基于分级共沉淀法制备锂离子电池LiNi0.5Co0.2Mn0.3O2正极材料

通过分级共沉淀（分级进料）方法,结合高温热处理合成了金属元素（Ni,Mn）浓度从中心到表面呈梯度分布（中心富Ni,表面富Mn）的球形三元正极材料LiNi_0.5Co_0.2Mn_0.3O₂。利用X射线衍射（XRD）、场发射扫描电镜（FESEM）、能谱仪（EDS）和电感耦合等离子质谱仪（ICP-MS）等表征了所制备材料的成分、形貌和元素分布。通过恒流充放电和循环伏安、交流阻抗等方法对材料的电化学性能进行测试。结果表明,与传统的一级共沉淀方法相比,分级共沉淀所制备材料展现出更高的倍率性能（20 C放电比容量为104.1 mAh·g^-1）、循环保持率（0.5 C循环200次容量保持率为95.8%）和快速充放电性能（20 C/20 C放电比容量为85.4 mAh·g^-1）。这种分级进料制备技术可以有效提高共沉淀法制备锂离子电池三元正极材料的电化学性能。     

Effect of niobium doping on the structure and electrochemical performance of LiNi0.5Co0.2Mn0.3O2 cathode materials for lithium ion batteries

Key issues including poor rate capability and limited cycle life span should be addressed for the extended application of LiNi_0.5Co_0.2Mn_0.3O₂ cathode. The suppressed Li⁺/Ni²⁺ site exchange, enlarged LiO₂ inter-slab space and reduced impedance, which could facilitate the structure stability, were achieved by controlled Niobium (Nb) doping and contributed to enhanced performance even at elevated temperature (55 °C). The detailed role of the doped Nb was investigated thoroughly and systematically with the help of XRD, SEM, XPS and related electrochemical tests. The full and accurate results demonstrate that the Li(Ni_0.5Co_0.2Mn_0.3)_0.99Nb_0.01O₂ sample with appropriate Nb doping amount possess high capacity retention of 93.77% after 100 cycles at 1.0 C and improved rate performance with 125.5 mA h g⁻¹ at 5.0 C, which are much better than that of the LiNi_0.5Co_0.2Mn_0.3O₂. Moreover, at high temperature of 55 °C, Nb doping shows more remarkable effect on stabilizing the structure and 88.63% of the initial reversible capacity could be retained, which is ~20% higher than the LiNi_0.5Co_0.2Mn_0.3O₂. This study intensively determines that controlled Nb doping could be effectively maintain the structure stability of advanced LiNi_0.5Co_0.2Mn_0.3O₂ cathode and promote the development of high energy density lithium ion batteries.     

掺混工艺对LiNi0.5Co0.2Mn0.3O2 正极材料性能的影响

以碳酸锂及镍钴锰氢氧化物前驱体为原料,通过固相烧结法制备成D50为7.7、19.92 μm的两种规格的锂离子电池三元材料NCM-S和NCM-B。按NCM-B质量占比为20%~90%,将上述两种材料掺混获得系列化的样品。采用激光粒度分析仪、振实密度仪、扫描电子显微镜、充放电测试仪对材料的物理及电化学性能进行分析测试。结果表明：与大颗粒样品NCM-B相比,NCM-80%样品振实密度由2.90 g/cm3提高至2.96 g/cm3,放电比容量由 176.3 mA·h/g提升到178.6 mA·h/g,100周循环容量保持率由91.9%提升至92.7%。以上结果可以归因于小颗粒在紧密堆积的大颗粒中的填隙作用,改善了活性材料的导电网络,提高了电池的能量密度。     

A green and economical route to the precursor for the synthesis of single crystal LiNi0.5Co0.2Mn0.3O2

Single crystal LiNi_1-x-yCo_xMn_yO₂(NCM) cathode materials are typically synthesized using spherical polycrystalline hydroxides which are often prepared via coprecipitation reactions. However, the spherical morphology of polycrystalline hydroxides is not essential for the precursor in the synthesis of single crystal NCM, and also the coprecipitation process is not environmentally friendly and cost-effective enough. Herein a new process based on room-temperature solid-state metathesis reactions is developed to prepare the precursor for the synthesis of single crystal LiNi_0.5Co_0.2Mn_0.3O₂(NCM523). The whole process is free of any undesirable chemicals, and the resulting nanosize precursor can facilitate the synthesis of micron-level single crystal NCM523 at relatively lower sintering temperatures with less lithium excess. Moreover, the obtained single crystal NCM523 can exhibit comparable reversible capacities as compared with that synthesized from the coprecipitated spherical polycrystalline hydroxides. This work demonstrates a green and economical route to the precursor for the synthesis of single crystal NCM.     

Direct regeneration of LiNi0.5Co0.2Mn0.3O2 cathode material from spent lithium-ion batteries

At present, metal ions from spent lithium-ion batteries are mostly recovered by the acid leaching procedure, which unavoidably introduces potential pollutants to the environment. Therefore, it is necessary to develop more direct and effective green recycling methods. In this research, a method for the direct regeneration of anode materials is reported, which includes the particles size reduction of recovered raw materials by jet milling and ball milling, followed by calcination at high temperature after lithium supplementation. The regenerated LiNi_0.5Co_0.2Mn_0.3O₂ single-crystal cathode material possessed a relatively ideal layered structure and a complete surface morphology when the lithium content was n(Ni + Co + Mn):n(Li) = 1:1.10 at a sintering temperature of 920 ℃, and a sintering time of 12 h. The first discharge specific capacity was 154.87 mA·h·g^-1 between 2.75 V and 4.2 V, with a capacity retention rate of 90% after 100 cycles.     

烧结温度对LiNi0.5Co0.3Mn0.2O2物理及其电化学性能的影响

以共沉淀法制备出的球形Ni0.5Co0.3Mn0.2(OH)2为前驱体,以碳酸锂为锂源,通过高温固相法合成了球形LiNi0.5Co0.3Mn0.2O2正极材料。通过热重分析(TGA/DSC)、X射线衍射(XRD)、扫描电子显微镜(SEM)、粒度分布、以及电化学性能的测试考查了不同烧结温度对LiNi0.5Co0.3Mn0.2O2的物理性能及电化学性能的影响。结果表明,900℃下烧结得到的LiNi0.5Co0.3Mn0.2O2晶体结构完整、球形形貌规则、粒度分布均匀,并表现出了优异的电化学性能,0.2 C首次放电容量达到了166.7 mA.h/g;1 C首次放电容量为151.6 mA.h/g,20次循环后,容量保持率高达97.9%。     

硼高效掺杂LiNi0.5Co0.2Mn0.3O2正极材料及其性能提升机制

高键能异质原子的高效掺杂是稳定高电压LiNi_0.5Co_0.2Mn_0.3O₂（NCM）三元正极材料并提升其电化学性能的有效策略。借助含硼前体在二次颗粒表面富集及随后高温煅烧强化B³⁺体相扩散的策略,构建了硼离子高效掺杂NCM正极材料（NCM-B）。引入B—O键（键能：809 kJ·mol^-1）抑制了电化学反应过程中晶格氧析出,进而稳定材料的氧离子框架;此外,表面残余的高锂离子导体Li₂O-B₂O₃包覆层可以在一定程度上稳定电极-电解液界面。与改性前NCM相比,改性后的NCM-B正极材料在3.0~4.5 V电压区间的可逆比电容量可以达到193.7 mA·h·g^-1,在10 C大功率下,比电容量仍保持120 mA·h·g^-1（NCM仅为78.2 mA·h·g^-1）。1 C下连续循环100圈后,比电容量保持率从73%提升到90%。表面富集和扩散强化的思想也有望实现其他正极材料的高效掺杂。     

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。     

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.     

Enhanced electrochemical performance of ZrO2 modified LiNi0.6Co0.2Mn0.2O2 cathode material for lithium ion batteries

LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) cathode has been modified by incorporating ZrO₂ nanoparticles to improve its electrochemical performance. Compared to the pristine electrode, the cycling stability and rate capability of 0.5 wt% ZrO₂ modified-NCM622 have been improved significantly. The 0.5 wt% ZrO₂ modified-NCM622 cathode shows a capacity retention of 83.8% after 100 cycles at 0.1 C between 2.8 and 4.3 V, while that of the pristine NCM622 electrode is only 75.6%. When the current rate is set as 5C, the capacity retention of the 0.5 wt% ZrO₂-modified NCM622 is 10% higher than that of the pristine NCM622. Also, the rate capability of 0.5 wt% ZrO₂-modified NCM622 is better than that of the pristine NCM622 at various C-rates in a voltage range of 2.8–4.3 V. The enhanced electrochemical performances of the ZrO₂-modified NCM622 cathodes can be attributed to their high Li-ion conductivity and structural stability.     

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。     

Impact of coatings on the electrochemical performance of LiNi0.5Mn1.5O4 cathode materials: A focused review

The application of Lithium-ion batteries (LIBs) in portable electronics and electric vehicles (EVs) has increased in the past decade. Extended commercialization of LIBs for advanced applications requires the development of high-performance electrode materials. LiNi_0.5Mn_1.5O₄ (Lithium Nickel Manganese Oxide referred to as LNMO) has attracted much attention as a cathode material due to its high voltage and energy density, lower cost, and environmental friendliness. However, LNMO cathodes are currently suffering from poor cyclability and capacity degradation at elevated temperatures. Many strategies have been suggested in the literature to address the challenges associated with numerous families of cathode materials. Among those, surface modification techniques like surface coatings have proven to be promising. Surface coatings have a good effect on the electrochemical performance of LNMO, as these result in increasing electronic and ionic conductivity, fast ions mobility and high diffusivity. Towards this direction, a systematic review of research progress carried out in the area of coated LNMO has been summarized. More precisely, the impact of numerous coating materials in improving cyclability and capacity retention at elevated temperatures of LNMO has been discussed along with a variety of coating synthesis technologies.     

Realization of a high voltage Ni rich layer LiNi0.5Co0.2Mn0.3O2 single crystalline cathode for LIBs by surface modification

Single crystalline ternary cathode material LiNi_0.5Co_0.2Mn_0.3O₂(NCM523) can operate at extremely high voltages and could offer exceptional energy density. The single crystal morphology is less easy to form the cracks and could express better structure stability compared to the polycrystalline counterpart. However, irreversible parasitic side reactions in the interface during cycling may lead to rapid electrochemical degradations. Herein, a simple chemical wet method that modifies the single-crystal NCM523 particles with Al₂O₃ coating is proposed. The coating layer can effectively suppress the phase transformation and irreversible phase transition on the NCM surface during cycling. Furthermore, the cladding layer can prevent the erosion of by-products such as HF. As a result, the Al₂O₃ modified NCM523 delivers a high specific capacity of 192.5mAh g^?1, excellent cycling stability and rate capability. The capacity retention was 91.7% after 50 cycles even at ultra-high cut-off voltage of 4.7 V. This surface engineering strategy paves the way to promote the development of small size single crystal NCM523 materials for next generation LIBs.     

Effect of molybdenum substitution on electrochemical performance of Li[Li0.2Mn0.54Co0.13Ni0.13]O2 cathode material

Molybdenum doping is introduced to improve the electrochemical performance of lithium-rich manganese-based cathode material. X-ray diffraction (XRD) results illustrate that the crystallographic parameters a, c and lattice volume V become larger with the increase of Mo content. The scanning electron microscope (SEM) shows that the molybdenum substitution increases the crystallinity of the primary particles. When evaluated as cathode material, the as-prepared Li[Li_0.2Mn_0.54-x/3Ni_0.13-x/3Co_0.13-x/3Mo_x]O₂ (x = 0.007) delivers a discharge capacity of 155.5 mA h g⁻¹ at 5 C (1 C = 250 mA g⁻¹) and exhibits the capacity retention of 81.8% at 1 C after 200 cycles. The results of cyclic voltammetry (CV) and electronic impedance spectroscopy (EIS) tests reflect that the molybdenum substitution is able to significantly reduce the electrode polarization and lower the charge-transfer resistance. Within appropriate amount of Mo doping, the lithium ion diffusion coefficient of the material can reach to 8.92 × 10^–15 cm² s⁻¹, which is ~ 30 times higher than that of pristine materials (2.65 × 10^–16 cm² s⁻¹).     

退火工艺对LiNi0.5Mn1.5O4正极材料 电化学性能的影响

采用共沉淀法合成LiNi0.5Mn1.5O4正极材料并对其进行退火处理,研究退火温度对材料电化学性能的影响。结果表明,退火温度会导致LiNi0.5Mn1.5O4正极材料中Mn3+含量的变化,进而影响材料的倍率性能和循环性能。其中,625 ℃退火8 h所制备的样品表现出最好的电化学性能,其0.2 C倍率首次放电容量为130.8 mA·h/g;1 C倍率首次放电容量为126.5 mA·h/g,50次循环后,容量保持率高达100.8%。     

金属离子浓度对LiNi_(0.5)Co_(0.2)Mn_(0.3)O_2材料结构及电化学性能影响研究

采用液相共沉淀+高温煅烧法制备正极材料LiNi0.5Co0.2Mn0.3O2,利用XRD、SEM及恒电流充放电等等分析手段,研究不同金属离子浓度合成镍钴锰酸锂前驱体对最终产品晶体结构、形貌及其电化学性能的影响。结果表明:金属离子浓度为2.0 mol/L时,所制备材料晶型层状结构发育完整,粒径分布均匀,球形度高且表面光滑,材料首次放电比容量达172.5 mAh/g,首次库伦效率为90.84%。     

Highly enhanced electrochemical performances of LiNi0.815Co0.15Al0.035O2 by coating via conductively LiTiO2 for lithium-ion batteries

LiTiO₂ film-coated layered LiNi_0.815Co_0.15Al_0.035O₂ (NCA) material was successfully synthesised through in situ hydrolysis–lithiation to improve electrochemical properties. Herein, NCA was synthesised using solid state reaction, coated by hydrolysis of tetrabutyl titanate and subjected to lithiation process. The optimal molar ratio (LiTiO₂: NCA) was found to be 1.0 mol%, and the thickness of LiTiO₂ film coated on the surface of NCA of 18 nm was observed through HRTEM images. Compared with pristine NCA, 1.0 mol% LiTiO₂-coated NCA demonstrated better electrochemical performance with larger capacity of 20 mAh g⁻¹ under 1 C after 100 cycles. Its related capacity retention was 90.8%. The 1.0 mol% LiTiO₂-coated sample exhibited high discharge capacity of 157.6 mAh g⁻¹ at a current rate of 10 C, whereas the pristine sample only presented 145.3 mAh g⁻¹. The considerably improvement of the rate and cycling properties of the NCA cathode material is achieved using LiTiO₂ as a Li⁺-conductive coating layer. These new findings contribute towards the design of a stable-structured Ni-rich material for lithium-ion batteries.     

前驱体对三元正极材料LiNi0.5Co0.2Mn0.3O2性能影响的研究

以碳酸锂为锂源,将三种不同厂家的镍钴锰氢氧化物前驱体通过固相烧结法制备锂离子电池三元材料LiNi0.5Co0.2Mn0.3O2(简称NCM),并用纳米氧化铝溶液对其进行了包覆.采用X射线衍射仪、扫描电子显微镜、恒电流充放电测试仪等对材料的物理和电化学性能进行分析测试.结果表明:在前驱体元素组成基本一致的情况下,包覆前后三种前驱体制备的正极材料半电池首次容量由166.7 mAh/g、166.0 mAh/g和166.1 mAh/g改变为169.8 mAh/g、167.4 mAh/g和165.9 mAh/g,而100周循环保持率由92.6％、92.3％和93.2％上升到96.2％、96.0％和96.3％.这种改善应源于包覆过程中形成的快离子导体抑制了循环过程中电池直流内阻(DCIR)的增加.但对于不同前驱体制备的正极材料,包覆后电子传导能力以及界面相容性会有所不同.     

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.     

Electrochemical performance of Li[Co0.1Ni0.15Li0.2Mn0.55]O2 modified by carbons as cathode materials

To enhance specific capacity, cycle performance and rate-capability of lithium-ion battery cathode materials, the Li[Co_0.1Ni_0.15Li_0.2Mn_0.55]O₂ (LCMNO) is modified by coating them with amorphous carbons and by preparing nanocomposites with nanostructured carbons (carbon nanotube and graphene). The carbon-treated LCMNO powders and their cathodes are characterized by morphological observation, crystalline property analysis, galvanostatic charge–discharge, and electrochemical impedance spectroscopy. The LCMNO nanocomposite shows a superior discharge capacity of ca. 290 mAh g⁻¹ at low C-rates, due to a greater number of active sites embedded by nanostructured carbon species. In contrast, the carbon-coated LCMNO shows higher discharge capacity in high rate regions due to the carbon-coated layer in the carbon-coated LCMNO, suppressing the side reactions and enhancing the electrical conductivity.