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.     

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%.     

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.     

Enhancing high-potential stability of Ni-rich LiNi0.8Co0.1Mn0.1O2 cathode with PrF3 coating

It is still a huge challenge to improve the safety and stability of Ni-rich (LiNi_0.8Co_0.1Mn_0.1O₂) cathode materials at elevated potential. Herein, the PrF₃ layer is employed to protect LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) via a simple wet chemical process. It was confirmed by XRD, HR-SEM, TEM, EDS, and XPS tests that PrF₃ is evenly covered throughout the surface of NCM811 without affecting the particle size and surface morphology. In particular, 1 wt% PrF₃ coated NCM811 exhibits excellent stability and rate capability with the capacity retention of 86.3% after 100 cycles at 1 C under a cut-off potential of 4.3 V, while the retention of pristine one is only 73.8%. Moreover, the capacity retention of 1 wt% PrF₃ coated samples enhances from 74.5% to 88.5% after 50 cycles at 1 C under higher cut-off voltage of 4.6 V. The superior performance for coated samples can be attributed to the fact that PrF₃ can effectively isolate the active material and the electrolyte from HF corrosion, and at the same time, reduce the generation of micro-cracks on the surface during prolonged cycles. Furthermore, as a physical barrier, PrF₃ alleviates the dissolution of transition metals in the electrolyte largely. These results suggest that the stability of NCM811 can be greatly upgraded at high voltage by PrF₃ coating.     

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。     

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.     

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。     

Li3VO4修饰富镍LiNi0.8Co0.1Mn0.1O2正极材料的电化学性能

采用湿法融合技术及高温固相法合成Li₃VO₄包覆的LiNi_0.8Co_0.1Mn_0.1O₂正极材料。通过X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）等方法研究材料的结晶相、形貌、微观结构。研究表明,Li₃VO₄均匀地包覆在LiNi_0.8Co_0.1Mn_0.1O₂表面,未改变原材料的材料结构和形貌,包覆层厚度为1～2 nm。不同含量的Li₃VO₄对LiNi_0.8Co_0.1Mn_0.1O₂正极材料进行修饰研究表明,3%（质量）Li₃VO₄包覆的LiNi_0.8Co_0.1Mn_0.1O₂在1 C下100次循环后容量保持率为94.13%,具有最佳的倍率性能和循环性能。此外,循环伏安（CV）和交流阻抗（EIS）分析表明,Li₃VO₄能提高Li⁺电导率,抑制活性材料与电解液之间的副反应,提高材料的电化学性能。     

Influence of oxygen percentage in calcination atmosphere on structure and electrochemical properties of LiNi0.8Co0.1Mn0.1O2 cathode material for lithium-ion batteries

Different calcination atmospheres of air, 50% oxygen (vs. N₂) and pure oxygen have been used to prepare special LiNi_0.8Co_0.1Mn_0.1O₂ cathode materials to observe the influence of oxygen composition. To investigate the structure and electrochemical property of the samples using different oxygen compositions, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), cycling performance tests and electrochemical impedance spectroscopy (EIS) were carried out. XRD, SEM, and XPS results show that the sample made using higher oxygen composition has less cation mixing and lower levels of Ni²⁺. However, both samples have almost the same oxygen environments on their surfaces as well as micro-morphology and size. The sample with a higher oxygen composition shows better electrochemical performance. Interestingly, the electrochemical performance of the sample made using 50% oxygen is similar to that made with pure oxygen and much better than the sample made with air. It has a specific capacity of 202.4 mAh g⁻¹ at 0.1C and a capacity retention of 85.2% after 300 cycles at 1C, which may be meaningful for balancing cost and performance.     

Investigating the effect of pH on the growth of coprecipitated Ni0.8Co0.1Mn0.1(OH)2 agglomerates as precursors of cathode materials for Li-ion batteries

Understanding how the morphology and microstructure of secondary particles are affected by pH is essential to design spherical and dense hydroxide aggregates as precursors of high-performance cathode materials for lithium-ion batteries. To investigate the interplay between thermodynamic reaction conditions and the physicochemical properties of precursors, a chemical equilibrium model is used to describe the evolution of metal ammonia complexes. Furthermore, the formation and growth of aggregates are studied by monitoring the changes in surface morphologies and crystal structures of precursors at different reaction times. As the pH value varied, two notable phenomena occurred during crystal growth: the fast growth of grains in the early stage as the pH decreased and the layered growth of grains in the later stage with increased pH values. Such findings could be explained from the following two perspectives. First, the decrease in pH causes a significant increase in the complex ion concentration, thereby facilitating the growth of crystals along the [010] direction. Second, an increase in pH generally accelerates deprotonation of the crystal surface, thus strengthening the adsorption of complex ions on the crystal surface and promoting layer-by-layer growth of primary grains along the [001] direction.     

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。     

Effects of Al doping on the electrochemical performances of LiNi0.83Co0.12Mn0.05O2 prepared by coprecipitation

The Ni-rich LiNi_0.83Co_0.12Mn_0.05O₂ (NCM83) cathode materials have drawn intensive attention due to the high energy density and low cost. However, Ni-rich LiNi_1-x-yCo_xMn_yO₂ still has the fatal weakness of poor cycle stability, limiting its further wide application. Bulk doping is an effective means to enhance the cycle stability, yet the electrochemical performances are very sensitive to the doping quantity. Here a facile method of co-precipitation is adopted to coat (Ni_0.4Co_0.2Mn_0.4)_1-xAl_x(OH)_2+x on precursor particles of NCM83. Al ions diffuse evenly in the NCM83 particles after sintering. The cells are operated at a high cut-off voltage of 4.5 V. The discharge capacity of NCM83 is 187.8 mAh g^?1, and decays fast with cycles. The doped sample even exhibits a higher discharge capacity of 195 mAh g^?1, and the capacity retention is improved to 83.8% after 200 cycles.     

Surface modification of Ni-rich LiNi0.8Co0.1Mn0.1O2 cathode materials via a novel mechanofusion alloy route

This study aimed to prepare a composite coating material comprising a solid ionic conductor of lithium aluminum titanium phosphate (Li_1.4Al_0.4Ti_1.6(PO₄)₃, LATP) and porous carbon through a sol-gel method. LiNi_0.8Co_0.1Mn_0.1O₂ (LNCM811) cathode material with dual-functional composite conductors (i.e., LATP@porous carbon), denoted as LATP-PC, was prepared. The dry-coating method, also called the “mechanical-fusion alloy route,” was used to modify Ni-rich LNCM811 cathode materials. X-ray diffraction (XRD), micro-Raman spectroscopy, and X-ray photoelectron spectroscopy confirmed that the LATP ionic conductor generated herein was uniformly deposited on 3D porous carbon and served as a dual-functional composite coating on LNCM811. Furthermore, the capacity retention of LATP-PC@LNCM811 was approximately 85.57% and 80.86% after 100 cycles at −20 °C and 25 °C, respectively. By contrast, pristine LNCM811 had the capacity retention of 78% and 74.96% at −20 °C and 25 °C, respectively. Furthermore, the high-rate capability of the LATP-PC@LNCM811 material was markedly enhanced to 169.81 mAh g⁻¹ at 10C relative to that of pristine LNCM811, which was approximately 137.67 mAh g⁻¹. The electrochemical performance of LNCM811 was enhanced by the uniform dual-conductive composite coating. The results of the study indicate that the LATP-PC@LNCM811 composite material developed herein is a potentially promising material for future high-energy Li-ion batteries.     

陈化温度对LiNi0.5Co0.2Mn0.3O2型正极 材料电化学性能的影响

以简单的球磨-干燥-煅烧法,制备了具有稳定α-NaFeO2型层状结构（R-3m空间群）的LiNi0.5Co0.2Mn0.3O2 型的三元正极材料。通过X射线衍射分析、傅里叶红外光谱、扫描电子显微镜、充放电循环、循环伏安、交流阻抗谱等手段测试了样品的理化性能。研究表明：球磨浆料的陈化温度对样品性能有明显的影响。在0.1C、1C、2C、3C、5C、6C、8C和10C倍率电流和连续充放电下,经过50 ℃陈化浆料制备的亚微米样品的放电容量分别为172.3、161.4、151.5、145.2、136.9、133.2、126.3、121.4 mA·h/g,表现出较好的大倍率电流放电性能。随着循环次数的增加,该样品的锂离子扩散系数和电荷传递阻抗均发生变化。该样品的未循环、充放电循环1次及循环40次样品的锂离子扩散速率分别为1.45×10-16、6.60×10-16、7.92×10-15 cm/s。     

WO3 membrane-encapsulated layered LiNi0.6Co0.2Mn0.2O2 cathode material for advanced Li-ion batteries

Despite Nickel-rich materials have all the advantages of high capacity, long cycle life and low cost, there is still a disadvantage that the capacity decreases rapidly as the number of cycles increases. In order to solve this problem, WO₃ was uniformly coated on the surface of LiNi_0.6Co_0.2Mn_0.2O₂ cathode materials by wet coating, and its cycling performance was greatly improved with the higher capacity. The coated materials were analyzed by X-ray diffraction(XRD), Scanning electron microscope (SEM), high resolution Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy(XPS). The results showed that the coating thickness was around 3.15?nm, and some tungsten ions were doped into the lattice of the near surface area of the LiNi_0.6Co_0.2Mn_0.2O₂ material. In addition, the results of charge-discharge test showed that 1?wt%WO₃ coating LiNi_0.6Co_0.2Mn_0.2O₂ had the best performance, and delivered a discharge capacity of 140 mAh g^?1 (the capacity retention rate is 84.8%) in the potential interval of 2.8–4.3?V at 1?C (1?C?=?165?mA?g^?1) after 200 cycles, while the bare cathode material only delivered a discharge capacity of 120 mAhg^?1 (the capacity retention rate is 75%). The phenomenon indicates that the WO₃ coating plays a role in inhibiting the harmful side reactions between the cathode material and the electrolyte, improving the electrochemical and structure stability of LiNi_0.6Co_0.2Mn_0.2O₂ cathode materials.     

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.     

Dual functions of three-dimensional hierarchical architecture on improving the rate capability and cycle performance of LiNi0.8Co0.1Mn0.1O2 cathode material for lithium-ion battery

The main obstacles in lithium-ion battery are limited by rate performance and the rapid capacity fading of LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811). Herein, a novel three-dimensional (3D) hierarchical coating material has been fabricated by in situ growing carbon nanotubes (CNTs) on the surfaces of Ni–Al double oxide (Ni–Al-LDO) sheets (named as LDO&CNT) with Ni–Al double hydroxide (Ni–Al-LDH) as both the substrate and catalyst precursor. The resultant LDO&CNT nanocomposites are uniformly coated on the surfaces of NCM811 by the physical mixing method. The rate capability of the resultant cathode material retains to 78.80% at a current rate of 3C. Its capacity retention increases by 6.7–14.42% compared with pristine NCM811 after 100 cycles within a potential range of 2.75–4.3 V at 0.5C. The improved rate capability and cycle performance of NCM811 are assigned to the synergistic effects between Ni–Al-LDO and CNTs. The hierarchical LDO&CNT nanocomposites coating on the surface of NCM811 avoids the aggregation of conductive CNTs and the stacking of Ni–Al-LDO nanosheets. Furthermore, it accelerates Li⁺ and electrons shuttle and reduces the reaction of Li₂O with H₂O and CO₂ in air, which results in Li₂CO₃ and LiOH alkali formation on the NCM811 surface.     

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...     

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%。     

Influence of synergistic effect of LiNi0.8Co0.15Al0.05O2@Cr2O5 composite on the electrochemical properties

LiNi_(0.8)Co_(0.15)Al_(0.05)O_2@Cr_2O_5(NCA)@Cr_2 O_5 composite electrode combines the high rate-capability characteristics of NCA with the stability of Cr_2 O_5, playing a synergistic role in improving the cyclic stability, initial discharge capacity and the security of low cut-off voltage(2.0 V). When the mass ratio of Cr_2 O_5 in NCA is 45%(mass), the capacity retention rate increases from 58.5% without Cr_2 O_5 to 69.3% in the range of 2.0–4.3 V.The initial discharge capacity of NCA@Cr_2 O_5 composite material is 211.4 m A·h·g~(-1), its first coulombic efficiency is 94.2%, and the charging capacity remains approximately constant when mixed with 15%(mass)Cr_2 O_5. The reason for the improvement of the initial charge–discharge efficiency(ICDE) was explained.Impedance and cyclic voltammetry analysis reveal more detailed reasons of the observed improvements.Compared with NCA cathode material, the NCA@Cr_2 O_5 composite material can provide not only additional stable sites and channels for Li+insertion/extraction to make up for the loss of active Li+sites and prevent the accumulation of Li+in the circulation process, but also protect the NCA electrode from the corrosion of the electrolyte decomposition by the Cr_2 O_5 nanoparticles adhering to NCA interface.