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.     

合成条件对氢氧化物共沉淀法制备锂离子电池层状正极材料Li[Ni_（1/3）Co_（1/3）Mn_（1/3）]O_2的影响

以共沉淀法制备的过渡金属氢氧化物前驱体合成锂离子电池层状正极材料Li[Ni1/3Co1/3Mn1/3]O2。考察氨与过渡金属阳离子的配位效应对Li[Ni1/3Co1/3Mn1/3]O2材料的结构和电化学性能的影响。SEM分析结果表明,当NH3·H2O与过渡金属阳离子的总摩尔比为2.7：1时,获得了分布均一的颗粒为过渡金属氢氧化物共沉淀,合成的Li[Ni1/3Co1/3Mn1/3]O2材料的平均粒径约为500nm,振实密度接近2.37g/cm3,接近商品化的LiCoO2正极材料的振实密度。XRD分析结果表明,合成的Li[Ni1/3Co1/3Mn1/3]O2材料具有六角晶格层状结构。Li/Li[Ni1/3Co1/3Mn1/3]O2电池在2.8-4.5V电压范围内的0.1C倍率测试结果表明,首次放电容量达181.5mA·h/g,0.5C倍率循环50次后的放电容量为170.6mA·h/g。     

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。     

层状LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料的多元掺杂改性

采用共沉淀法制备锂离子电池掺杂型层状LiNi1/3Co1/3Mn1/3-xMxO2(M=Mg、Al、Cr)正极材料。采用X射线衍射、扫描电镜、充放电实验和交流阻抗实验对LiNi1/3Co1/3Mn1/3-xMxO2正极材料的结构、形貌、电化学性能以及动力学参数进行表征。结果表明:当掺杂量x=0.05时,Mg2+、Al3+掺杂的正极材料在2.8～4.3V、0.1C下的首次放电比容量分别为139.2、151.6mA·h/g,20次循环后的容量保持率分别为98.8%和96.7%;掺杂Mg2+或Al3+均能提高LiNi1/3Co1/3Mn1/3O2的交换电流密度和锂离子扩散系数。结合实验结果和掺杂离子的离子半径和化学稳定性,解释了掺杂离子在LiNi1/3Co1/3Mn1/3O2晶格中的占位及其在充放电过程中的作用。     

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.     

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。     

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。     

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...     

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...     

锂离子电池正极材料Li1+xNi1/3Co1/3Mn1/3O2的合成

采用碳酸盐共沉淀法合成了Li1+xNi1/3Co1/3Mn1/3O2正极材料。用X射线粉末衍射仪、高频电感耦合等离子体原子发射光谱仪和扫描电子显微镜对材料的晶体结构、化学元素组成和表面形貌进行了分析研究。将正极材料Li1+xNi1/3Co1/3Mn1/3O2制成电极极片,组装成混合动力车用3Ah高功率电池进行测试。分析测试结果表明,合成的正极材料Li1+xNi1/3Co1/3Mn1/3O2具有典型的α-NaFeO2结构,粒径约为10μm。在室温(25℃),电池经2000次充放电循环后容量可保持80%;在50%DOD下,电池10 s脉冲输出功率密度为2100 W/kg,输入功率密度为2700 W/kg。     

LiNi1/3Co1/3Mn1/3O2和LiNi3/8Co1/4Mn3/8O2纳米纤维的合成与电化学性能

以溶胶前驱体为纺丝液,通过静电纺丝法合成锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2和LiNi3/8Co1/4Mn3/8O2纳米纤维.采用原子力显微镜(AFM)、X射线衍射(XRD)、充放电实验对纳米纤维的形貌、结构和电化学性能进行研究.结果表明,纳米纤维的直径在150～200 nm之间,且具有典型的α-NaFeO2层状结构.LiNi1/3Co1/3Mn1/3O2和LiNi3/8Co1/4Mn3/8O2纳米纤维的首次放电容量均超过170 mAh·g-1,50次循环后容量保持率在90%以上.     

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%.     

Pseudocapacitance properties of AC/LiNi1/3Co1/3Mn1/3O2 asymmetric supercapacitor in aqueous electrolyte

NH₂NH₂·H₂O which was used as controlling agent was applied to prepare the precursor Ni_1/3Co_1/3Mn_1/3(OH)₂ in the hydroxide co-precipitation method. The precursor was used to synthesize LiNi_1/3Co_1/3Mn_1/3O₂. The samples were characterized by XRD, XPS and SEM. It has been found that sintered sample at 800 °C for 16 h is considered as the optimal synthetic condition. The LiNi_1/3Co_1/3Mn_1/3O₂ was used as positive electrode and the activated carbon as negative electrode of the asymmetric supercapacitor. The electrochemical capacitance performance was tested by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge/discharge. The results indicate that species of aqueous electrolyte, current density, scan rate and potential limit, etc. have influence on the capacitance property of AC/LiNi_1/3Co_1/3Mn_1/3O₂ supercapacitor. The initial discharge specific capacitance of 298 F g^?1 was obtained in 1 mol L^?1 Li₂SO₄ solution within potential range 0–1.4 V at the current density of 100 mA g^?1 and was cut down less than 0.058 F g^?1 per cycling period in 1000 cycles. The asymmetric supercapacitor exhibited a good cycling performance.     

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.     

Preparation of LiNi1/3Co1/3Mn1/3O2 cathode materials from spent Li-ion batteries

A recycling process including separation of electrode materials by ultrasonic treatment, acid leaching, Fe-removing, precipitation of cobalt, nickel, manganese and lithium has been applied successfully to recycle spent lithium-ion batteries and to synthesize LiNi1/3Co1/3Mn1/3O2. When ultrasonic treatment with 2-nitroso-4-methylphenol（NMP） at 40 ℃ for 15 min, the electrode materials are separated completely. Above 99% of Co, Ni, Mn and Li, 95% of Fe in the separated electrodes are acid-leached in the optimized conditions of 2 mol/L H2SO4, 1：2 H2O2：H2SO4 （molar ratio）, 70 ℃, 1：10 initial S：L ratio, and l h. 99.5% of Fe and less than 1% of Co, Ni, Mn in the leaching solution can be removed in the conditions of initial pH value 2.0-2.5 adjusted by adding 18% Na2CO3, 90 ℃ and stirring time 3 h. After adjusted to be equal by adding NiSO4, COSO4 and MnSO4 solution, 97.1% of Ni, Co, Mn in the Fe-removing surplus leaching solution can be recovered as Ni1/3Co1/3Mn1/3（OH）2. 94.5% of Li in the surplus filtrate after the deposition of Co, Ni and Mn can be recovered as LiECO3. The LiNi1/3Co1/3Mnl/3O2, prepared from the recovered compounds, is found to have good characteristics of the layered structure and elecrtochemical performance.     

层状LixNi1/3Mn1/3Co1/3O2阴极材料的结构、电化学与热稳定性

用NO2BF4作为脱锂剂,通过化学反应定量脱去材料中的锂离子,合成出不同嵌锂量的LixNi1/3Mn1/3-Co1/3O2(0≤x≤1)系列材料.通过电感耦合等离子体质谱(ICP-MS)、光电子能谱(XPS)、X射线衍射(XRD)、循环伏安(CV)等方法表征手段发现,当锂脱出量超过总量的49%后,材料的结构、过渡金属的价态、电化学性能等方面都发生显著变化,这些变化中的不可逆因素影响了其首次充放过程的可逆性.结合TPD-MS以及TG分析,结果表明,在脱锂过程中晶格氧的活性增强,更加容易在较低温度下脱出,影响了材料的热稳定性.     

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.