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.     

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。     

微波共沉淀法制备锂离子电池正极材料LiNi0.8Co0.2O2

采用微波共沉淀法合成了制备LiNi0.8Co0.2O2的前驱体球形α-Ni0.8Co0.2(OH)2,将其与LiOH·H2O混合,在氧气氛围下,用不同的烧结温度分别烧结10小时获得LiNi0.8Co0.2O2正极材料。用XRD、SEM对所制备的正极材料进行结构和形貌分析,用恒流充放电测试材料的电化学性能。结果表明,烧结温度对材料结构和电化学性能影响较大,所合成材料均具有α-NaFeO2的层状结构,烧结温度越高材料结晶越完善。900℃烧结的LiNi0.8Co0.2O2材料初级颗粒结晶最完善而且其二次团聚粒子的平均粒径最小,其表现出的电化学性能也最好,首次放电容量为189.1mA·h·g-1,首次循环放电效率达到92.5%。30循环后放电容量保持在148 mA·h·g-1,显示出较好的循环稳定性。     

锂离子电池正极材料LiNi0.8Co0.2O2的研究

低成本、高比容量的LiNi0.8Co0.2O2是取代已商品化锂电池正极材料LiCoO2的候选材料。用工业原料,通过共沉淀法(pH=11 2±0 05)合成了β Ni0.8Co0.2(OH)2,将其和LiOH·H2O混合,在空气中先后于650℃和750℃烧结8h和20h,制得具有良好层状结构的LiNi0.8Co0.2O2。用合成的材料制备电池,在0 2C、3 0～4 1V进行充放电实验,其放电平台在3 8V以上,首次放电容量超过170mA·h/g,10次循环后,放电容量还能保持在164mA·h/g左右,且库仑效率达到96%以上。     

高浓度下溶剂热法制备锂离子电池富锂正极材料

溶剂热法因具有操作简单、封闭体系易于控制等特点已然成为目前实验室制备富锂正极材料的一种高效方法。目前报导的实验室制法往往在低浓度下进行,限制了实际生产需求。高浓度下利用溶剂热法制备优良性能的富锂正极材料得到了实现,同时利用扫描电子显微镜、透射电子显微镜、能谱分析、激光粒度分析和恒电流充放电测试等研究了不同浓度对其结构和电化学性能的影响。结果表明:乙酸锂浓度为1.0 M时制备的材料具有良好的六边形结构,粒径小,分布均匀,0.1C时放电比容量高达296.1mA·h/g。50次循环后,库仑效率仍保持在97%以上。     

锂离子电池正极材料LiNi0.8M0.2O2的制备

在增加氧气压力的条件下，采用固相反应制得一系列掺杂不同元素M的锂离子电池正极材料LiNi0.8M0.2O2. 研究发现，掺杂Al, Mn, Ti可以改善材料的耐过充性和循环性能，在充电电压为4.2~4.8 V的范围内循环3次，材料的放电容量没有显著的改变. X射线衍射和扫描电镜分析表明，掺杂Al, Mn, Ti提高了镍酸锂材料的六方菱型结构的有序性，维持了在充放电过程中的层状结构的稳定性. 其它掺杂元素降低了材料结构的有序性，影响了其电化学性能. 说明形成完整的晶体结构是掺杂元素的选择依据.     

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.     

锂离子电池LiNi0.6Co0.2Mn0.2O2正极材料的硼元素掺杂改性调控

采用草酸盐共沉淀法结合后续热处理技术制备硼掺杂LiNi0.6Co0.2Mn0.2O2正极材料.研究了不同硼源(B2O3,H3BO3和LiBO2)掺杂对材料形貌、结构和电化学性能的影响.通过X射线衍射仪和Rietveld精修分析证明了硼(B)元素掺杂到材料晶格中.电化学性能研究表明:B2O3掺杂效果最佳,具有优异的倍率性...     

锂离子电池用层状高镍正极材料的研究进展

层状高镍正极材料(Ni≥80%)以其较高的比容量和良好的循环寿命,被认为是极具前景的高比能量动力电池正极材料。文章总结了高镍正极材料存在的问题,介绍了高镍正极材料的改性研究进展,展望了高镍正极材料的应用和发展方向。     

A simple and effective method to synthesize layered LiNi0.8Co0.1Mn0.1O2 cathode materials for lithium ion battery

Nanocrystalline materials of Ni_0.8Co_0.1Mn_0.1(OH)₂ are successfully synthesized by fast co-precipitation method. The crystalline structure and morphology of the precursors and LiNi_0.8Co_0.1Mn_0.1O₂ materials are characterized by XRD, SEM and Rietveld refinement analyses. It is found that the nanocrystalline phase and low crystallinity of Ni_0.8Co_0.1Mn_0.1(OH)₂ could help achieve its uniform mixing with lithium source, and further attribute to highly ordered layered LiNi_0.8Co_0.1Mn_0.1O₂ with low cation mixing degree. Electrochemical studies confirm that the LiNi_0.8Co_0.1Mn_0.1O₂ exhibits a good electrochemical property with initial discharge specific capacity of 192.4 mAh g^− 1 at a current density of 18 mA g^− 1, and the capacity retention after 40 cycles is 91.56%. This method is a simple and effective method to synthesize cathode material.     

Effects of gradient concentration on the microstructure and electrochemical performance of LiNi0.6Co0.2Mn0.2O2 cathode materials

Nickel(Ni)-rich layered materials have attracted considerable interests as promising cathode materials for lithium ion batteries (LIBs) owing to their higher capacities and lower cost. Nevertheless, Mn-rich cathode materials usually suffer from poor cyclability caused by the unavoidable side-reactions between Ni⁴⁺ ions on the surface and electrolytes. The design of gradient concentration (GC) particles with Ni-rich inside and Mn-rich outside is proved to be an efficient way to address the issue. Herein, a series of LiNi_0.6Co_0.2Mn_0.2O₂ (LNCM622) materials with different GCs (the atomic ratio of Ni/Mn decreasing from the core to the outer layer) have been successfully synthesized via rationally designed co-precipitation process. Experimental results demonstrate that the GC of LNCM622 materials plays an important role in their microstructure and electrochemical properties. The as-prepared GC3.5 cathode material with optimal GC can provide a shorter pathway for lithium-ion diffusion and stabilize the near-surface region, and finally achieve excellent electrochemical performances, delivering a discharge capacity over 176 mAh·g⁻¹ at 0.2 C rate and exhibiting capacity retention up to 94% after 100 cycles at 1 C. The rationally-designed co-precipitation process for fabricating the Ni-rich layered cathode materials with gradient composition lays a solid foundation for the preparation of high-performance cathode materials for LIBs.     

LiNi0.1Mn0.1Co0.8O2 electrode material: Structural changes upon lithium electrochemical extraction

We reported here on the synthesis, the crystal structure and the study of the structural changes during the electrochemical cycling of layered LiNi_0.1Mn_0.1Co_0.8O₂ positive electrode material. Rietveld refinement analysis shows that this material exhibits almost an ideal α-NaFeO₂ structure with practically no lithium-nickel disorder. The SQUID measurements confirm this structural result and evidenced that this material consists of Ni²⁺, Mn⁴⁺ and Co³⁺ ions.Unlike LiNiO₂ and LiCoO₂ conventional electrode materials, there was no structural modification upon lithium removal in the whole 0.42 ≤ x ≤1.0 studied composition range. The peaks revealed in the incremental capacity curve were attributed to the successive oxidation of Ni²⁺ and Co³⁺ while Mn⁴⁺ remains electrochemically inactive.     

Ultrathin CeO2 coating for improved cycling and rate performance of Ni-rich layered LiNi0.7Co0.2Mn0.1O2 cathode materials

In this study, we have successfully coated the CeO₂ nanoparticles (CeONPs) layer onto the surface of the Ni-rich layered LiNi_0.7Co_0.2Mn_0.1O₂ cathode materials by a wet chemical method, which can effectively improve the structural stability of electrode. The X-ray powder diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS) are used to determine the structure, morphology, elemental composition and electronic state of pristine and surface modified LiNi_0.7Co_0.2Mn_0.1O₂. The electrochemical testing indicates that the 0.3?mol% CeO₂-coated LiNi_0.7Co_0.2Mn_0.1O₂ demonstrates excellent cycling capability and rate performance, the discharge specific capacity is 161.7?mA?h?g^?1 with the capacity retention of 86.42% after 100 cycles at a current rate of 0.5?C, compared to 135.7?mA?h?g^?1 and 70.64% for bare LiNi_0.7Co_0.2Mn_0.1O₂, respectively. Even at 5?C, the discharge specific capacity is still up to 137.1?mA?h?g^?1 with the capacity retention of 69.0%, while the NCM only delivers 95.5?mA?h?g^?1 with the capacity retention of 46.6%. The outstanding electrochemical performance is assigned to the excellent oxidation capacity of CeO₂ which can oxidize Ni²⁺ to Ni³⁺ and Mn³⁺ to Mn⁴⁺ with the result that suppress the occurrence of Li⁺/Ni²⁺ mixing and phase transmission. Furthermore, CeO₂ coating layer can protect the structure to avoid the occurrence of side reaction. The CeO₂-coated composite with enhanced structural stability, cycling capability and rate performance is a promising cathode material candidate for lithium-ion battery.     

A novel method for the preparation of submicron-sized LiNi0.8Co0.2O2 cathode material

A novel method has been employed to synthesize layered LiNi_0.8Co_0.2O₂ cathode material by calcination of Ni–Co hydroxide–carbonate precursor prepared by a route involving separate nucleation and aging steps (SNAS) together with LiOH under air atmosphere. Thermogravimetry (TG) and differential thermal analysis (DTA) combined with on-line evolved gas mass spectrometry (EGMS) analysis were employed to study the reaction process. The synthesized material was characterized by means of X-ray diffraction (XRD), laser particle size distribution analysis, field emission scanning electron microscope (FE-SEM) and galvanostatic charge/discharge cycling. The synthesized LiNi_0.8Co_0.2O₂ presents a narrow distribution of submicron-sized particles and exhibits a good electrochemical property with initial discharge specific capacity of 194.8 mAh g⁻¹ in the voltage range 2.75–4.5 V (versus Li/Li⁺). The novel method for the preparation of submicron-sized LiNi_0.8Co_0.2O₂ material has the particular advantage of simple synthesis process and low synthesis cost.     

Hydrothermal synthesis of LiNi0.9Co0.1O2 cathode materials

Ultrafine powders of LiNi_0.9Co_0.1O₂ were prepared under mild hydrothermal conditions. The product was characterized by XRD, TEM and EDS tests, which indicated that the obtained products were pure and well-crystallized LiNi_0.9Co_0.1O₂. The ICP-AES results indicated the products were lithium-deficient compounds. The addition of KOH hardly effected the crystallinity of the product but gave larger crystals.     

LiNi0.8Co0.15Al0.05O2 cathode materials prepared by TiO2 nanoparticle coatings on Ni0.8Co0.15Al0.05(OH)2 precursors

Synthesis, electrochemical, and structural properties of LiNi_0.8Co_0.15Al_0.05O₂ cathodes prepared by TiO₂ nanoparticles coating on a Ni_0.8Co_0.15Al_0.05(OH)₂ precursor have been investigated by the variation of coating concentration and annealing temperature. TiO₂-coated cathodes showed that Ti elements were distributed throughout the particles. Among the coated cathodes, the 0.6 wt% TiO₂-coated cathode prepared by annealing at 750 °C for 20 h exhibited the highest reversible capacity of 176 mAh g⁻¹ and capacity retention of 92% after 40 cycles at a rate of 1C (=190 mA g⁻¹). On the other hand, an uncoated cathode showed a reversible first discharge capacity of 186 mAh g⁻¹ and the same capacity retention value to the TiO₂-coated sample at a 1C rate. However, under a 1C rate cycling at 60 °C for 30 cycles, the uncoated sample showed a reversible capacity of 40 mAh g⁻¹, while a TiO₂-coated one showed 71 mAh g⁻¹. This significant improvement of the coated sample was due to the formation of a possible solid solution between TiO₂ and LiNi_0.8Co_0.15Al_0.05O₂. This effect was more evident upon annealing the charged sample while increasing the annealing temperature, and at 400 °C, the coated one showed a more suppressed formation of the NiO phase from the spinel LiNi₂O₄ phase than the uncoated sample.     

Performance of LiNi1/3Co1/3Mn1/3O2 prepared from spent lithium-ion batteries by a carbonate co-precipitation method

Spherical LiNi_1/3Co_1/3Mn_1/3O₂ cathode particles were resynthesized by a carbonate co-precipitation method using spent lithium-ion batteries (LIBs) as a raw material. The physical characteristics of the Ni_1/3Co_1/3Mn_1/3CO₃ precursor, the (Ni_1/3Co_1/3Mn_1/3)₃O₄ intermediate, and the regenerated LiNi_1/3Co_1/3Mn_1/3O₂ cathode material were investigated by laser particle-size analysis, scanning electron microscopy–energy-dispersive spectroscopy (SEM-EDS), thermogravimetry–differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), inductively coupled plasma–atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). The electrochemical performance of the regenerated LiNi_1/3Co_1/3Mn_1/3O₂ was studied by continuous charge–discharge cycling and cyclic voltammetry. The results indicate that the regenerated Ni_1/3Co_1/3Mn_1/3CO₃ precursor comprises uniform spherical particles with a narrow particle-size distribution. The regenerated LiNi_1/3Co_1/3Mn_1/3O₂ comprises spherical particles similar to those of the Ni_1/3Co_1/3Mn_1/3CO₃ precursor, but with a narrower particle-size distribution. Moreover, it has a well-ordered layered structure and a low degree of cation mixing. The regenerated LiNi_1/3Co_1/3Mn_1/3O₂ shows an initial discharge capacity of 163.5 mA h g^?1 at 0.1 C, between 2.7 and 4.3 V; the discharge capacity at 1 C is 135.1 mA h g^?1, and the capacity retention ratio is 94.1% after 50 cycles. Even at the high rate of 5 C, LiNi_1/3Co_1/3Mn_1/3O₂ delivers the high capacity of 112.6 mA h g^?1. These results demonstrate that the electrochemical performance of the regenerated LiNi_1/3Co_1/3Mn_1/3O₂ is comparable to that of a cathode synthesized from fresh materials by carbonate co-precipitation.     

Characterization of yttrium substituted LiNi0.33Mn0.33Co0.33O2 cathode material for lithium secondary cells

LiNi_0.33−xMn_0.33Co_0.33Y_xO₂ materials are synthesized by Y³⁺ substitute of Ni²⁺ to improve the cycling performance and rate capability. The influence of the Y³⁺ doping on the structure and electrochemical properties are investigated by means of X-ray diffraction (XRD), scanning electron microscope (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and galvanostatic charge/discharge tests. LiNi_0.33Mn_0.33Co_0.33O₂ exhibits the capacity retentions of 89.9 and 87.8% at 2.0 and 4.0 C after 40 cycles, respectively. After doping, the capacity retentions of LiNi_0.305Mn_0.33Co_0.33Y_0.025O₂ are increased to 97.2 and 95.9% at 2.0 and 4.0 C, respectively. The discharge capacity of LiNi_0.305Mn_0.33Co_0.33Y_0.025O₂ at 5.0 C remains 75.7% of the discharge capacity at 0.2 C, while that of LiNi_0.33Mn_0.33Co_0.33O₂ is only 47.5%. EIS measurement indicates that LiNi_0.305Mn_0.33Co_0.33Y_0.025O₂ electrode has the lower impedance value during cycling. It is considered that the higher capacity retention and superior rate capability of Y-doped samples can be ascribed to the reduced surface film resistance and charge transfer resistance of the electrode during cycling.