改性LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料的合成及其电化学性能

采用固相反应法制备Mg2+掺杂的锂离子电池正极材料LiNil/3Col/3Mnl/3O2,并将Mg2+最佳掺杂量为0.03(摩尔分数)的样品进行CuO复合。通过X射线衍射(XRD)、扫描电镜(SEM)和电池测试系统等手段对制备的LiNil/3Col/3Mnl/3O2样品的结构、形貌及电化学性能进行表征。结果表明:Mg2+掺杂没有改变LiNil/3Col/3Mnl/3O2的层状结构,Mg2+掺杂量为0.03的LiNil/3Col/3Mnl/3-0.03Mg0.03O2材料具有最好的电化学性能和循环性能,在0.2C倍率下,首次放电比容量达158.5 mA·h/g,10次循环后容量保持率为91.2%。添加CuO的LiNil/3Col/3Mnl/3-0.03Mg0.03O2的首次放电容量为167.4 mA·h/g,高电压下达到181.0 mA·h/g;循环10次后,放电比容量为159.4 mA·h/g,容量保持率为95.3%,改性后的放电比容量、循环性能及在高倍率和高电压下的性能均得到改善。     

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。     

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。     

热处理过程中锂离子电池正极材料LiNi_(0.5)Co_(0.2)Mn_(0.3)O_2的结构变化及电化学性能

将前驱体Ni0.5Co0.2Mn0.3(OH)2以及前驱体和碳酸锂的混合物分别进行热处理,初步探讨其在高温热处理过程中的结构变化以及热处理方式对材料电化学性能的影响。采用X射线衍射(XRD)、热重-差热分析(TG-DSC)、扫描电镜(SEM)以及恒流充放电测试技术对合成材料物理性能和电化学进行测试和表征。结果表明:前驱体在热处理过程中,其结构经历由Me(OH)2→NiCoOOH→Mn(Ni,Co)2O4的转变过程;而前驱体与碳酸锂的混合物则经历由两相混合物→三元材料+Li2CO3→三元材料的结构转变过程;相比于单一高温平台热处理而言,采用低高温双平台热处理所合成的材料可有效降低阳离子混排,使其具有更好的电化学性能。电化学测试结果表明:在3.0~4.4V电压范围内,其在25℃、0.5C下首次放电比容量为160.5 mA·h/g,60次循环后,容量保持率达98.9%。     

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。     

锂离子电池正极材料LiNi_(0.5)Co_(0.5)O_2制备与电化学性能

采用球磨湿混和旋转合成相结合的新工艺制备了锂离子电池正极材料LiNi0.5Co0.5O2,并对材料进行了粒度、化学成分以及电化学性能测试。球磨湿混工艺能将原料混合均匀,并能有效地使粒度细化。旋转合成工艺能使混合料在均匀的温度场中进行反应,并使反应产物粒度均匀和成分均匀。制备的LiNi0.5Co0.5O2为单一的α-NaFeO2层状结构,粉末粒度分布范围窄,平均粒径约为8μm-10μm。电化学性能测试结果表明,在0．2mA/cm^2充放电流密度和3．0V－4．2V电压范围内,首次充电容量为173mAh/g,放电容量为148mAh/g。循环次数达30次时, 放电容量还有129mAh/g,循环稳定性良好。球磨湿混和旋转合成相结合的固相合成新工艺能制备出电化学性能良好的LiNi0.5Co0.5O2正极材料。     

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.     

锂离子电池正极材料LiNi_(0.5)Co_(0.5)O_2制备与电化学性能

采用球磨湿混和旋转合成相结合的新工艺制备了锂离子电池正极材料 L i Ni0 .5Co0 .5O2 ,并对材料进行了粒度、化学成分以及电化学性能测试。球磨湿混工艺能将原料混合均匀 ,并能有效地使粒度细化。旋转合成工艺能使混合料在均匀的温度场中进行反应 ,并使反应产物粒度均匀和成分均匀。制备的 L i Ni0 .5Co0 .5O2 为单一的 α- Na Fe O2 层状结构 ,粉末粒度分布范围窄 ,平均粒径约为 8μm～ 10μm。电化学性能测试结果表明 ,在 0 .2 m A/cm2 充放电流密度和 3 .0 V～ 4 .2 V电压范围内 ,首次充电容量为 173 m Ah/g,放电容量为 14 8m Ah/g。循环次数达 3 0次时 ,放电容量还有 12 9m Ah/g,循环稳定性良好。球磨湿混和旋转合成相结合的固相合成新工艺能制备出电化学性能良好的L i Ni0 .5Co0 .5O2 正极材料。     

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。     

F~-掺杂LiNi_(0.5)Mn_(1.5)O_4材料的制备及性能研究

为改善LiNi_(0.5)Mn_(1.5)O_4的倍率性能和循环性能,采用二步固相法制备了F-掺杂的LiNi_(0.5)Mn_(1.5)O_(4-x)F_x(x=0,0.05,0.1,015,0.2)正极材料,讨论了不同F掺杂量对材料性能的影响。X射线衍射、扫描电镜结果表明,掺杂和未掺杂的正极材料都为单一的尖晶石结构,粒度分布均匀。充放电测试、循环伏安和交流阻抗测试结果表明:当F的掺杂量为x=0.1时(LiNi_(0.5)Mn_(1.5)O_(3.9)F_(0.1))正极材料的性能最好,0.1,0.5,1,2及5C倍率的首次放电比容量依次为129.07,123.59,118.49,114.49和92.57 mAh/g。1C倍率下循环30次,容量保持率仍为98.84%。     

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.     

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...     

Structural evolution of mesoporous graphene/LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 composite cathode for Li-ion battery

Layered LiMO_2(M=Ni,Co,and Mn) is a type of promising cathode materials for high energy density and high work voltage lithium-ion batteries.However,the poor rate performance and low power density hinder its further applications.The capacity fade is related to the structural transformation in the layered LiMO_2.In this work,the structural changes of bi-material cathode composed of mesoporous graphene and layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2(NCM) were studied via in situ X-ray diffraction(XRD).During different C-rate charge-discharge test at the voltage range of 2.5-4.1 V,the composite cathode of NCM-graphene(NCM-G) reveals better rate performances than pure NCM cathode.The NCM-G composite electrode displays a higher rate capability of 76.7 mAh·g~(-1) at 5 C rate,compared to the pure NCM cathode of 69.8 mAh·g~(-1)discharge capacity.The in situ XRD results indicate that a reversible phase transition from hexagonal H1 to hexagonal H2 occurs in layered NCM material during 1 C chargedischarge process.With the current increasing to 2 C/5 C,the structure of layered NCM material for both electrodes reveals few changes during charge and discharge processes,which indicates the less utilization of NCM component at high C-rates.Hence,the improved rate performance for bi-material electrode is attributed to the highly conductive mesoporous graphene and the synergistic effect of mesoporous graphene and NCM material.     

Electrochemical performance of LiNi_(0.5)Mn_(0.5)O_2 with different synthesis methods

Li Ni0.5Mn0.5O2 as a cathode material for Li-ion battery was prepared by the metal acetate decomposition method, sol–gel method, and carbonate co-precipitation method, respectively. The influences of synthesis methods on the physical and electrochemical behaviors of Li Ni0.5Mn0.5O2 were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and electrochemical tests. XRD patterns show that both the sol–gel and carbonate co-precipitation methods can form single phase of layered structure, while a trace of Ni O impurity is observed via the metal acetate decomposition method. SEM results show the as-prepared carbonate particle has a spherical morphology with an average diameter of 10 lm, consisted of primary nano-sized particles with particle diameter of200 nm. The sample prepared by the carbonate co-precipitation method exhibits the highest discharge specific capacity and the best cycling stability, which results from the steady homogeneity of precursor constant by the fixation of CO2-3group. It can deliver an initial discharge specific capacity of 186.3 m Ahág-1, and retain 170 m Ahág-1after100 cycles at a current rate of 20 m Aág-1in the voltage range of 2.5–4.7 V at 25 °C. Moreover, even at the high temperature of 55 °C, it still delivers a reversible specific capacity of 222.6 m Ahág-1with little capacity loss after 30 cycles.     

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%。     

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。