Al2O3包覆LiNi0.03Co0.05Mn1.92O4正极材料的制备及其电化学性能

以Al(NO3)3?9H2O为包覆原料,通过燃烧法制备得到LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料。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,Al2O3包覆没有改变LiNi0.03Co0.05Mn1.92O4的尖晶石型结构,包覆层厚度约10.6nm。LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料电化学性能得到了明显改善,1 C和10 C倍率下初始放电比容量分别为119.9 mAh?g-1和106.3 mAh?g-1,充放电循环500次后容量保持率分别为88.4%和78.2%,而未包覆的LiNi0.03Co0.05Mn1.92O4在1 C和10 C倍率下初始放电比容量分别为121.2 mAh?g-1和104.0 mAh?g-1,500次循环后容量保持率分别为84.1%和67.6%。LiNi0.03Co0.05Mn1.92O4@Al2O3活化能为32.92 kJ?mol-1,而未包覆材料的活化能为36.24 kJ?mol-1,包覆有效降低了材料Li+扩散所需克服的能垒,提高了材料的电化学性能。     

尖晶石LiNi_(0.5)Mn_(1.5)O_4中掺杂Fe的作用机理

利用湿化学法结合固相反应法制备了尖晶石LiNi_(0.5)Mn_(1.5)O_4和掺杂Fe的LiNi_(0.45)Fe_(0.1)Mn_(1.45)O_4材料,从晶体结构、表面形貌、充放电曲线特点、倍率性能等方面比较了掺杂Fe以后对材料的影响,并结合热重实验,通过测试失重量,进而分析了材料中的氧缺陷含量,推导出掺杂Fe的作用机理:尖晶石LiNi_(0.5)Mn_(1.5)O_4材料中掺杂Fe元素,能够使材料晶体中保持一定的氧缺陷,从而使得材料含有一定量的Mn~(3+),提高了材料充放电倍率性能。     

Zn对锂电池材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2结构和电化学性能的影响

采用共沉淀法掺入少量Zn得到Li(Ni1/3Co1/3Mn1/3)1-xZnxO2材料。通过X射线衍射、光电子能谱(XPS)和电化学测试研究掺杂对其晶体结构、元素价态和电化学行为的影响。结果表明:掺入Zn增大晶格常数;在粉末颗粒表面的Zn含量是颗粒内部的数十倍;掺杂后Co、Mn依然保持+3、+4价,但是Ni由+2、+3混合价态组成;掺入少量Zn阻止电极在4.5V电位下的不可逆氧化反应;掺入Zn有效改善高截止电压下的循环容量保持能力,其作用与改变材料表面状态有关。     

Synthesis and characterization of LiNi0.95-xCoxAl0.05O2 for lithium-ion batteries

Samples of LiNi0.95-xCoxAl0.05O2 （x = 0.10 and 0.15） and LiNiO2, synthesized by the solid-state reaction at 725℃ for 24 h from LiOH-H2O, Ni2O3, Co2O3, and AI（OH）3 under an oxygen stream, were characterized by TG-DTA, XRD, SEM, and electrochemical tests. Simultaneous doping of cobalt and aluminum at the Ni-site in LiNiO2 was tried to improve the cathode performance for lithium-ion batteries. The results showed that co-doping （especially, 5 at.% A1 and 10 at.% Co） definitely had a large beneficial effect in increasing the capacity （186.2 mA.h/g of the first discharge capacity for LiNio.s.42OoaoAlo.0502） and cycling behavior （180.1 mA-h/g after 10 cycles for LiNio.85CooaoAlo.osO2） compared with 180.7 mA.h/g of the first discharge capacity and 157.7 mA.h/g of the tenth discharge capacity for LiNiO2, respectively. Differen- tial capacity versus voltage curves showed that the co-doped LiNio.95_xCoxmlo.osO2 had less intensity of the phase transitions than the pristine LiNiO2.     

高振实密度球形LiNi_(0.5)Co_(0.3)Mn_(0.2)O_2粉末的合成及性能

以共沉淀法制备的球形Ni_(0.5)Co_(0.3)Mn_(0.2)CO_3粉末为前驱体,按一定的比例将碳酸锂与前驱体混合,然后采用高温固相法合成高振实密度球形LiNi_(0.5)Co_(0.3)Mn_(0.2)O_2正极材料.该材料的振实密度达到2.60 g/cm~3,与商品化LiCoO_2的密度相当.SEM分析表明, LiNi_(0.5)Co_(0.3)Mn_(0.2)O_2正极材料与前驱体形貌有良好的继承性,均为理想的球形.XRD物相分析表明,在不同合成温度下的Li Ni_(0.5)Co_(0.3) Mn_(0.2)O_2产物均为具有α-NaFeO_2层状结构的纯相物质,在较高合成温度下所得材料的结晶度较高.电化学性能研究表明,在2.7～4.3 V的电压范围内,电池的放电比容量在0.2C倍率下为168.1 mA-h/g,在1C倍率下为157.6 mA-h/g;经50次循环后,两种放电条件下的电池容量保持率分别为95.1%和97.2%,显示出良好的电化学性能.     

Effects of synthesis conditions on the structural and electrochemical properties of layered LiNi1/3Co1/3Mn1/3O2 cathode material via oxalate co-precipitation method

The uniform layered LiNi1/3Co1/3Mn1/3O2 cathode material for lithium ion batteries was prepared by using (Ni1/3Co1/3Mn1/3)C2O4 as precursor synthesized via oxalate co-precipitation method in air. The effects of calcination temperature and time on the structure and electrochemical properties of the LiNi1/3Co1/3Mn1/3O2 were systemically studied. XRD results revealed that the optimal calcination conditions to prepare the layered LiNi1/3Co1/3Mn1/3O2 were 950°C for 15 h. Electrochemical measurement showed that the sample prepared under the such conditions has the highest initial discharge capacity of 160.8 mAh/g and the smallest irreversible capacity loss of 13.5% as well as stable cycling performance at a constant current density of 30 mA/g between 2.5 and 4.3 V versus Li at room temperature.     

Synthesis and electrochemical characterization of layered Li[Ni1/3CO1/3 Mn1/3]O2 cathode material for Li-ion batteries

1 INTRODUCTIONDue to the high cost of LiCoO2,a commonlyused cathode material in commercial rechargeablelithium-ion batteries , much efforts have been madeto develop cheaper cathode materials than LiCoO2,Li Ni O2and Li MnO2have been studied extensivelyas possible alternatives to LiCoO2[1 4 ]. Stoichio-metric Li Ni O2is knownto be difficult to synthesizeandits multi-phase reaction during electrochemicalcyclingleads to structural degradation,andlayeredLi MnO2has a significant drawback…     

基于基团贡献法估算锂离子动力电池正极材料LiNixCoyMnzO2的ΔHf,298θ和ΔGf,298θ

基于基团贡献法对裡离子动力电池正极材料LiNi0.6Co0.2Mn0.2O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.1Mn0.1O2和LiNi1/3Co1/3Mn1/3O2的△Hf,298θ和△Gf,298θ进行估算。首先采用基团贡献法对56种固体无机化合物的△Hf,298θ和△Gf,298θ进行估算,估算值与文献值相比,相对误差绝对值都在4%之内。基于基团贡献法首次构建了估算锂离子动力电池正极材料LiNixCOyMnzO2的△Hf,298θ和△Gf,298θ的数学模型,结合XPS实验数据分析结果,对LiNi0.6Co0.2Mn0.2O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.1Mn0.1O2和LiNi1/3Co1/3Mn1/3O2正极材料的Hθf,298和ΔGθf,298进行估算,对应正极材料的△Hf,298θ和△Gf,298θ估算值分别为-705.39,-703.90,-695.67,-705.17 kJ·mol^-1和-647.98,-640.04,-631.10,-642.41 kJ·mol^-1。     

烧结温度对LiNi（0.8）Co（0.1）Mn（0.1）O2材料倍率性能和循环性能的影响

以共沉淀法制备的球形Ni0.8Co0.1Mn0.1（OH）2和Li OH·H2O为原料,研究烧结温度对LiNi0.8Co0.1Mn0.1O2材料形貌、结构以及材料循环性能和倍率性能的影响。SEM和XRD结果表明：温度对材料形貌和结构有较大的影响,控制适当温度既能保证材料具有良好的形貌,也能抑制材料中锂镍的混排。电化学测试结果显示,当烧结温度从700℃升高至750℃时,材料性能逐渐提高,但是温度过高会恶化材料的性能。750℃和780℃烧结材料的循环性能几乎一致,200次循环后容量保持率为71.9%,但780℃烧结材料的倍率性能低于750℃材料的,其原因归结于温度过高,锂镍的混排加剧。在小电流充放电时,对材料性能影响有限,但是在大电流充放电时,3a位的Ni2＋将严重阻碍锂离子的扩散。     

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.     

Preparation and electrochemical characteristics of CO3（PO4）2-coated LiNi0.8Co0.2O2 by solid-state reaction at room temperature

LiNi0.8Co0.2O2 particles were modified by Co3（PO4）2 coating. The effects of the Co3（PO4）2 coating on the structure and electrochemical properties of the LiNi0.8Co0.2O2 cathode material were investigated. The Co3（PO4）2 coating forms a thin layer on the surface of the LiNi0.8Co0.2O2 material and a solid solution by interacting with the LiNi0.8Co0.2O2 core material during calcination at 700℃ for 4 h. Charge-discharge experiment results show that the Co3（PO4）2 coating improves the cycling stability of the LiNi0.8Co0.2O2 cathode material. The capacity retention of the pristine LiNi0.8Co0.2O2 cathode after 50 cycles is 83.6%, whereas it is 91.7% in the case of the LiNi0.8Co0.2O2 cathode coated with 1 wt.% Co3（PO4）2. Storage tests of the 4.35 V charged electrode at 60℃ after a month show that the Co3（POg）2-coated sample exhibits good storage properties compared with the pristine sample.     

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.     

共沉淀法制备LiNi0.8Co0.1Mn0.1O2过程中加料速度对其性能的影响

采用共沉淀法制备Ni0.8Co0.1Mn0.1(OH)2前驱体,与LiOH.H2O混合后在氧气气氛中焙烧得到LiNi0.8Co0.1Mn0.1O2正极材料,探讨共沉淀反应过程中快速加料和慢速加料制度对前驱体形貌和LiNi0.8Co0.1Mn0.1O2正极材料性能的影响。通过X射线衍射(XRD)、扫描电镜(SEM)和电化学测试对样品进行表征。结果表明:慢速加料法减小了材料的粒径,合成了平均粒径在0.5μm左右的球形Ni0.8Co0.1Mn0.1(OH)2前驱体,且粒径分布比较集中;所合成LiNi0.8Co0.1-Mn0.1O2正极材料具有良好的层状结构,且无杂相存在;缓慢加料法得到的样品的电化学性能有很大提高,在0.1 C、0.5 C和1 C下首次放电比容量分别达到223.5、194.3和190.7 mA.h/g,循环30次后,容量保持率为80.09%、80.80%和85.84%。     

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...     

快速共沉淀过程pH值对Ni_(0.8)Co_(0.1)Mn_(0.1)(OH)_2及LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2性能的影响

采用快速共沉淀法制备Ni0.8Co0.1Mn0.1(OH)2前驱体,利用前驱体与LiOH.H2O的高温固相反应得到锂离子电池层状正极材料LiNi0.8Co0.1Mn0.1O2,探讨pH值对材料结构和电化学性能的影响。通过X射线衍射(XRD)、扫描电镜(SEM)和电化学测试对合成样品进行表征。结果表明,pH值为11.00~12.00时,合成的Ni0.8Co0.1Mn0.1(OH)2前驱体均无杂相;pH值为11.50时,合成的前驱体制备出的正极材料具有良好的电化学性能,0.1C倍率下首次放电比容量为192.4 mA.h/g;经过40次循环,容量保持率为91.56%。     

正极材料LiNi0.4Co0.2Mn0.4O2阴离子掺杂改性研究

采用溶胶-凝胶法合成了层状LiNi0.4Co0.2Mn0.4O1.97X0.03(X=O,F,Cl)正极材料。以XRD、SEM、CV、EIS和充放电测试等手段对材料的晶体结构、表观形貌和电化学性能进行表征。XRD结果显示F-和Cl-掺杂没有改变晶体的六方单层状结构;CV结果表明掺杂提高了材料的可逆性;充放电测试表明,F-和Cl-掺杂均提高了材料的放电容量,并改善了材料的循环性能;EIS测试结果发现,F-和Cl-掺杂均有效地抑制其在循环过程中电化学反应阻抗的增加。     

Effect of ball milling and electrolyte on properties of high-voltage LiNi_(0.5)Mn_(1.5)O_4 spinel

1 INTRODUCTIONRecently ,several research groups have repor-ted transition-metal-substituted spinel materials(Li MxMn2 -xO4, M: Cr , Co , Fe , Ni , Cu) withhigh-voltage plateaus above 4 .5 V[1 5]. Amongthese materials ,Li Ni0 .5Mn1 .5O4is the most prom-ising and attractive one because of its good cyclicproperty and relatively high capacity with a plateauat around 4 .7 V[3 ,6].Now, a variety of methods were used forpreparation of Li Ni0 .5Mn1 .5O4,such as solid-statereaction[4 ,7 ,8]…     

Electrochemical characterization of AlPO_4 coated LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 cathode materials for high temperature lithium battery application

Aluminum phosphate(AlPO_4) was used to modify the surface of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2(NCM) cathode material.The surface structure and electrochemical properties of the coated materials were investigated by X-ray photoelectron spectroscopy(XPS) and electrochemical impedance spectroscopy(EIS).The results confirm the formation of aluminum-containing solid solution on the surface of NCM particles.An aluminum phosphate coating blocks the Li~+ insertion-extraction process in cells charged at high rates at room temperature,increasing surface film resistance and decreasing discharge capacity.However,an aluminum phosphate aids the formation of a stable solid electrolyte interface film on NCM surface and stabilizes the R_(ct) of cell as samples electrochemically cycled at 55℃.The electrochemical studies suggest that the initial columbic efficiency is significantly enhanced.An NCM sample coated with 1.0 wt% AlPO_4 delivers a higher discharge capacity and shows excellent capacity retention ability.     

LiNi0.7Co0.15Mn0.15O2 microspheres as high-performance cathode materials for lithium-ion batteries

Advanced uniform LiNi0.7Co0.15Mn0.15O2 microspheres were successfully synthesized and examined as cathode materials for lithium-ion batteries. The structure,morphology, and electrochemical performance of LiNi0.7-Co0.15Mn0.15O2 calcined at different temperatures ranging from 650 to 900 °C were systematically investigated. The XRD results show that the material has a well-ordered layered structure with small amount of cation mixing. A distinct spherical morphology of the obtained powders prepared at different temperatures can be seen from the SEM images. The as-synthesized LiNi0.7Co0.15Mn0.15O2 powders have a very high-tap density of about 2.37 g·cm^-3. Among all the samples,the sample calcined at 750 °C exhibits the best electrochemical performance with an initial discharge capacity of185.2 mAh·g^-1（3.0–4.3 V, 0.2C rate） and capacity retention〉94.77 %after50cycles.Moreover,thismaterialshowshighspecific capacity and good cycling stability. The LiNi0.7-Co0.15Mn0.15O2 microspheres with high-specific capacity and high-tap density are promising to use as cathode materials for next-generation high-energy-density lithium-ion batteries.     

Enhanced High-Voltage Cycling Stability of Nickel-Rich Cathode Materials by Surface Modification Using LaFeO3 Ionic Conductor

JOM - LaFeO3 is introduced as an ideal protective coating layer with excellent conductivity to enhance LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode material for use at higher operating voltage (especially...