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。     

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.     

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…     

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…     

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.     

Preparation of LiNi_(1-y)Co_yO_2 in certain oxygen pressure

1　INTRODUCTIONLi ionbatteryisthenewlydevelopedrecharge ablebatterysubsequenttoCd/NiandMH/Nibat tery .Itshighenergypropertyisnotonlyfitforthepowersupplyofsmallscaleelectricproductdevelop ingattopspeed ,butalsofitforthepowersupplyofthelargescalemotivepowertooltoavoid pollutingtheenvironment .Thepreparationofcathodematerialisthekeylinksforthedevelopmentoflithiumionbattery .Atpresent ,thecathodematerialsusedinlithiumionbatteryareLiCoO2 ,LiNiO2 ,LiMn2 O4 andtheirderivatives .Amongthem ,…     

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...     

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。     

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.     

Synthesis and electrochemical performance of 5V spinel LiNi0.5Mn1.5O4 prepared by solid-state reaction

Spinel compound LiNi0.5Mn1.5O4 with high capacity and high rate capability was synthesized by solid-state reaction. At first, MnCl2·4H2O and NiCl2·6H2O were reacted with (NH4)2C2O4·H2O to produce a precursor via a low-temperature solid-state route, then the precursor was reacted with Li2CO3 to synthesize LiNi0.5Mn1.5O4. The effects of calcination temperature and time on the physical properties and electrochemical performance of the products were investigated. Samples were characterized by thermal gravimetric analysis(TGA), scanning electron microscopy(SEM), X-ray diffractometry(XRD), charge-discharge tests and cyclic voltammetry measurements. Scanning electron microscopy(SEM) image shows that as calcination temperature and time increase, the crystallinity of the samples is improved, and their grain sizes are obviously increased. It is found that LiNi0.5Mn1.5O4 calcined at 800 ℃ for 6 h exhibits a typical cubic spinel structure with a space group of Fd3m. Electrochemical tests demonstrate that the sample obtained possesses high capacity and excellent rate capability. When being discharged at a rate as high as 5C after 30 cycles, the as-prepared LiNi0.5Mn1.5O4 powders can still deliver a capacity of 101 mA-h/g, which shows to be a potential cathode material for high power batteries.     

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%。     

Influence of Cr-Substitution on the Electrochemical Performance of LiNi0.5Mn0.5O2 Cathode Material for Lithium Ion Batteries

采用低温燃烧法合成了锂离子电池正极材料LiNi0.5Mn0.5-xCrxO2(x=0,0.01,0.02,0.05,0.1),研究了Cr取代部分Mn对其结构和电化学性能的影响。充放电测试结果表明:Cr取代部分Mn对正极材料LiNi0.5Mn0.5-xCrxO2的电化学性能有重要的影响,用适量的Cr取代Mn(x=0.02)能够提高正极材料的放电比容量和循环稳定性。X射线衍射(XRD)分析和循环伏安(CV)测试显示,Cr对Mn的适量取代能抑制正极材料中的阳离子混排,降低电极材料的极化,改善其可逆性能。LiNi0.5Mn0.48Cr0.02O2在2.5~4.6 V之间以0.1 C速率充放电,首次放电容量为179.9 mAh/g,第50次循环放电容量仍保有171.0 mAh/g,容量保持率达到95.1%     

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。     

Co~（2＋）掺杂对Li_2FeSiO_4/C电化学性能的影响

采用溶胶-凝胶法,合成纳米复合材料硅酸亚铁锂（Li2FeSiO4/C）。用XRD、TEM和电化学方法,研究了Co2＋掺杂对Li2FeSiO4/C的影响。结果表明,掺杂适量的Co2＋不会改变Li2FeSiO4的正交晶系结构,可稳定材料结构,改善高倍率充放电性能。室温下,Li2Fe0.97Co0.03SiO4/C以0.1C放电的首次放电比容量为151.8（mA.h）/g,20次充放电循环后放电比容量为131.2（mA.h）/g;Li2FeSiO4/C的首次放电比容量为122.0（mA.h）/g,20次循环后,比容量衰减率为20.3%。交流阻抗测试表明：Li2Fe0.97Co0.03SiO4/C在1.5～4.5V下充放电的可逆性优于Li2FeSiO4/C。     

Al离子掺杂对LiNi0.5Mn1.5O4高电压材料性能的影响

用固相法合成了Al掺杂的高电压LiNi0.5Mn1.5-xAlxO4材料,研究了材料晶胞参数、材料可逆比容量、放电电压及循环性能随掺Al量的变化规律。结果表明,随着掺Al量的增加,材料的可逆比容量在逐渐减小;当Al掺杂量为0.06(LiNi0.5Mn1.44Al0.06O4)时,样品具有最佳的循环性能,100周的容量保持率在97%左右。与此同时,使用以Al掺杂量为0.06的样品为正极,石墨为负极组装的全电池显示了良好的循环性能。     

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.     

Mg-Y共掺杂高电压钴酸锂正极材料的合成及其性能研究

将Co₃O₄、Li₂CO₃、Mg(OH)_2和Y₂O₃按一定化学计量比称取并混合均匀后,采用高温固相法合成LiCo_1-x-yMg_xY_yO₂正极材料并探究了Mg-Y共掺杂对钴酸锂高电压性能的影响。采用X射线衍射(XRD)和扫描电镜(SEM)分别表征其晶体结构和形貌。LiCo_1-x-yMg_xY_yO₂正极材料高电压性能测试结果表明选择Mg掺杂量为0.2%(质量分数),当Y的掺杂量为0.10%(质量分数)时,在3.0~4.6 V电压范围内0.5 C倍率下的初始放电比容量为212 mAh/g,循环50周的容量保持率为96.3%。4 C大倍率下,未掺杂Y元素样品容量保持率为54.9%,相比之下Y掺杂后容量保持率提高为60.4%。     

Effect of commercial AB5 alloy addition on the electrochemical properties of Ml-Mg-Ni-based hydrogen storage alloys

A commercial AB5 hydrogen storage alloy was used as an additive to improve the electrochemical properties of Ml-Mg-Ni-based hydrogen storage alloys.The effect of AB5 alloy addition on the phase structure,charge/discharge characteristics,and electrochemical kinetics of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 alloy was investigated.The maximum discharge capacity of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 + 4 wt.% AB5 electrode reaches 406 mAh/g.The anodic polarization,cyclic voltammetry,and potential step discharge experiments show that the electrochemical kinetics of the electrode with additives was promoted,with the LaNi5 phase of AB5 alloy acting as electro-catalytic sites in the electrode alloy.The high-rate dischargeability of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 + 4 wt.% AB5 alloy electrode at 1100 mA/g reaches 60.9%,which is 9.4% higher than that of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 alloy electrode.The cycling stability of the electrode with 4 wt.% AB5 alloy has also been improved.     

机械球磨Mg2Ni0．95Sn0．05＋x％Ni非晶复合物的微结构和电化学性能

用机械球磨法合成了Mg2Ni0．95Sn0．05＋x％Ni（质量分数，x=25，50，75，100，125）非晶复合物，研究了其微结构和电化学性能。微结构分析表明，不添加Ni粉的Mg2Ni0．95Sn0．05合金经100h球磨后仍然难以形成非晶结构，加入镍粉有助于非晶结构的形成。电化学研究表明，铸态最大放电容量仅为16mAh／g，球磨100h后容量改善不明显；加入Ni粉球磨后，容量大幅上升，随着Ni添加量的增加，复合物最大放电容量先增后减，在x=75时达到最大值625.6mAh／g。把x=50时的复合物，延长球磨时间t，复合物最大放电容量提高，当t=200h时达到670mAh／g。     

5 V正极材料LiNi0.5Mn1.5O4的草酸共沉淀法合成及性能

通过草酸共沉淀法成功合成了5 V正极材料LiNi0.5Mn1.5O4,采用XRD、SEM、充放电试验和循环伏安法对合成产物进行表征。XRD和SEM分析结果表明,所合成的正极材料LiNi0.5Mn1.5O4具有立方尖晶石结构（空间群为Fdˉ3 m）,结晶度高,粒度适中且比较均匀。电化学测试结果表明,合成产物具有优良的电化学性能,它仅在4.7 V附近有一个放电平台,0.1 C的放电容量高达133 mAh/g,50次循环后放电容量仍保持在128 mAh/g以上,1和3 C的放电容量在30次循环后也分别保持在122和101 mAh/g以上