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。     

锂离子电池正极材料LiAl_yCo_(1-y)O_2的制备及其性能研究

用高温固相法制备了锂离子电池正极材料LiAlyCo1-yO2。掺杂前后该材料的物理性能无太大变化;利用XRD与能谱仪观察到了铝元素的特征峰。通过对电化学性能的研究,发现其电化学比容量明显高于原始的钴酸锂,但其循环性能下降;当铝的掺杂量增加时,复合物的放电时间明显减少;实验得出铝元素的摩尔掺杂量为0.10时各方面性能最佳。     

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LiAlyCo1-yO2的制备及其性能研究

用高温固相法制备了锂离子电池正极材料LiAlyCo1-yO2.掺杂前后该材料的物理性能无太大变化;利用XRD与能谱仪观察到了铝元素的特征峰.通过对电化学性能的研究,发现其电化学比容量明显高于原始的钴酸锂,但其循环性能下降;当铝的掺杂量增加时,复合物的放电时间明显减少;实验得出铝元素的摩尔掺杂量为0.10时各方面性能最佳.     

5V正极材料LiNi_(0.5)Mn_(1.5)O_(4-x)F_x(x=0,0.1)的流变相法制备与表征

采用流变相法结合高温热处理制备LiNi0.5Mn1.5O4-xFx(x=0,0.1)。用X射线衍射、扫描电镜和电化学测试等手段对合成材料进行了表征。结果表明,F的掺入抑制了LiNi0.5Mn1.5O4颗粒长大,增强了Li+在固相中的扩散能力,改善了电极与电解质溶液之间的界面性质,有效地提高了LiNi0.5Mn1.5O4的循环性能和倍率性能。0.2C放电时LiNi0.5Mn1.5O3.9F0.1的首次放电容量达到147.8mA.h/g,经80次循环后平均每次循环的容量衰减仅为0.0068%。而0.5C和2.0C放电时首次放电容量达到0.2C放电时的94.2%和83.8%。     

锂离子电池正极材料铌掺杂LiNiO2 的制备与电化学性能

为了提高LiNiO₂的电化学性能,用固相反应法制备了铌掺杂LiNiO₂材料,并用X射线衍射（XRD）分析、恒电流滴定技术（GITT）、电化学阻抗谱（EIS）等方法研究铌掺杂量对LiNiO₂的结构和性能的影响。结果表明适量的铌（Nb）掺杂可以提高LiNiO₂层状结构的有序程度,降低Li⁺/Ni²⁺混合程度,降低电荷转移阻抗,提高活性材料中锂离子的扩散系数。其中LiNi_0.99Nb_0.01O₂在0.5C循环100次的容量保持率为91.4%,5C时放电比容量为143 mA·h/g。而未掺杂铌的LiNiO₂在相同条件下的容量保持率和比容量仅为69.2%和127 mA·h/g。结果说明铌掺杂能够有效提高LiNiO₂的电化学性能。     

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.     

富镍三元正极材料LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2的制备及电化学性能

Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_2是一种高比容量锂离子电池正极材料。本文研究通过活性炭中孔道吸附钴、锰、镍盐的混合溶液的途径来制备纳米LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2材料。XRD研究显示,600℃和800℃焙烧得到的材料相比,700℃下焙烧得到的材料具有低的阳离子混排程度,因而具有好的充放电性能,在0.2C电流下充放,该材料的首次比容量为188.3mAh g~(-1),50圈循环后,容量仍达140.9m Ah g~(-1),容量保持率为74.0%。     

高压正极材料LiNi_(0.5)Mn_(1.5)O_4锂离子电池阻燃电解液的研究

研究了甲基磷酸二甲酯(DMMP)含量对1 mol/L Li PF6/EC∶DEC∶EMC(1∶1∶1)电解液的电化学稳定性、热稳定性及电导率的影响,并首次将含DMMP的阻燃电解液应用于高压材料LiNi_(0.5)Mn_(1.5)O_4中。结果表明,加入DMMP添加剂后电解液的热稳定性得到提高,但是该添加剂电解液的电导率有所降低。研究了DMMP对LiNi_(0.5)Mn_(1.5)O_4扣式电池的电化学性能的影响,循环伏安测试表明,几乎不影响电解液在高压条件下的使用,充放电测试结果表明,DMMP的使用会降低电池的循环性能,当DMMP含量为5%时,对电池的循环性能影响较小。此外,交流阻抗(EIS)分析表明,DMMP对循环性能影响的主要原因是内阻随着循环的增加而增大。     

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.     

Preparation and characterization of LiNi0.8Co0.15Al0.05O2 with high cycling stability by using AlO2- as Al source

We report the preparation of a series of LiNi_0.8Co_0.15Al_0.05O₂ materials with different reaction time (10, 20, 30 and 40 h) of precursor and their electrochemical properties as cathode material for lithium-ion batteries (LIBs). The preparation of LiNi_0.8Co_0.15Al_0.05O₂ was divided into two steps: a co-precipitation process to obtain Ni_0.8Co_0.15Al_0.05(OH)₂ precursor and a calcination step with LiOH. During the co-precipitation process, AlO₂^- was employed as Al source so as to guarantee Ni²⁺, Co²⁺ and Al³⁺ co-precipitation. The impacts of different synthesis time of the precursor on crystal structure, morphology and electrochemical performance of LiNi_0.8Co_0.15Al_0.05O₂ were systematically investigated. The samples with various synthesis time of precursor possessed spherical morphology and a layered α-NaFeO₂ structure with R-3m space group. Especially, when the reaction time of precursor was 30 h, the LiNi_0.8Co_0.15Al_0.05O₂ had the weakest degree of Li⁺/Ni²⁺ ions mixing and the best uniformity and integrity. When used as cathode materials for LIBs, the LiNi_0.8Co_0.15Al_0.05O₂ with 30 h exhibited high discharge capacity, good cycling performance and remarkable rate capability. The maximum discharge capacity was 202.3 mAh g⁻¹ at 0.1 C and the capacity retention approached 99.4% after 100 cycles at 1 C. At 10 C, the discharge capacity exceeded 140 mAh g⁻¹, suggesting a possible application in the high rate LIBs. The excellent electrochemical performance might be attributed to the uniform co-precipitation of Ni²⁺, Co²⁺ and Al³⁺ and well layered structure with less Li⁺/Ni²⁺ mixing.     

熔融盐法合成高密度锂离子电池正极材料LiNi0.8 Co0.2 O2

采用热分析法对不同组成的LiOH-LiNO3二元体系进行研究,绘制了具有最低共熔点的该二元体系的步冷曲线和t-x相图,该体系的最低共熔点为175.7℃。利用低共熔混合物LiNO3-LiOH为锂盐,与高密度前驱体Ni0.8Co0.2(OH)2混合经2个恒温阶段烧结(600℃恒温6 h、800℃恒温24 h)制备出了振实密度高达3.23 g/cm3的锂离子电池正极材料LiNi0.8Co0.2O2。X射线衍射分析表明合成的LiNi0.8Co0.2O2具有规整的层状NaFeO2结构。电性能测试表明:在0.5 mA/cm2放电电流密度和3.0—4.3 V的电压范围内,LiNi0.8Co0.2O2首次放电比容量达175(mA.h)/g,放电比容量为163(mA.h)/g,库仑效率为93%。实验结果表明采用该工艺能够制备出电化学性能良好的锂离子正极材料。     

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.     

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。     

低共熔混合锂盐合成LiNi_(0.8)Co_(0.2)O_2的研究

在空气气氛中,采用低共熔混合物L iNO3-L iOH为锂盐,制备出了锂离子电池正极材料L iN i0.8Co0.2O2。XRD分析表明:此工艺制得的正极材料具有完整的层状结构。电性能测试表明:在0.5 mA/cm2的充放电电流密度和2.7~4.2 V的电压范围内,L iN i0.8Co0.2O2首次放电比容量为145.2 mA.h/g,充放电库仑效率为83.8%;循环20次后,放电比容量为124.8 mA.h/g。该方法能制备出电化学性能良好的L iN i0.8Co0.2O2正极材料。     

锂离子电池正极材料研究的进展

锂离子电池由于有高能量密度、高输出电压、无记忆效应和无环境污染等优点,得到越来越多的应用。作者简述了锂离子电池的结构和充放电原理,详细介绍了近年来应用于锂离子电池的一些正极材料。并讨论了它们的优缺点及在锂离子电池中的应用前景。指出今后电极材料的研究与开发重点将朝着高比容量、高充放电效率、高循环性能以及低成本方向发展。     

Improved electrochemical performance of Li1.2Ni0.2Mn0.6O2 cathode material for lithium ion batteries synthesized by the polyvinyl alcohol assisted sol-gel method

Li-rich Mn-based cathode materials (Li_1.2Ni_0.2Mn_0.6O₂) have been synthesized by a polyvinyl alcohol (PVA)-assisted sol-gel method. The influence of PVA content on the structure and electrochemical performance of Li_1.2Ni_0.2Mn_0.6O₂ has been investigated respectively. XRD results of the Li_1.2Ni_0.2Mn_0.6O₂ powders show that they exhibit similar XRD patterns as those of Li-rich Mn-based cathode materials, and the crystalline nature of the layered compound are improved by the presence of PVA. Physical characterizations indicate that the as-synthesized oxide is composed of uniform and separated particles compared to the larged aggregated ones of the product synthesized under the same condition but without PVA. As cathode for lithium ion battery, the material synthesized with 10% PVA exhibits not only a relatively high discharge capacity of 254.2 mA h g⁻¹, but also excellent rate performance and good cycling performance. EIS results show that the material synthesized with PVA decreases the charge-transfer resistance and enhances the reaction kinetics, which is considered to be the major factor for higher rate performance.     

锂离子电池正极材料锰酸锂的制备与改性研究

锂离子电池是绿色高能可充电池,具有工作电压高、比能量大、自放电少、循环寿命长、无记忆效应、无环境污染等突出优点.尖晶石型锰酸锂正极材料具有无毒、成本低、电容量高等优点,近年来引起广泛关注.但在高温环境下,锰酸锂正极材料的充放电容量迅速下降,成为制约其发展的主要缺点.从锰酸锂的制备与改性研究方面综述了锂离子电池正极材料锰酸锂的研究进展,在此基础上,提出了正极材料锰酸锂的发展方向.     

Phase structure and electrochemical performance of layered-spinel integrated LiNi0.5Mn0.5O2-LiMn1.9Al0.1O4 composite cathodes for lithium ion batteries

In recent years, multi-component integrated composite cathodes for lithium ion batteries have attracted considerable attention. In this work, novel layered-spinel integrated cathode materials of (1−x)LiNi_0.5Mn_0.5O₂-xLiMn_1.9Al_0.1O₄ were synthesized by a sol-gel method, and their phase structures, morphologies and electrochemical performance were investigated. The crystal structure of the (1−x)LiNi_0.5Mn_0.5O₂-xLiMn_1.9Al_0.1O₄ is changed from layered to spinel structure with increasing x. All the samples exhibit nanoscale grains with the minimum grain size of ~130 nm when x = 0.5. The composite electrode with x = 0.5 exhibits the optimal discharge capacity, presenting a large initial discharge capacity of 236 mAh g⁻¹ at the current density of 20 mA g⁻¹. Good rate capability is also obtained at the composite electrode with x = 0.5 where the electrode displays the relatively high discharge capacity of 64.9 mAh g⁻¹ at the high rate of 5 C. The improved electrochemical performance is related to the introduction of spinel structure into layered structure and small grain size. The spinel structure can stabilize the layered structure, which leads to the improvement in the electrochemical performance of the composites; and the small grain size in the sample with x = 0.5 provides short lithium ion diffusion way and thus enhances the electrochemical performance.