一步固相法合成Li1.2Ni0.13Co0.13Mn0.54O2正极材料的工艺优化

以球形前驱体Ni0.13Co0.13Mn0.54(OH)0.8以及Li2CO3为原料,用正交实验方法优化一步固相法制备Li1.2Ni0.133Co0.133Mn0.534O2正极材料的合成工艺,考察焙烧温度、焙烧时间以及锂盐过量分数等因素对材料电化学性能的影响,得到最佳工艺组合:焙烧温度850℃;焙烧时间18 h;锂盐过量分数2%。按最佳工艺合成的样品0.2 C、1 C首次放电容量分别为262.6 mAh/g和234.6mAh/g,且表现出良好的循环稳定性。     

电解液浸泡对锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的影响

主要考察了电解液浸泡对Li Ni1/3Co1/3Mn1/3O2粉料的影响,通过扫描电镜(SEM)观察了不同条件下粉体的形貌,采用X射线衍射仪及拉曼光谱仪表征晶体的结构,并将样品组装成电池,比较了不同条件处理下样品的首次放电及倍率性能。结果表明,电解液浸泡对Li Ni1/3Co1/3Mn1/3O2的形貌和晶体结构影响较小,但对粉体的电阻率和电池的容量有较大影响,而且随着浸泡温度的升高,其粉体电阻率和放电比容量均下降。     

Li[Ni1/2Mn1/2]O2的制备及电化学性能研究

介绍了一种采用前驱体碳酸盐共沉淀法制备锂离子电池正极材料Li[Ni1/2Mn1/2]O2的工艺路线。通过对样品进行X射线衍射(XRD)测试,可知产品具有类似钴酸锂的层状结构。通过对产品进行扫描电镜(SEM)观察可以看出,产品具有规则的球形形貌,且粒径在5~10μm;电化学测试表明,材料的首次放电比容量大于170 mA.h/g,循环20次后容量保持率大于98%。     

正极材料LiCo1/3Ni1/3Mn1/3O2共沉淀合成法的研究

讨论了焙烧温度对LiCo1/3Ni1/3Mn1/3O2的共沉淀法合成过程的影响,结合XRD、SEM、振实密度分析和充放电测试等手段获得了共沉淀法制备LiCo1/3Ni1/3Mn1/3O2的最佳合成温度。获得了共沉淀法制备LiCo1/3Ni1/3Mn1/3O2的最佳焙烧温度为900℃,在上述最佳焙烧温度条件下合成的正极材料具有优异的电化学性能。     

锂离子电池正极材料LiNi1/2Co1/6Mn1/3O2的制备与性能

采用Co2+浓度递增的金属离子混合溶液分次共沉淀方法制备Ni1/2Co1/6Mn1/3(OH)2,以其为前驱体,通过高温固相反应得到具有Co含量梯度的层状LiNi1/2Co1/6Mn1/3O2,探讨了焙烧温度及Co含量梯度对材料的结构和电化学性能的影响. 通过X射线衍射、扫描电镜、热重分析及恒电流充放电测试对合成的样品进行了表征. 结果表明,700℃合成产物即具有类LiNiO2的六方层状结构,800和850℃合成产物阳离子排列有序度高,层状结构显著. 材料结晶度好,粒度均匀,粒径在亚微米级. 合成温度800℃的梯度材料具有最佳的电化学性能, 2.5~4.2 V, 0.1 C倍率充放电50次后,梯度材料的容量仍保持在171.2 mA×h/g. 相同的焙烧温度,梯度材料比均匀材料的电化学性能更加优异.     

共沉淀法制备Li[Ni1/3Co1/3Mn1/3]O2及电化学性能研究

采用NH3-NaOH共沉淀法合成了L[Ni1/3Co1/3Mn1/3]O2正极材料,通过改变NH3·H2O浓度及加料方式研究材料的电化学性能.采用XRD、SEM对晶体的结构和形貌作表征.将正极材料Li[Ni1/3Co1/3Mn1/3]O2制成电极极片,组装成电池进行测试.分析测试结果表明,合成的极材料Li[Ni1/3Co1/3Mn1/3]O2具有典型的α-NaFeO2结构,粒径分布较好,呈类球形.     

锂离子电池正极材料LiNi0.5Co0.2Mn0.3O2合成工艺优化

以球形三元前驱体Ni0.5Co0.2Mn0.3(OH)2以及LiOH.H2O为原料,用正交实验优化锂离子电池正极材料LiNi0.5Co0.2Mn0.3O2合成工艺,考察烧结温度、保温时间以及锂与金属元素(Ni、Co、Mn总量)物质的量比等因素对材料电化学性能的影响。得到最佳条件:烧结温度为800℃,保温时间为12 h,锂与金属元素物质的量比为1.06。按最佳工艺合成的样品在0.2 C、1 C首次放电比容量分别为165.1 mA.h/g和151.6 mA.h/g,且表现出良好的循环稳定性。     

锂离子电池LiNi1/3Co1/3Mn1/3O2正极材料的性能研究(Ⅰ)

采用共沉淀法和高温固相烧结相结合,合成了锂离子电池层状LiNi1/3Co1/3Mn1/3O2正极材料。采用ICP-AES元素分析方法、XRD和SEM对LiNi1/3Co1/3Mn1/3O2正极材料的成分、结构和形貌进行了表征。SEM测试结果表明,LiNi1/3Co1/3Mn1/3O2的形貌近似为球形,且颗粒分布均匀。并对其进行了充放电性能测试,结果表明:LiNi1/3Co1/3Mn1/3O2在25℃、2.5～4.6 V、0.1 C倍率下,首次放电容量达189.32 mAh.g-1(锂为负极),C/LiNi1/3Co1/3Mn1/3O2在1 C、2.75～4.2 V下,初始放电比容量为145.5 mAh/g,循环100次后,容量保持率为98.41%。是一种有发展前景的锂离子电池正极材料。     

正极材料LiCo1/3Ni1/3Mn1/3O2的制备与电化学性能

采用固相法和沉淀法合成了锂离子电池正极材料LiCo1／3Ni1／3Mn1／3O2探讨了合成温度、不同合成方法对材料的电化学性能的影响。利用充放电测试、循环伏安测试方法对合成的LiCo1／3Ni1／3Mn1／3O2进行了表征。结果表明,固相法900℃煅烧合成的材料电化学性能较好,沉淀法合成的材料电化学性能最好,以10．0mA／g的电流充放电,首次放电比容量为576．0C／g,循环50次后放电比容量仍保持501．5C／g。以100．0mA／g的大电流放电,放电比容量达到430．2C／g。     

锂离子电池正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2的研究进展

锂离子电池正极材料Li Ni1/3Co1/3Mn1/3O2具有比商业化正极材料——LiCoO2更低廉的成本、更低的毒性、更好的热稳定性,近年来受到广大科研工作者的关注。主要介绍了Li Ni1/3Co1/3Mn1/3O2正极材料的合成改性方法及其近年来在电化学性能方面所取得的成果和进展,并简要概括了该材料结构和发展趋势。不断提高Li Ni1/3Co1/3Mn1/3O2正极材料的振实密度以及电化学性能特别是其在高倍率充放电条件下的循环性能将成为相关科研工作者的研究重点。     

ICP-AES原子发射分析法检测LiNi1/3Co1/3Mn1/3O2中Ni含量

建立了一套可用于实际电池及材料生产、研制的电池材料镍钴锰酸锂中Ni的测定方法。在解决了原子发射法的基体效应及光谱干扰问题后,选定合适的分析条件,进行方法的准确度和精密度实验,数据结果显示方法可以满足实际分析工作的要求。     

Broadband dielectric spectroscopy of PbMg1/3Nb2/3O3–PbSc1/2Nb1/2O3 ceramics

Broadband dielectric spectroscopy results of various ordered and disordered (1 ? x)Pb(Mg_1/3Nb_2/3)O₃–(x)Pb(Sc_1/2Nb_1/2)O₃ (PMN–PSN) ceramics are investigated in the temperature range from 80 K to 300 K and frequency range from 20 Hz to 2 THz. Dielectric dispersion is very broad and in the ferroelectrics case (x = 1, 0.95) consists of two parts: low-frequency part caused by ferroelectric domains and higher frequency part caused by soft mode. The relaxational soft mode exhibits pronounced softening close to phase transition temperature, as it is typical for order–disorder phase transitions. By substituting Sc³⁺ by Mg²⁺ in PMN–PSN ceramics relaxation slows down, and for relaxors (x = 0.2) the most probable relaxation frequency decreases on cooling according to Vogel–Fulcher law.     

Ferroelectric Ceramics in the PbMg1/3Nb2/3O3-PbCd1/3Nb2/3O3 System

Solid solutions (1-x)PbMg_1/3Nb_2/3O₃ + xPbCd_1/3Nb_2/3O₃ with x = 0-0.30 are investigated with purpose to work out a capacitor ceramics with good dielectric properties and low sintering temperature. It is found that the perovskite phase forms at sintering near to 980°C and begins to decompose at higher temperatures. When x grows from 0 to 0.30, the Curie temperature linearly grows from -10°C to +25°C, the dielectric permittivity ε_m in the Curie point T_C decreases from 18000 to 6800 and the phase transition becomes more diffused. The dielectric permittivity at room temperature is rather high and the temperature stability is improved. The system is of interest, because it can serve as a base for working out some ceramic materials for capacitors with low sintering temperature, which needs of no special atmosphere at burning.     

CeF3-modified LiNi1/3Co1/3Mn1/3O2 cathode material for high-voltage Li-ion batteries

A facile chemical deposition method has been adopted to prepare cerium fluoride (CeF₃) surface modified LiNi_1/3Co_1/3Mn_1/3O₂ as cathode material for lithium-ion batteries. Structure analyses reveal that the surface of LiNi_1/3Co_1/3Mn_1/3O₂ particles is uniformly coated by CeF₃. Electrochemical tests indicate that the optimal CeF₃ content is 1 wt%. The 1 wt% CeF₃-coated LiNi_1/3Co_1/3Mn_1/3O₂ can deliver a discharge capacity of 107.1 mA h g⁻¹ even at 5 C rate, while the pristine does only 57.3 mA h g⁻¹. Compared to the pristine, the 1 wt% CeF₃-coated LiNi_1/3Co_1/3Mn_1/3O₂ exhibits the greatly enhanced capacity and cycling stability in the voltage range of 3.0–4.5 V, which suggests that the CeF₃ coating has the positive effect on the high-voltage application of LiNi_1/3Co_1/3Mn_1/3O₂. According to the analyses from electrochemical impedance spectra, enhanced electrochemical performance is mainly because the stable CeF₃ coating layer can prevent the HF-containing electrolyte from continuously attacking the LiNi_1/3Co_1/3Mn_1/3O₂ cathode and retard the passivating layer growth on the cathode.     

不同铝源对LiNi1/3Co1/3Mn1/3O2材料的包覆改性研究

分别以纳米氧化铝、氢氧化铝及异丙醇铝为原料,采用液相浸渍法对LiNi1/3Co1/3Mn1/3O2材料进行氧化铝包覆,考察不同包覆源在LiNi1/3Co1/3Mn1/3O2材料表面进行氧化铝包覆后对材料电化学性能的影响。SEM及XRD结果显示,产物为层状α-NaFeO2结构,氧化铝均匀包覆在LiNi1/3Co1/3Mn1/3O2材料表面。充放电性能测试结果表明,在3种铝源中,以异丙醇铝为包覆源的材料性能最佳：在3.0~4.6 V的电压下,0.1 C倍率下首次放电比容量为196.1 mA·h/g, 1 C下循环50周后容量保持率为95.6%。     

Local atomic characterization of LiCo1/3Ni1/3Mn1/3O2 cathode material

Co, Ni and Mn K-edge XAFS investigation of LiCo_1/3Ni_1/3Mn_1/3O₂ as alternative cathode material to commercially used LiCoO₂ in lithium rechargeable battery has been performed. Parameters of a local atomic structure such as radii of metal-oxygen and metal-metal coordination shells and disorder in those shells have been determined. It has been found that the radius of the first coordination shell (metal-oxygen) as well as a local disorder in the second shell (metal-metal) around each of the 3d-metals are in a good agreement with obtained for superlattice model of [√3 × √3] R30° type in triangular lattice of sites by first principle calculation. Other parameters of the local atomic structure around Co, Ni and Mn atoms do not provide evidence for presence of superstructure in LiCo_1/3Ni_1/3Mn_1/3O₂.     

锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2研究进展

层状结构材料LiNi1/3Co1/3Mn1/3O2具有高比容量、高循环性能、低成本和环保等优点,有望取代LiCoO2成为新一代锂离子电池正极材料。在介绍LiNi1/3Co1/3Mn1/3O2的结构特点和电化学反应特性的基础上,对其主要合成方法进行了详细评述,总结了该正极材料的阴阳离子掺杂、复合离子掺杂以及表面包覆改性等技术,指出国内外目前锂离子电池材料研究中存在的问题和未来的发展方向。     

Storage behavior of LiNi1/3Co1/3Mn1/3O2/artificial graphite Li-ion cells

A series of Li-ion cells containing LiNi_1/3Co_1/3Mn_1/3O₂ and artificial graphite as the active materials, have been stored at various temperatures from 0 to 70 °C. The 3-electrode impedance study shows that both the solid electrolyte interphase (SEI) film resistance and charge-transfer resistance of the negative electrode first decrease and then increase during storage at 70 °C, while both resistances for the positive electrode increase under this condition. The reversible capacity loss of the 3-electrode cell, which is possibly attributed to dissolution of SEI film, accounts for over half of the total capacity loss after 5 weeks of storage. Gases generated from the swelling aged cell at 60 °C are mainly attributed to the reduction of the electrolyte on the negative electrode. A further study on the side-reaction has been done on graphite electrodes and separators, indicating that SEI films may be rearranged and reformed on negative electrodes, and that some pores on the positive electrode side of separator are blocked due to the oxidation of electrolyte, resulting in poor Li-ion transfer and rise of the ohmic resistance during storage at elevated temperature. However, at 0 °C, this side-reaction is impeded.     

Synthesis and characterization of LiNi1/3Mn1/3Co1/3O2 by wet-chemical method

A series of LiNi_1/3Mn_1/3Co_1/3O₂ samples with α-NaFeO₂ structure belonging to the D_3d⁵ space group were synthesized using tartaric acid as a chelating agent by wet-chemical method. Different acid to metal-ion ratios R have been used to investigate the effect of this parameter on the physical and electrochemical properties. We have characterized the reaction mechanism, the structure, and morphology of the powders by TGA, XRD, SEM and TEM imaging, completed by magnetic measurements, Raman scattering spectroscopy, and complex impedance experiments. We find that the LiNi_1/3Mn_1/3Co_1/3O₂ sintered at 900 °C for 15 h with an acid to metal-ion ratio R = 2 was the optimum condition for this synthesis. For this optimized sample, only 1.3% of nickel-ions occupied the 3b Wyckoff site of the lithium-ions sublattice. The electrochemical performance has been investigated using a coin-type cell containing Li metal as the anode. The electronic performance is correlated to the concentration of the Ni(3b) defects that increase the charge transfer resistance and reduce the lithium diffusion coefficient. The optimized cell delivered an initial discharge capacity of 172 mAh g⁻¹ in the cut-off voltage of 2.8-4.4 V, with a coulombic efficiency of 93.4%.     

Synthesis and characterization of (Zr1/3Nb1/3Ti1/3)C metal carbide solid-solution ceramic

(Zr_1/3Nb_1/3Ti_1/3)C metal carbide solid-solution ceramic has been successfully fabricated by hot pressing sintering at 2473 K using ZrC, NbC, and TiC powders as raw materials. The results show that the as-prepared solid-solution ceramic possesses a single rock-salt crystal structure of metal carbides and simultaneously exhibits high compositional uniformity from nanoscale to microscale. By taking advantage of these unique features, it shows relatively high hardness of 38.8 ± 4.4 Gpa and elastic modulus of 481.8 ± 31.0 Gpa and relatively low thermal conductivity of 17.1 ± 0.3 W/(m·K) and thermal diffusivity of 6.1 ± 0.1 mm²/s, which may attribute primarily to the presence of solid solution effects.