎不变.在x=0.04时MR值在温度TMI处达到最大值,约为220%(8T).而对V-LYCMO系统,其转变温度TMI约为50 K,在温度40～50 K左右最大的磁电阻值超过106%.认为很大的磁电阻效应与用离子半径小的Y部分替代离子半径大的La有关,它会破坏双交换作用,从而导致Jahn-Teller效应.     

前处理工艺对Li[Ni1/3Mn1/3Co1/3]O2正极材料结构、形貌和电化学性能的影响（英文）

以[Ni1/3Co1/3Mn1/3]3O4和氢氧化锂为原料,分别采用球磨法和液相法前处理工艺制备层状正极材料Li[Ni1/3Mn1/3Co1/3]O2。采用X？射线衍射（XRD）、场发射扫描电镜（FESEM）、恒流充放电等手段对材料的物理和电化学性能进行表征。结果表明：采用不同前处理工艺制备出的Li[Ni1/3Mn1/3Co1/3]O2材料在结构、形貌和电化学性能上有较大差异;与球磨处理法制备的材料相比,采用液相法前处理工艺制备的Li[Ni1/3Mn1/3Co1/3]O2不但保持了前驱体较好的球形形貌,同时还具有较好的循环稳定性和倍率性能;该样品在20mA/g电流密度下,首次放电容量为178mA·h/g,50次循环后,容量保持率达98.7%;在1000mA/g电流密度下,样品容量为135mA·h/g。