镍钴铝酸锂正极材料改性研究进展及展望

综述了锂离子电池镍钴铝三元正极材料LiNi_xCo_yAl_(1-x-y)O_2(NCA,x≥0.8)存在的不可逆容量大、循环性能差等问题及其性能优化改性技术的研究进展,从表面包覆和体相掺杂两个方面对近年来国内外NCA正极材料的电化学性能改善研究进行系统性总结,分析了各类包覆物以及掺杂元素的作用机理,并对NCA正极材料的未来研究方向进行了展望。     

高能量密度锂离子电池LiNi_(0.8)Co_(0.15)Al_(0.05)O_2正极材料改性的研究进展

镍钴铝酸锂(LiNi_(0.8)Co_(0.15)Al_(0.05)O_2,NCA)因具有高能量密度、高性价比等优点,被视为最具发展潜力的动力锂电池正极材料.但NCA在使用过程中安全性、循环稳定性、高温性能较差,需要通过离子掺杂、表面包覆等方式改性,以改善材料的电化学性能.本工作对NCA的改性研究进行总结,并展望了未来的研究方向.     

硼酸喷雾包覆改性镍钴铝酸锂的制备及其电化学性能研究

针对镍钴铝酸锂（NCA）三元正极材料普遍存在的循环寿命差、浆料容易凝胶等缺点进行了硼酸喷雾包覆的改性。采用X 射线衍射仪（XRD）、扫描电镜（SEM）、透射电镜（TEM）及电化学测试等方法对硼酸包覆改性前后的材料性能进行了对比表征和分析。结果表明：喷雾包覆后可以在NCA正极材料表面形成一层保护层,改性后的NCA三元正极材料循环寿命有明显提升,特别是高温（45 ℃）1C/1C倍率下循环50次容量保持率由改性前的88.0%提升至改性后的95.2%,提升近7%;硼酸包覆可以改善NCA表面特性,使正极浆料稳定性大大提高。改性后的NCA正极浆料可以稳定放置168 h（7 d）,解决了NCA正极材料容易凝胶的问题。     

高镍三元正极材料镍钴铝的掺杂改性研究进展

高镍三元正极材料镍钴铝（NCA）因具有较高的能量密度及工作电压、成本低、环境友好等优点极有可能成为下一代广泛应用的锂离子电池正极材料之一。然而镍含量的提高导致材料结构不稳定、循环性能和倍率性能降低,限制了其进一步发展。主要从锂位、过渡金属位、氧位掺杂及复合共掺杂4个方面综述了不同位置离子掺杂的改性机理。大量研究结果表明,通过复合共掺杂方式进行改性,能够结合单离子掺杂的优点有效提升镍钴铝正极材料的电化学性能。     

锂离子电池正极材料LiNi_xCoyAl_(1-x-y)O_2制备方法的研究进展

锂离子电池正极材料LiNi_xCo_yAl_(1-x-y)O_2(简称"NCA")具有比容量高、功率性能好、安全性较好、成本较低等优点,成为研究的热点,并在电动汽车、电动工具等领域实现商业化应用。文章总结了正极材料NCA制备方法的研究进展,为不同电化学性能要求的NCA制备提供重要参考。     

锂离子电池正极材料LiFePO4的改性研究进展

橄榄石型结构的磷酸亚铁锂( LiFePO4)作为备受关注的锂离子电池正极材料,可望成为新一代首选的可代替钴酸锂的锂离子二次电池正极材料.详细地叙述了近年来国内外对LiFePO4改性所做的研究,着重介绍了导电剂掺杂包覆、金属离子掺杂和合成方法对LiFePO4电化学性能的影响,以及这些改性方法存在的问题.     

镁离子掺杂锂离子电池硅酸锰锂正极材料

以MgAC2为掺杂剂,葡萄糖碳化为碳包覆源,通过溶胶凝胶法制备了含有镁离子的硅酸锰锂正极材料前驱体,在惰性气保护下经高温焙烧得到碳包覆的硅酸锰锂正极材料.对镁离子掺杂对硅酸锰锂物理和电化学性能的影响进行了探讨.交流阻抗和循环伏安测试表明,碳包覆和低含量镁离子掺杂不会破坏硅酸锰锂的材料,并且显著提高了电子传导过程的电导率...     

聚并苯/氧化铝双层包覆对高镍三元正极材料电化学性能的影响

通过表面包覆对锂离子电池正极材料-镍钴锰三元材料进行改性,提高其结构稳定性和界面稳定性。采用导电聚合物聚并苯(PAS)和金属氧化物Al₂O₃对KCl掺杂改性的LiNi_0.5Co_0.2Mn_0.3O₂(NCM523)进行双层包覆改性,以进一步提高其综合性能。通过XRD、SEM、TEM分析及电化学性能测试表明,包覆没有改变材料结构,包覆层改善了材料界面的电导率,阻止了电极活性材料表面的副反应,有利于提高锂离子电池的大倍率性能。     

锂离子电池三元正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2的制备方法及其改性研究进展

三元正极材料(LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2)具有较好的安全性能和循环性能,兼顾了其它二元电极材料的诸多优点,成为目前高性能锂离子电池正极材料的研究重点之一,其市场占有率已经超过40%。详细叙述了近年来国内外对三元正极材料的制备和改性所做的研究,着重介绍了其高温固相法、共沉淀法、溶胶-凝胶法等制备方法及掺杂、包覆改性方法对LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2电化学性能的影响,以及这些改性方法存在的问题。     

天津力神开发高能动力锂电池

正天津力神项目团队在氧化镍钴铝锂(NCA)正极材料前期研究基础上,开发高比能量、长循环寿命、良好安全性能的锂离子动力电池用高镍系正极材料;通过纳米制备、纳米分散、包覆及预嵌锂等多种技术,研制容量高、首次效率高、循环稳定性及倍率性能好的硅碳负极材料。该项目团队基于该体系开发了电芯单体的比能量达到302 Wh/kg,体积能量密度大于642 Wh/L,25℃下1C充放电循环710次,容     

尖晶石型锰酸锂锂离子筛的合成研究

为了比较不同合成方法对锰酸锂(Li4Mn5O12)锂离子筛的结构、饱和交换容量和分离因子的影响,采用低温固相反应法和溶胶-凝胶法合成了锰酸锂锂离子筛,并用X射线衍射(XRD)表征了所得材料的结构.结果表明,低温固相反应法和溶胶-凝胶法制备的锰酸锂及其离子筛均为尖晶石结构.低温固相反应法合成的锂离子筛,其锂离子饱和交换容量为16.06 mg/g(2.31 mmol/g)、分离因子αLiNa为23;溶胶-凝胶法合成的锰酸锂锂离子筛,其锂离子饱和交换容量为26.39 mg/g(3.80 mmol/g),分离因子αLiNa为216,优于低温固相反应法所得锂离子筛的性能.     

Rechargeable lithium battery anodes: alternatives to metallic lithium

This review is concerned with alternatives to metallic lithium for use in rechargeable lithium batteries. Emphasis is placed on the use of various materials and combinations of materials in different types of electrodes rather than on the properties of the materials themselves. The review includes carbon based electrodes, alloys, conducting polymers and transition metal compounds. Special consideration is given to electrodes and materials used in organic liquid and polymer electrolytes, whereas liquid cathode and molten salt systems are excluded.     

Graphene nanosheets for enhanced lithium storage in lithium ion batteries

Graphene nanosheets were synthesized in large quantities using a chemical approach. Field emission electron microscope observation revealed that loose graphene nanosheets agglomerated and crumpled naturally into shapes resembling flower-petals. High resolution transmission electron microscope analysis, Raman spectroscopy and ultraviolet-visible spectroscopy measurements confirmed the graphitic crystalline structure of the graphene nanosheets. The nanosheets exhibited an enhanced lithium storage capacity as anodes in lithium-ion cells and good cyclic performance.     

锂离子电池材料钛酸锂钠的研究进展

Na₂Li₂Ti₆O₁₄电池具有较低的电位平台（1.3 V）以及经济成本低的特点,对便携式电子设备、能源汽车、生态环境等领域具有重大意义。由于钛酸锂钠电池固有离子电导率低的特点,因此提高钛酸锂钠电池锂离子扩散系数是目前研究中的主流方向,为此综述了钛酸锂钠的结构特点以及合成方法对钛酸锂钠材料粒径、形貌及电池电化学性能的影响;对比了不同掺杂离子和表面包覆改性对钛酸锂钠电池的放电比容量、循环性能及离子扩散系数的影响。掺入适量元素铌具有更高的锂离子扩散系数;包覆碳纳米管有更大的容量保持率,更有助于进一步提高钛酸锂钠电池电化学性能。     

Extracting lithium from waste solutions of chemico-metallurgical lithium carbonate production

In order to reduce the loss of lithium in waste solutions of chemico-metallurgical lithium carbonate production, it is suggested to extract lithium from these solutions in the form of poorly soluble hydroxodialuminate under the action of sodium and potassium aluminates. Technological tests showed that the proposed method ensures almost complete isolation of lithium from waste solutions of lithium carbonate production.     

The dynamic evolution of aggregated lithium dendrites in lithium metal batteries

Lithium (Li) metal anodes promise an ultrahigh theoretical energy density and low redox potential,thus being the critical energy material for next-generation batteries.Unfortunately,the formation of Li den-drites in Li metal anodes remarkably hinders the practical applications of Li metal anodes.Herein,the dynamic evolution of discrete Li dendrites and aggregated Li dendrites with increasing current densities is visualized by in-situ optical microscopy in conjunction with ex-situ scanning electron microscopy.As revealed by the phase field simulations,the formation of aggregated Li dendrites under high current den-sity is attributed to the locally concentrated electric field rather than the depletion of Li ions.More specif-ically,the locally concentrated electric field stems from the spatial inhomogeneity on the Li metal surface and will be further enhanced with increasing current densities.Adjusting the above two factors with the help of the constructed phase field model is able to regulate the electrodeposited morphology from aggregated Li dendrites to discrete Li dendrites,and ultimately columnar Li morphology.The methodol-ogy and mechanistic understanding established herein give a significant step toward the practical appli-cations of Li metal anodes.     

四氟硼锂和六氟砷锂的合成与拉曼光谱分析

介绍了合成高纯无水的ＬｉＢＦ４和ＬｉＡｓＦ６的新方法，并讨论了其合成条件，指出制备多孔状ＬｉＦ和控制反应温度是合成的关键。     

锂离子电池磷酸铁锂正极材料的研究进展

橄榄石结构的磷酸铁锂的安全性非常高,而且其循环性能优异,在高温下也可以使用,是最有发展前景的电池正极材料。磷酸铁锂的循环寿命较长,而且其放电性能是其他的离子电池不能比的,在高温下稳定性比较好,使磷酸铁锂成为电池正极常用的材料。但是,磷酸铁锂的电导率并不是特别的理想,而且锂离子的扩散系数不足,在低温下不能发挥较好的效果,所以产生一定的局限性。通过分析磷酸铁锂的结构、性能等,在一定程度上可以完善磷酸铁锂的性能。     

Structure and electrochemical behavior of lithium vanadate materials for lithium batteries

New vanadate compounds having the molecular structure Li_xMg_1−xV_2−xMo_xO₆ (0 ≤ x ≤ 1) were studied. Six samples were prepared by sol-gel process from precursor using the following ratios of x = 0, 0.2, 0.4, 0.6, 0.8 and 1, respectively. These samples were labeled S1, S2, S3, S4, S5 and S6. The final process of firing occurred at 750 °C for 18 h in air. The prepared materials were characterized by XRD, SEM, IR, electron spin resonance (ESR) and magnetic measurements. The morphologies of S1, S2, S5 and S6 are prismatic as they have monoclinic crystal structures. S3 and S4 differ in the crystal morphology from the other previous samples due to their triclinic crystal lattice structure. IR spectra revealed that the bond lengths of the vanadyl groups ν_VO, ν_{sy V-O} and σ_V-O increase in the same direction from S1 to S6. The data of the ESR explain the existence of V⁴⁺ beside V⁵⁺ in S1, S4 and S6 and also presence of Mo⁵⁺ with Mo⁶⁺ in S4 and S6. S4 exhibited better magnetic susceptibility and saturated magnetization than the other samples. The first specific discharge capacities of the samples were performed. S4 showed the maximum specific capacity of 265 mAh g⁻¹ in comparison with the other samples. Cyclic voltammogram of S4 exhibited the highest current intensity in comparison with the other samples. This sample showed two peaks at 0.53 and 1.3 V versus Li/Li⁺ characterizing double de-insertions of two lithium atoms from Li_1.6Mg_0.4V_1.4Mo_0.6O_6−x and Li_0.6Mg_0.4V_1.4Mo_0.6O₆, respectively. Also, two additional peaks were characterized for the oxidation of Mo⁵⁺ to Mo⁶⁺ and V⁴⁺ to V⁵⁺ at 3.5 and 4 V, respectively.     

锂离子电池正极材料锰酸锂的改性研究

用氟化锂对预先合成的锰酸锂(LiMn2O4)进行氟化处理,研究了处理温度对材料电化学比容量与高温下循环稳定性的影响.结果表明,氟化锂/锰酸锂混合体系在500 ℃以上开始反应,所形成材料的特性发生了明显的变化;氟化锂处理可以改善锰酸锂材料的结晶度,热处理温度越高,处理后材料的结晶度越好;随着处理温度的升高,锰酸锂材料经历了从"烧结型"到"结晶型"的转变,700 ℃以上烧结的材料形成了八面体的晶体颗粒;初始比容量与循环性能也随着处理温度的不同而变化,600 ℃条件下处理的材料初始比容量最低,但循环性能最好.