共沉淀法制备LaF_3表面修饰LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2及性能研究

以LiNi1/3Co1/3Mn1/3O2为正极材料,采用共沉淀合成方法制备LaF3表面修饰LiNi1/3Co1/3Mn1/3O2正极材料,利用X射线衍射(XRD)、扫描电镜(SEM)和电化学测试等方法对合成材料的结构、形貌以及电化学性能进行表征。结果表明:经过LaF3表面修饰的LiNi1/3Co1/3Mn1/3O2材料保持了LiNi1/3Co1/3Mn1/3O2层状结构,其中LaF3表面修饰量为0.59%时,在电压为2.75～4.50V范围内,以0.3mA/cm2电流密度下经恒电流充放电测试,其首次放电比容量为172.7mAh/g,经过50周充放电循环后放电比容量为163.5mAh/g,表现出较高的初始放电比容量和良好的抗过充电性能。     

Comparative experiment on layered Li（Ni1/3Co1/3Mn1/3）O2 as the alternative material for LiCoO2

This work was financially supported by the National Natural Science Foundation of China （No.50472093）.     

共沉淀法制备LaF3表面修饰LiNi1／3C01／3Mn1／302及性能研究

以LiNi1／3CO1／3Mn1／302为正极材料,采用共沉淀合成方法制备LaF3表面修饰LiNimCo1/3Mnm02正极材料,利用X射线衍射（XRD）、扫描电镜（SEM）和电化学测试等方法对合成材料的结构、形貌以及电化学性能进行表征。结果表明：经过LaF3表面修饰的LiNi1／3C01／3Mn1／302材料保持了LiNi1／3Co1／3Mn1/302层状结构,其中LaFs表面修饰量为0．59％时,在电压为2．75-4．50V范围内,以0．3mA／cm。电流密度下经恒电流充放电测试,其首次放电比容量为172．7mAh／g,经过50周充放电循环后放电比容量为163．5mAh／g,表现出较高的初始放电比容量和良好的抗过充电性能。     

Preparation of spherical and dense LiNi0.8Co0.2O2 lithium-ion battery particles by spray pyrolysis

With citric acid as a polymeric agent layered LiNi0.8Co0.2O2 materials were synthesized by a spray pyrolysis method. The LiNi0.sCo0.2O2 particles were characterized by means of XRD, SEM and TEM. The electrochemical performances of LiNi0.8Co0.2O2 particles were studied in a voltage window of 3.00-4.35 V and at a current density of 30 mA/g. The results show that in the pilot-scale spray pyrolysis process, the morphology of particles is dependent upon the precursor concentration and flux of carrier gas. The initial discharge capacity of the LiNi0.8Co0.2O2particles at 720 ℃ for 12 h is 187.3 mA.h/g, and the capacity remains 96.8% with excellent cycleability after 30 cycles. The LiNi0.8Co0.2O2 samples synthesized under the optimized conditions by the spray pyrolysis method shows a good electrochemical performance.     

锌对Li（Ni_（1/3）Co_（1/3）Mn_（1/3））O_2电极首次脱锂过程电化学性能的影响

共沉积法制备不同含锌量的锂离子电池正极材料Li（Ni1/3Co1/3Mn1/3）O2.采用交流阻抗谱分析该正极材料在首次脱锂过程中的电化学特性以及锌对电极阻抗和锂离子扩散系数的影响.电极阻抗图谱分析结果表明：3.7～4.4V为电极发生电化学反应的电位区间;锌减小了电极材料的SEI膜阻抗和电荷转移阻抗;少量固溶锌提高了锂离子在材料固相中的扩散能力.     

Characteristics of LiCoO2, LiMn2O4 and LiNi0.45Co0.1Mn0.45O2 as cathodes of lithium ion batteries

LiNi0. 45 Co0. 10 Mn0. 4sO2 was synthesized from Li2CO3 and a triple oxide of nickel, cobalt and manganese at 950 ℃ in air. The structures and characteristics of LiNi0. 45 Co0.10 Mn0. 45 O2, LiCoO2 and LiMn2 O4 were investigated by XRD, SEM and electrochemical measurements. The results show that LiNi0.4s Co0.10 Mn0. 45 O2 has a layered structure with hexagonal lattice. The commercial LicoO2 has sphere-like appearance and smooth surfaces, while the LiMn2 O4 and LiNi0.45 Co0. 10 Mn0. 45 O2 consist of cornered and uneven particles. LiNi0. 45 Co0.10 Mn0. 45 O2 has a large disLiMn2 O4 and LiCoO2, respectively. LiCoO2 and LiMn2 O4 have higher discharge voltage and better rate-capability than LiNi0. 45Co0.10 Mn0. 45 O2. All the three cathodes have excellent cycling performance with capacity retention of above 89.3 % at the 250th cycle. Batteries with LiMn2 O4 or LiNi0.45 Co0.10 Mn0. 45 O2 cathodes show better safety performance under abusive conditions than those with LiCoO2 cathodes.     

正极材料LiNi_（0.4）Mn_（0.4）Co_（0.2）O_2的制备和性能

采用草酸共沉淀法合成了锂离子正极材料LiNi0.4Mn0.4Co0.2O2。用XRD、SEM和充放电实验对合成产物的结构、形貌和电化学性能进行了表征;用DSC对合成产物在不同充电状态下的热稳定性进行了研究。结果表明,采用草酸共沉淀法合成的正极材料LiNi0.4Mn0.4Co0.2O2具有α-NaFeO2型层状结构,阳离子有序度高,粒度均匀适中,电化学性能良好,首次放电比容量达到158.7 mAh/g,30次循环后放电比容量还有144.8 mAh/g;过充电状态下具有良好的热稳定性。     

Synthesis and electrochemical properties of Mg-doped LiNi<Subscript>0.6</Subscript>Co<Subscript>0.2</Subscript>Mn<Subscript>0.2</Subscript>O<Subscript>2</Subscript> cathode materials for Li-ion battery

The layered LiNi0.6Co0.2-xMn0.2MgxO2 (x=0.00,0.03,0.05,0.07) cathode materials were prepared by a co-precipitation method.The properties of the Mg-doped LiNi0.6Co0.2Mn0.2O2 were investigated by X-ray diffraction (XRD),scanning electron microscopy (SEM),and electrochemical measurements.XRD studies showed that the Mg-doped LiNi0.6Co0.2Mn0.2O2 had the same layered structure as the undoped LiNi0.6Co0.2Mn0.2O2.The SEM images exhibited that the particle size of Mg-doped LiNi0.6Co0.2Mn0.2O2 was finer than that of ...     

以Mn3O4为锰源合成高性能LiMn2O4正极材料

以Mn3O4为锰源,采用固相反应法,在较低的温度(650℃)制得尖晶石LiMn2O4正极材料。采用X射线衍射(XRD)、扫描电镜(SEM)、循环伏安和恒流充放电等技术对其相组成、微结构和电化学性能进行表征。结果表明该正极材料结晶良好,一次粒径约为150 nm。它的电化学性能,尤其是循环性能,明显优越于在较高温度合成的LiMn2O4。在电流密度为74 mA?g-1时,测得比容量为128 mAh?g-1,在1 480 mA?g-1时,比容量为105 mAh?g-1;在室温、148 mA?g-1充放电200次循环后,容量保持率为93%。     

Synthesis and characterization of Mg3(PO4)2-coated Li1.05Ni1/3Mn1/3Co1/3O2 cathode material for Li-ion battery

Mg₃(PO₄)₂-coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode materials were synthesized via co-precipitation method. The morphology, structure, electrochemical performance and thermal stability were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS), charge/discharge cycling and differential scanning calorimeter (DSC). SEM analysis shows that Mg₃(PO₄)₂-coating changes the morphologies of their particles and increases the grains size. XRD and CV results show that Mg₃(PO₄)₂-coating powder is homogeneous and has better layered structure than the bare one. Mg₃(PO₄)₂-coating improved high rate discharge capacity and cycle-life performance. The reason why the cycling performance of Mg₃(PO₄)₂-coated sample at 55 °C was better than that of room temperature was the increasing of lithium-ion diffusion rate and charge transfer rate with temperature rising. Mg₃(PO₄)₂-coating improved the cathode thermal stability, and the result was consistent with thermal abuse tests using Li-ion cells: the Mg₃(PO₄)₂ coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode did not exhibit thermal runaway with smoke and explosion, in contrast to the cells containing the bare Li_1.05Ni_1/3Mn_1/3Co_1/3O₂. Funded by the National Natural Science Foundation of China (No. 20273047)     

Synthesis and characterization of high-voltage cathode material LiNi0.5Mn1.5O4 by one-step solid-state reaction

LiNi0. 5 Mn1. 5 O4 was prepared under various conditions by one-step solid-state reaction in air and its properties were investigated by X-ray diffractormetry (XRD), scanning electron microscopy (SEM) and electrochemical measurement. XRD patterns show that LiNi0. 5 Mn1. 5 O4 synthesized under various conditions has cubic spinel structure. SEM images exhibit that the particle size increases with increasing calcination temperature and time. Electro chemical test shows that the LiNi0. 5 Mn1.5 O4 calcined at 700 ℃ for 24 h delivers up to 143 mA · h/g, and the capacity retains 132 mA · h/g after 30 cycles.     

Na+掺杂对LiNi1/3Co1/3Mn1/3O2结构和电化学性质的影响

采用高温固相法成功制备了不同Na+掺杂浓度的Li_1-xNa_xNi_1/3Co_1/3Mn_1/3O₂锂离子电池正极材料,探究了Na元素掺杂对层状氧化物正极材料结构以及电化学性能的影响。通过X射线粉末衍射仪和扫描电子显微镜表征了材料的结构和形貌,结果表明,当x≤0.3时,样品不会出现其它杂相;当x＞0.3时,样品中会出现NaNi_1/3Co_1/3Mn_1/3O₂的杂相。同时随着掺杂浓度的增加,样品的阳离子混排度逐渐增加。电化学性能结果表明,少量Na+的掺入可以提高LiNi_1/3Co_1/3Mn_1/3O₂在0.2C,0.5C下的放电比容量并增强其循环稳定性,但会损坏材料的倍率性能。     

Modification of LiCo1/3Ni1/3Mn1/3O2 cathode material by CeO2-coating

Science China Technological Sciences - LiCo1/3Ni1/3Mn1/3O2 was coated by a layer of 1.0 wt% CeO2 via sol-gel method. The bared and coated LiMn1/3Co1/3Ni1/3O2 was characterized by X-ray diffraction...     

Al/Y_2W_3O_(12)复合材料的制备、热膨胀及电性能研究

采用固相法制备Al/Y_2W_3O_(12)复合材料,研究了Al与Y_2W_3O_(12)以不同质量比合成样品的特性。X射线衍射表明:样品只含有Al和Y_2W_3O_(12),不存在Al对Y的取代。SEM和EDS分析表明:小颗粒Y_2W_3O_(12)嵌入在块状Al基底中,为嵌入式复合结构。热膨胀性能和电导率测试分析表明:当Al与Y_2W_3O_(12)的质量比7∶3时,Al/Y_2W_3O_(12)样品的线膨胀系数14.76×10-6/K(RT~600℃)约为Al的一半,呈现良好的导电性,其导电率为18.2 S/m可达Al的电导率的1/2,且Al/Y_2W_3O_(12)样品几乎不表现出吸水性。研究认为,该复合材料具有低膨胀和较高导电性是由于其特有的嵌入式结构所致。     

Al2O3对3Ti/Si/2C体系自蔓延高温合成Ti3SiC2的影响

以3Ti/Si/2C粉体为原料,通过自蔓延高温合成技术合成了Ti3SiC2材料。研究了Al2O3助剂对自蔓延高温合成Ti3SiC2的影响。研究结果表明,3Ti/Si/2C粉体会发生自蔓延反应,产物的组成相为TiC、Ti3SiC2和Ti5Si3,产物中Ti3SiC2含量约为23%。添加适量的细粒度Al2O3可显著促进反应合成Ti3SiC2,3Ti/Si/2C/0.1Al2O3原料反应后得到的产物中Ti3SiC2含量达64%。     

Al2O3-NbAl／TiAl基高温复合材料的研究

以Ti-Al-TiO2-Nb2O5为反应体系,利用热压烧结工艺原位合成了Al2O5／TiAl复合材料．通过Mo元素掺杂对体系进行增强,借助X射线衍射（XRD）、扫描电镜（SEM）等分析研究了掺入不同含量Mo时,Ti-Al-TiO2-Nb2O5体系的热压反应过程及其对体系微观组织结构、力学性能等的影响．结果表明：放热反应加速了系统的反应,从而降低了该体系的反应温度;产物体积密度随着Mo掺杂量的增大而增大;抗弯强度和断裂韧性呈峰值变化．     

Li_(1.52)Ni_(0.30)Mn_(0.78)Co_(0.06)O_(2.00)正极材料的电化学性能

以Li2CO3、Ni(CH3COO)2·2H2O、Mn(CH3COO)2·4H2O、Co(CH3COO)2·4H2O和Na2CO3为原料,通过直接沉淀法制备了具有α-NaFeO2型层状结构的微米Li1.52Ni0.30Mn0.78Co0.06O2.00正极材料.通过X射线衍射、扫描电镜、恒电流充放电、交流阻抗、循环伏安法等方法研究了样品的结构和电化学性能.结果表明:充电截止电压4.6V时样品的充放电性能最佳.在电流200 mAh·g-1时,该样品第1循环和第40循环的放电容量分别为150.2 mAh·g-1、155.0 mAh·g-1;样品的电化学反应受电荷传递阻抗和和Li+扩散的共同控制.     

Synthesis and electrochemical characterization of LiNi0.78Co2Al0.02O2 cathode material in a novel co-precipitation method

LiNi0.78Co2Al0.02O2 cathode materials were prepared with a novel co-precipitation method followed by heat-treating. The properties of the materials were characterized. XRD patterns showed that no secondary phase appeared and the hexagonal lattice parameter c of LiNi0.78Co2Al0.02O2 was larger than that of LiNi0.8Co0.2O2. The SEM images indicated that the powders of the material were submicron size. The results of the ICP-AES analysis proved that elemental compositions of the material were similar to those of the targeted one. Cyclic voltammetry (3.0-4.2 V) illustrated that the new material had good lithium-ion intercalation/de-intercalation performance. The results of galvanostatic cycling showed that the initial specific discharge capacity of the prepared ma-terial was 181.4 mAh/g, and the specific discharge capacity was 177.3 mAh/g after 100 cycles (0.2C,3.0-4.2 V, vs. Li /Li) with the capacity retention ratio of 97.7%.     

Synthesis and electrochemical characterization of LiNi0.78Co0.2Al0.02O2 cathode material in a novel co-precipitation method

LiNi0.78 Co0.2 Al0.02O2 cathode materials were prepared with a novel co-precipitation method followed by heat-treating. The properties of the materials were characterized. XRD patterns showed that no secondary phase appeared and the hexagonal lattice parameter c of LiNi0.rsCoo.2AI~0202 was larger than that of LiNi0.8Co0.2O2. The SEM images indicated that the powders of the material were submicron size. The results of the ICP-AES analysis proved that elemental compositions of the material were similar to those of the targeted one. Cyclic voltammetry （3.0- 4. 2 V） illustrated that the new material had good lithium-ion intercalation/de-intercalation performance. The results of galvanostatic cycling showed that the initial specific discharge capacity of the prepared material was 181.4 mAh/g, and the specific discharge capacity was 177.3 mAh/g after 100 cycles （0. 2C, 3.0 - 4. 2 V, vs. Li^＋/Li） with the capacity retention ratio of 97.7%.     

Synthesis of LiNi0.8Co0.2O2 in Air Atmosphere and its Characterization

The commercialized lithium secondary cells need the electrode materials with high speeific capacity, lower pollution and lower price. Certain industrial materials ( NiSO_4, CoSO_4 , LiOH·H_2O)were used to synthesize Ni_(0.8)Co_(0.2)(OH)_2 of a stratified structure, when various synthesis conditions such as pH, reaction temperature et al. were controlled strictly. After LiOH·H_2O and Ni_(0.8)Co_(0.2) (OH)_2were calcinated in air atmosphere, LiNi_(0.8)Co_(0.2)O_2 positive electrode materials with good layered crystal structure was obtained. Tests showed that the optimal calcination temperature in air atmosphere was about at 720℃ and LiNi_(0.8)Co_(0.2)O_2 synthesized in the above conditions had good electrochemical properties and a low cost. The first specific: discharge capacity of the material was 186 mAh/g, and the specific discharge capacity was 175 mAh/g after 50 cycles at a 0.2C rate, between 3.0～4.2 V with a discharge deterioration ratio of 0.22% each cycle. Tests showed that LiNi_(0.8)Co_(0.2)O