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化学进展 2019, Vol. 31 Issue (2/3): 442-454 DOI: 10.7536/PC180714 前一篇   后一篇

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富镍三元层状氧化物LiNi0.8Co0.1Mn0.1O2正极材料

冯泽, 孙旦, 唐有根**(), 王海燕**()   

  1. 中南大学化学化工学院 化学电源湖南省重点实验室 锰资源高效清洁利用湖南省重点实验室 长沙 410083
  • 收稿日期:2018-07-11 出版日期:2019-02-15 发布日期:2018-12-20
  • 通讯作者: 唐有根, 王海燕
  • 基金资助:
    国家科技重点研发项目(2018YFB0104000); 湖南省科技计划重大专项(2017GK1040); 湖南省科技计划重大专项(2017GK5040); 湖南省科技计划项目(2016TP1007); 湖南省科技计划项目(2017TP1001); 中南大学创新驱动计划(2016CXS009)
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Rich-Nickel Ternary Layered Oxide LiNi0.8Co0.1Mn0.1O2 Cathode Material

Ze Feng, Dan Sun, Yougen Tang**(), Haiyan Wang**()   

  1. Hunan Provincial Key Laboratory of Chemical Power Sources, Hunan Provincial Key Laboratory of Efficient and Clean Utilization of Manganese Resources, College of Chemistry and Chemical Engineering, Central South University, Changsha 410083,China
  • Received:2018-07-11 Online:2019-02-15 Published:2018-12-20
  • Contact: Yougen Tang, Haiyan Wang
  • About author:
    ** E-mail: (Yougen Tang);
    (Haiyan Wang)
  • Supported by:
    National Key R&D Program of China(2018YFB0104000); Science and Technology Major Project of Hunan Province(2017GK1040); Science and Technology Major Project of Hunan Province(2017GK5040); Science and Technology Plan Project of Hunan Province(2016TP1007); Science and Technology Plan Project of Hunan Province(2017TP1001); Innovation-Driven Project of Central South University(2016CXS009)

富镍三元层状氧化物LiNi0.8Co0.1Mn0.1O2(NCM811)由于其可逆容量高、环境友好、价格低廉等优势,被认为是下一代锂离子电池最具潜力的正极材料之一。然而,NCM811存在着热稳定性差、充放电过程中结构易发生相变、安全性低等缺点,阻碍了其大规模生产。随着材料制备技术的不断进步,NCM811的电化学性能有了极大的提高。本文综述了近几年来富镍层状氧化物NCM811正极材料的最新研究进展,重点对该材料存在的问题与失效机制、合成方法、改进措施和理论计算模拟研究进行了深入阐述,并对NCM811未来发展作了展望。

关键词： LiNi0.8Co0.1Mn0.1O2, 相变, 合成方法, 模拟

Nickel-rich ternary layered oxide LiNi0.8Co0.1Mn0.1O2 (NCM811) is considered to be one of the most potential cathode materials in the next generation lithium-ion batteries due to its high reversible capacity, environmentally friendly feature and low cost. However, this kind of cathode material is suffering from the poor thermal stability, phase transition during the charge-discharge process and safety issue, which hinders its further practical application. With the deepening of researches and development of fabrication methods, the electrochemical properties of NCM811 have been significantly improved. In this paper, the recent research progress of nickel-rich layered oxide NCM811 cathode material has been reviewed. We mainly focus on the problems and declined mechanisms, synthesis methods, improvement measures and theoretical calculation simulation studies of NCM811, and also make a brief outlook for the future development of nickel-rich ternary layered oxide NCM811.

Key words: LiNi0.8Co0.1Mn0.1O2, phase transition, preparation method, simulation
()
表1 商业化正极材料主要性能参数[7,8,9]
Table 1 Main performance parameters of commercial cathode materials[7,8,9]
Parameter LiMn2O4 LiFePO4 LiCoO2 LiNixCoyMzO2
Crystal structure Spinel Olivine Layered Layered
Theoretical capacity(mAh·g-1) 148 170 274 278
Test capacity(mAh·g-1) 90~120 110~160 140~170 145~200
Operating Voltage(V) 3.8 3.5 3.7 3.6
Raw materials Abundant Abundant Lacking Sufficient
图1 高镍三元正极材料中不同区域的阳离子混排[14]
Fig. 1 Cation mixing of different regions in nickel-rich ternary cathode material[14]
图2 原位XRD和质谱联用分析三元材料结构相变示意图[19]
Fig. 2 Schematic diagram of phase transitions in ternary material structures results from in situ TR-XRD with MS analysis[19]
表2 经过3000次循环后电池负极指标的表征与计算结果[57]
Table 2 The results of characterization and calculation in anode after 3000 cycles[57]
Sample Estimated SEI thickness by XPS(nm) Calculated weight of Li in LiF as SEI(mg) Calculated capacity loss by Li in SEI(mAh) Estimated anode potential after capacity Loss(V)
Cell-Mo after 3000 cycles 10 2.65 10.2 0.56
Cell-Ref after 3000 cycles 20 5.30 20.4 0.63
图3 LixAlO2和LixTi2O4双包覆层修饰NCM811材料的合成过程[71]
Fig. 3 Synthesis process of LixAlO2 and LixTi2O4 coating layers on NCM811 cathode[71]
图4 球形梯度富镍材料[17]
Fig. 4 Spherical gradient nickel-rich material[17]
图5 多晶和单晶正极材料SEI膜形成模型[78]
Fig. 5 Formation model of SEI layer in polycrystalline and single crystal cathode materials[78]
图6 不同熔剂、温度下合成单晶NCM811材料[43]
Fig. 6 Synthesis of single crystal NCM811 material under different fluxes and temperatures[43]
图7 (a)、(b)分别为不同添加剂的结构和其线性伏安扫描[90]
Fig. 7 The structures of the different additives(a) and their linear volt-ampere scanning curves(b)[90]
图8 不同过渡金属间的键价强度[16]
Fig. 8 The bond strength between different transition metals[16]
图9 未掺杂、Al掺杂和Mg掺杂材料结构缺陷的生成焓,(a)氧空位,(b)镍占锂位,(c)锂镍交换[96]
Fig. 9 The formation energy of defective sites for structures of un-doped, Al-and Mg-doped in the case of(a) the oxygen vacancy(VO),(b) excess Ni(Ni Li), and(c) Li/Ni exchange(LiNi-NiLi)[96]
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