The relation between morphology of (Co)MoS2 phases and selective hydrodesulfurization for CoMo catalysts

A series of CoMo catalysts were prepared by various methods with three different supports (Al₂O₃-1 of γ phase, Al₂O₃-2 containing γ and δ mixed phases, SiO₂). And the effect of morphology of (Co)MoS₂ phases on selective hydrodesulfurization was studied systematically. The TEM images showed, in general, the average slab length, the stacking number and the ratio of edge/corner of the sulfided catalysts increase remarkably in the order: SiO₂ > Al₂O₃-2 > Al₂O₃-1, with the extent of metal–support interaction decreasing in the order: SiO₂ < Al₂O₃-2 < Al₂O₃-1. And the hydrodesulfurization selectivity correlates linearly with the slab length (or the ratio of edge/corner) of (Co)MoS₂ phases, the longer average slab length, the higher ratio of edge/corner, and then the better hydrodesulfurization selectivity. Among all the catalysts, sulfided CoMo/SiO₂ of the longest average slab length and the highest edge/corner ratio exhibits the best hydrodesulfurization selectivity.     

MoS2基催化剂加氢脱硫反应活性相和作用机理研究进展

加氢脱硫工艺在清洁油品生产过程中发挥着重要作用，而MoS₂基催化剂是加氢脱硫的主要催化剂，因此对MoS₂基催化剂活性相和催化反应机理的深入研究有助于从原子层面上对催化剂进行优化设计。本文首先介绍了国内外有关MoS₂基催化剂活性相形貌结构的研究，着重探讨了硫化气氛、助剂和载体类型对活性相结构的影响，以及现有表征技术在MoS₂基催化剂活性相形貌结构研究中所面临的挑战，总结了不同条件下活性相的微观结构特征；同时，从MoS₂基催化剂的活性相组成和结构角度分析了噻吩的加氢脱硫机理，发现了加氢脱硫活性与催化剂微观结构之间的紧密联系；最后展望了理论计算在设计和开发高效加氢脱硫催化剂过程中的重要指导作用。     

Li2MnO3复合LiNi0.8Co0.1Mn0.1O2材料制备及电化学性能研究

通过采用共沉淀法制备了Ni_0.8Co_0.1Mn_0.1（OH）₂前驱体,利用固相法研磨混合碳酸锰和碳酸锂,在氧气氛围下煅烧制备得到了Li₂MnO₃-LiNi_0.8Co_0.1Mn_0.1O₂复合材料,通过利用X射线衍射（XRD）、场发射扫描电镜（FESEM）和透射电镜（TEM）表征了所制备材料的结构、成分和形貌等。通过恒流充放电、交流阻抗等方法对材料的电化学性能进行测试。结果表明,与未改性材料进行对比,3%（质量分数）Li₂MnO₃复合改性材料0.5C下首次放电容量为183 mA·h/g,经过120次充放电循环,容量保持率为93.9%;同时,在高倍率下复合改性材料放电容量也得到提高。因此,采用固相法煅烧复合Li₂MnO₃-LiNi_0.8Co_0.1Mn_0.1O₂材料,可以制备出电化学性能优异的正极材料。     

Effects of Al2O3 and LiAlO2 Co-coating on electrochemical properties of LiNi0.8Co0.1Mn0.1O2 cathode materials

Lithium-ion batteries are widely used in aerospace, power vehicles, portable electronic devices and other fields because of their environmental friendliness, rechargeable cycle and high energy density. The nickel-cobalt-manganese ternary materials with high nickel has high specific discharge capacity and is regarded as one of the most promising cathode materials. However, with the increase of the number of cycles, the cycle performance becomes worse and the specific capacity decays sharply. In this work, Al₂O₃ and LiAlO₂ were coated on the surface of NCM811 by combining ball milling mixing and solid-phase synthesis to prepare the AL-NCM811 cathode material. The coating thickness formed by Al₂O₃ and LiAlO₂ was 10–70 nm, which effectively improves the cycle stability and rate performance of NCM811 material. When charged and discharged at 0.1C, the first discharge specific capacity and capacity retention rate after 100 cycles of 0.5AL-NCM811 were 196.26 mAh/g and 96.47%, respectively, while those of NCM811 were only 193.78 mAh/g and 72.18%, respectively. When the current density was 5.0C, the discharge specific capacity of 0.5AL-NCM811(139.16 mAh/g) was 55.368 mAh/g higher than that of NCM811(83.80 mAh/g).     

Enhanced electrochemical performance of LiNi0.8Co0.1Mn0.1O2 via titanium and boron co-doping

Titanium and boron are simultaneously introduced into LiNi_0.8Co_0.1Mn_0.1O₂ to improve the structural stability and electrochemical performance of the material. X-ray diffraction studies reveal that Ti⁴⁺ ion replaces Li⁺ ion and reduces the cation mixing; B³⁺ ion enters the tetrahedron of the transition metal layers and enlarges the distance of the [LiO₆] layers. The co-doped sample has spherical secondary particles with elongated and enlarged primary particles, in which Ti and B elements distribute uniformly. Electrochemical studies reveal the co-doped sample has improved rate performance (183.1 mAh·g^-1 at 1 C and 155.5 mAh·g^-1 at 10 C) and cycle stability (capacity retention of 94.7% after 100 cycles at 1 C). EIS and CV disclose that Ti and B co-doping reduces charge transfer impedance and suppresses phase change of LiNi_0.8Co_0.1Mn_0.1O_2.     

电解液添加剂PHS对LiNi0.8Mn0.1Co0.1O2锂离子电池性能的影响

以2-苯基-1-基1H-咪唑-1-磺酸酯(PHS)作为电解液添加剂,用于LiNi0.8Mn0.1Co0.1O2(NCM811)/石墨软包电池中.充放电测试和电化学测量的结果表明,PHS的添加可以提高NCM811/石墨软包电池的常温、低温和高温循环性能,令电池能够在-20～60°C的温度范围内工作,极大地提升了锂离子电池...     

Li2ZrO3包覆LiNi0.8Co0.1Mn0.1O2的复合材料及其电化学性能

以Zr（NO₃）₄·5H₂O和CH₃COOLi·2H₂O为原料,采用湿化学法,将Li₂ZrO₃包覆在LiNi_0.8Co_0.1Mn_0.1O₂锂离子电池正极材料的表面,研究Li₂ZrO₃不同包覆比例对LiNi_0.8Co_0.1Mn_0.1O₂电化学性能的影响。SEM、TEM、EDS谱图分析表明,Li₂ZrO₃层均匀地包覆在LiNi_0.8Co_0.1Mn_0.1O₂表面,其厚度约为8 nm。与纯相相比,1%（质量分数） Li₂ZrO₃包覆的LiNi_0.8Co_0.1Mn_0.1O₂复合材料在1.0 C下首次放电比容量为184.7 mA·h·g^-1、100次循环之后放电比容量为169.5 mA·h·g^-1,其容量保持率达到91.77%,表现出良好的循环稳定性。循环伏安（CV）和电化学阻抗（EIS）测试结果表明,Li₂ZrO₃包覆层抑制了正极材料与电解液之间的副反应,减小了材料在循环过程中的电荷转移阻抗,从而提高了材料的电化学性能。     

锂离子正极材料LiNi_(0.8)Mn_(0.1)Co_(0.1)O_2的制备及其性能研究

以尿素为沉淀剂,以乙二醇为溶剂,通过溶剂热法制备出多级前躯体Ni0.8Mn0.1Co0.1CO3,通过焙烧该前躯体和LiOH·H2O的混合物制备出高比容量的锂离子正极材料LiNi0.8Mn0.1Co0.1O2。采用XRD、FESEM及恒流充放电测试对材料的结构、形貌和电化学进行表征,结果表明,合成的产物形貌均一,有高结晶度。在0.1 C倍率下,放电比容量为194.6 mAh g-1;当放电倍率提高到2.0 C时,该材料仍然具有78.4mAhg-1的放电比容量,并且该材料在各个倍率下具有良好的稳定性。在1.0 C的放电倍率下,经过50次循环,放电容量保持率为92.5%。     

正极材料LiNi0.8Co0.1Mn0.1O2的合成工艺优化及电化学性能

采用高温固相法合成锂离子电池富镍三元材料LiNi_0.8Co_0.1Mn_0.1O₂,对其工艺条件进行优化,对产物进行X射线衍射（XRD（,扫描电镜（SEM（以及电化学性能分析。结果表明：在氧气气氛下,锂与金属元素摩尔比为1.05:1、烧结时间15 h、烧结温度750℃为最佳合成工艺条件。按最佳工艺合成的样品在1C首次放电容量高达174.9 mA·h·g^-1,50次循环后比容量为158.5 mA·h·g^-1,容量保持率为90.62%,表现出良好的循环稳定性。XRD和SEM表征表明,在氧气气氛下烧结的样品有良好的层状结构,阳离子混排程度小,具有较好的类球形,粒径均匀分布在10~20 μm。循环伏安（CV（和电化学阻抗（EIS（结果表明,工艺条件的优化有助于提高正极材料的电化学性能。     

Synthesis and characterization of mono-dispersion LiNi0.8Co0.1Mn0.1O2 micrometer particles for lithium-ion batteries

LiNi_0.8Co_0.1Mn_0.1O₂ cathode material for lithium-ion battery exhibits high capacity, but it suffers from interfacial side reactions and structural/thermodynamic instability, which leads to capacity reduction and safety problems. Cubic brick (Ni_0.8Co_0.1Mn_0.1)C₂O₄·2H₂O particles with micron size are synthesized by co-precipitation method. The oxalic precursor is sintered with lithium hydroxide to obtain cubic mono-dispersion LiNi_0.8Co_0.1Mn_0.1O₂ micrometer particles. Structural stability, cycling performance, rate capability and compacting density of the cubic mono-dispersion material are investigated. Conventional spherical and irregular mono-dispersion LiNi_0.8Co_0.1Mn_0.1O₂ are also prepared for comparison. The results reveal that the cubic mono-dispersion LiNi_0.8Co_0.1Mn_0.1O₂ dramatically enhances the structural stability and cycling performance at a little cost of capacity and rate capability.     

Recent progress in coatings and methods of Ni-rich LiNi0.8Co0.1Mn0.1O2 cathode materials: A short review

LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) is a typical nickel (Ni)-rich ternary cathode material with several advantages, such as high specific capacity, low-cost, and environmentally friendly, making it a good candidate for use in lithium-ion batteries. However, its Ni content is as high as 80%; therefore, several new problems have emerged with gradually increasing applications. In this review, Li–Ni disorder and corresponding modification methods are first briefly reviewed, and then the origin of complex surface defect, which has a crippling effect on diffusion processes of Li⁺ at electrolyte/cathode interface, is discussed in detail. Analyses showed the importance of selecting appropriate surface modification material/technique for enhancing electrochemical properties. Therefore, popular surface coating materials and methods including metal oxides, fluorides, phosphates, fast ion conductors, and other compounds/elements used for the development of NCM811 are subjected to extensive and thorough research. Finally, several new perspectives and insights related to stability and safety at high voltages and temperatures, and the optimization of production process are also proposed.     

Ultrathin-Y2O3-coated LiNi0.8Co0.1Mn0.1O2 as cathode materials for Li-ion batteries: Synthesis,performance and reversibility

Nickel-rich lithium material LiNi_xCo_yMn_1-x-yO₂(x > 0.6) becomes a new research focus for the next-generation lithium-ion batteries owing to their high operating voltage and high reversible capacity. However, the rate performance and cycling stability of these cathode materials are not satisfactory. Inspired by the characteristics of Y₂O₃ production, a new cathode material with ultrathin-Y₂O₃ coating was introduced to improve the electrochemical performance and storage properties of LiNi_0.8Co_0.1Mn_0.1O₂ for the first time. XRD, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), energy dispersive spectroscopy (EDS) and XPS were used to mirror the crystal and surface of LiNi_0.8Co_0.1Mn_0.1O₂ particles, results i that a uniform interface formed on as-prepared material. The impacts on the electrochemical properties with or without Y₂O₃ coating are discussed in detail. Notably, galvanostatic discharge-charge tests appear that Y₂O_3-coated sample especially 3% coating displayed a better capacity retention rate of 91.45% after 100 cycles than the bare one of 85.07%.     

Influence of lithium difluorophosphate additive on the high voltage LiNi0.8Co0.1Mn0.1O2/graphite battery

Lithium-ion batteries (LIBs) possessing high energy densities are driven by the growing demands of electric vehicles (EVs) and hybrid electric vehicles (HEVs). One of the most effective strategies to improve the energy density of LIBs is to enlarge the charge cut-off voltage via a lithium salt additive for the conventional electrolyte system. Herein, lithium difluorophosphate (LIDFP) is employed to optimize and reconstruct the composition of the structure and interface for both cathode and anode, which can effectively restrain the oxidation decomposition of electrolyte as well as refrain the dissolve out of transition metals. The LiNi_0.8Co_0.1Mn_0.1O₂ (LNCM811)/graphite pouch cell with 1 wt% LIDFP in electrolyte delivers a discharge capacity retention of 91.3% at a high voltage of 4.4 V over 100 cycles, which is higher than the 82.0% of that without LIDFP additive. Additionally, the remaining capacity of LNCM811/C battery with 1 wt% LIDFP additive which is left at 60 °C for 14 days is 85.2%, and the recovery capacity is 93.3%. The LIDFP-containing electrolyte demonstrates a great application future for the LiBs operating under the high-voltage condition and high-temperature storage performance.     

层状锂离子电池正极材料LiNi0.8Co0.1Mn0.1O2的制备及性能

采用共沉淀法得到前驱体Ni0.8Co0.1Mn0.1(OH)2,利用前驱体与LiOH×H2O的高温固相反应得到高振实密度的锂离子电池层状正极材料LiNi0.8Co0.1Mn0.1O2 (2.3~2.5 g/cm3). 初步探讨了合成条件对材料电化学性能的影响. 通过X射线衍射(XRD)、扫描电镜(SEM)、热重-差热分析(TG/DTG)以及恒电流充放电测试对合成的样品进行了测试和表征. 结果表明,在750℃、氧气气氛下合成的材料具有较好的电化学性能. 通过XRD分析可知该材料为典型的六方晶系a-NaFeO2结构;SEM测试发现产物粒子是由500~800 nm的一次小晶粒堆积形成的二次类球形粒子. 电化学测试表明,其首次放电容量和库仑效率分别为168.6 mA×h/g和90.5%, 20次循环后容量为161.7 mA×h/g,保持率达到95.9%,是一种具有应用前景的新型锂离子电池正极材料.     

Effect of micron sized particle on the electrochemical properties of nickel-rich LiNi0.8Co0.1Mn0.1O2 cathode materials

Particle size plays an important role in the electrochemical properties of cathode materials for lithium-ion battery, and the sizes of cathode powders are often designed to specific scales to obtain desired rate capacity, cyclic stability, etc. Nano-sized or micron-sized primary/secondary particles were both reported to be helpful to heighten the electrochemical properties of the same material system. However, the relationship between particle size and electrochemical properties of Ni-rich LiNi_0.8Co_0.1Mn_0.1O₂ (NCM-811) has not been discussed in detail. Here, we prepared the pristine NCM-811 powders with various micro-sized particles by using solid state reaction, and investigated the influence of particle size on the electrochemical properties of typical NCM-811 cathode material, to clarify the importance of size effect. The result indicates that pristine NCM-811 cathode powders with D₅₀ = 7.7 μm displayed the best initial discharge specific capacity (224.5 and 169.1 mA h/g at 1/20 C and 1 C rate, respectively) and retention capacity (71.0% at 1 C rate) after 100th cycling at room temperature. The mutual acting mechanism in terms of layered structure, cation mixing degree, polarization state, charge-transfer resistance, and the diffusion ability of lithium-ion was confirmed by XRD, XPS, CV and EIS analyses, respectively.     

LiAlO2-coated LiNi0.8Co0.1Mn0.1O2 and chlorine-rich argyrodite enabling high-performance all-solid-state lithium batteries at suitable stack pressure

All-solid-state lithium batteries (ASSLBs), which are consisted of Li_5.5PS_4.5Cl_1.5 electrolyte, metal lithium anode and LiNi_0.8Mn_0.1Co_0.1O₂ (NCM811) cathode, are speculated as a promising next generation energy storage system. However, the unstable oxide cathode/sulfide-based electrolyte interface and the dendrite formation in sulfide electrolyte using the lithium metal anode hinder severely commercialization of the ASSLBs. In this work, the dendrite formation in sulfide electrolyte is investigated in lithium symmetric cell by varying the stack pressure (3, 6, 12, 24 MPa) during uniaxial pressing, and uniformly nanosized LiAlO₂ buffer layer was carefully coated on NCM811 electrode (LiAlO₂@NCM811) to improve the cathode/electrolyte interface stability. The result shows that lithium symmetrical cell has a steady voltage evolution over 400 h under 6 MPa stacking pressure, and the assembled LiAlO₂@NCM811/Li_5.5PS_4.5Cl_1.5/Li battery under the stack pressure of 6 MPa exhibits large initial discharge specific capacity and excellent cycling stability at 0.05 C and 25 °C. The feasibility of using the lithium metal anode in all-solid-state batteries (ASSBs) under suitable stack pressure combined with uniformly nanosized LiAlO₂ buffer layer coated on NCM811 electrode supply a facile and effective measures for constructing ASSLBs with high energy density and high safety.     

锂离子电池高镍三元正极材料LiNi0.8Co0.1Mn0.1O2的性能研究

富镍正极材料(LiNi0.8Co0.1Mn0.1O2)具有高容量的优点,是锂离子电池正极材料最有潜力的材料之一。为确定最佳合成条件,本工作研究了合成温度对材料性能的影响,并详细分析了材料电化学性能衰减的原因以及循环过程中材料结构的变化。采用热重/差示扫描量热法(TG/DSC)、X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(HRTEM)、能谱仪(EDS)、X射线光电子能谱(XPS)等手段对合成的正极材料进行了物化表征,并对其电化学性能进行测试。结果表明,在低温段500℃保温4 h,高温段750℃保温14 h合成的正极材料NCM750在0.2 C首次放电比容量为186.2 mAh/g,首次充放电效率为82.5%,1 C放电比容量为185.1 mAh/g,100次循环后仍有175.2 mAh/g,容量保持率为95.2%。在此条件下合成的材料具有结构稳定,粒径均匀,电化学性能优异等优点,本工作对富镍正极材料的合成及结构变化进行研究,有助于加深对材料的了解。     

电解液添加剂FSOB对LiNi0.8Mn0.1Co0.1O2/石墨全电池性能的影响

以氟磺酰基氧基苯(FSOB)作为电解液添加剂,用于LiNi0.8Mn0.1Co0.1O2(NCM811)/石墨软包电池中.充放电测试和电化学测量的结果表明,FSOB的添加提高了该锂离子电池的常温、高温和低温长循环性能,令其可工作于?20～60°C的温度范围内.     

纳米MoS2的制备及其与聚吡咯物复合膜光学性能的研究

以有机热溶剂法制备MoS2,并以XRD对其结构进行表征.TEM形貌观察表明晶粒具有纳米尺寸。以电化方法在ITO导电玻璃基体上制备聚合物聚吡咯薄膜。在导电聚合物膜上涂布纳米MoS2晶体,荧光分析发现其荧光光谱相对于聚合物膜有一定程度的红移。Z-Scan测试其折射率的结果表明其具有非线性光学特性。