高镍锂离子电池三元正极材料的掺杂改性研究进展

doi:10.12422/j.issn.1006-396X.2025.03.003

摘要/Abstract

摘要：

高镍三元正极材料LiNi _x Co _y Mn_1-_x_-_y O₂（x≥0.6，NCM）由于其成本低廉、能量密度高、使用寿命长等优势，被认为是最具应用价值的锂离子电池正极材料之一。高镍虽然会显著提升NCM的比容量和能量密度，但也会导致其循环和热稳定性下降，因此其实际应用严重受限。对NCM进行掺杂改性是提升材料结构稳定性、改善其电化学性能的有效策略。详细介绍了NCM材料的掺杂方法；系统分析了多种掺杂元素对NCM容量、倍率性能、循环性能等的影响；对NCM的开发和未来所面临的挑战进行了展望，有望为NCM的应用提供参考。

关键词: 高镍, 三元正极材料, 掺杂策略, 锂电池

Abstract:

The high nickel cathode material LiNi _x Co _y Mn_1-_x_-_y O₂(x≥0.6,NCM) is considered to be one of the most valuable cathode materials for lithium?ion batteries due to its low cost,high energy density and long service life.Although the high nickel content leads to a significant increase in the specific capacity and energy density of NCM,the increase in nickel content leads to poor cycling and thermal stability,which severely limits its practical application.Doping modification is an effective strategy to improve the structural stability and electrochemical performance of NCM.In this review,the common doping preparation methods of NCM are first described in detail.Subsequently,the effects of various doped elements on the lithium storage,rate performance and cycling performance of NCM were systematically analyzed.Finally,the development and future challenges of NCM are prospected,which is expected to provide an important reference for the application of NCM.

Key words: Ni?rich, Ternary cathode material, Doping strategy, Lithium battery

中图分类号:

TQ152

温涛, 李小成, 凡纪鹏, 邓一坤, 邹菁, 王海涛. 高镍锂离子电池三元正极材料的掺杂改性研究进展[J]. 石油化工高等学校学报, 2025, 38(3): 20-31.

Tao WEN, Xiaocheng LI, Jipeng FAN, Yikun DENG, Jing ZOU, Haitao WANG. Research Progress on Doping Modification of Ternary Cathode Materials for Nickel⁃Rich Lithium Ion Batteries[J]. Journal of Petrochemical Universities, 2025, 38(3): 20-31.

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链接本文: https://journal.lnpu.edu.cn/syhg/CN/10.12422/j.issn.1006-396X.2025.03.003

https://journal.lnpu.edu.cn/syhg/CN/Y2025/V38/I3/20

图/表 11

图1 草酸盐前驱体和NCM-622粉末在不同温度下烧结产物的SEM[16]

Fig.1 SEM images of the oxalate precursor and NCM-622 powders sintered at different temperatures[16]

图2 正极样品的大范围XRD图谱、具有R-3m空间群的层状正极材料的晶体结构及正极样品的(003)和(104)面精细扫描XRD[20]

Fig.2 Wide-range XRD patterns of the cathode samples and crystal structure of a layered cathode material with anR-3m space group and fine-scan XRD patterns in the (003) and (104) planes of the cathode samples[20]

图3 含锂前驱体和NCM811正极材料的合成路线[24]

Fig.3 Synthetical routes of the Li-contained precursors and NCM811 cathode materials[24]

图4 不同温度下烧结LiNi0.6Co0.2Mn0.2O2的SEM[25]

Fig.4 SEM of LiNi0.6Co0.2Mn0.2O2 at differenttemperatures[25]

图5 FCG@TiO2-x 微球合成路线示意图及循环200次后微观形貌[31]

Fig.5 Schematic illustration of the synthetic route to FCG@TiO2-x and microspheres micro-topography after 200 cycles[31]

图6 LiNi0.6Co0.2Mn0.2O2和LiNi0.55Co0.2Mn0.2Zr0.05O2的PDOS投影图[37]

Fig.6 Schematic projected density of states (PDOS) for LiNi0.6Co0.2Mn0.2O2 and LiNi0.55Co0.2Mn0.2Zr0.05O2[37]

图7 Nb掺杂NCM811的粒子掺杂策略示意图[39]

Fig.7 Schematic diagram of the proposed doping strategy of Nb-doped NCM811 particles[39]

图8 不同循环次数下Ta-0和Ta-0.25%的EIS图[43]

Fig.8 EIS plots of Ta-0 and Ta-0.25% after different cycles[43]

图9 样品在2.8~4.3 V、恒流密度下的初始充放电曲线和循环性能[52]

Fig.9 Initial charge/discharge curves and cycle performance of the samples at a constant current density of 2.8~4.3 V[52]

图10 充放电循环过程中B掺杂对NCM90正极机械稳定性影响的示意图[66]

Fig.10 Schematic illustration of the effect of boron-doping on the NCM90 cathode's mechanical stability during charge and discharge cycling[66]

表1 元素掺杂的作用效果以及作用机理

Table 1 The effect and mechanism of element doping

掺杂元素	放电容量/（mA·h·g^-1)		循环性能		作用机理	文献
掺杂元素	初始样	改性样	初始样	改性样	作用机理	文献
Ti	188.0(0.5 C)	196.0(0.5 C)	循环100次后容量保持率为70.0%(1.0 C)	循环100次后容量保持率为84.0%(1.0 C)	Ti⁴⁺为NMC811晶格稳定性提供了额外的支持	[28]
Zr	178.3(2.0 C)	189.4(2.0 C)	循环200次后容量保持率为77.8%(1.0 C)	循环200次后容量保持率为79.5%(1.0 C)	Zr⁴⁺的加入使NMC811的结构稳定，内应力降低，保持颗粒结构的相对完整性	[31]
Nb	148.8(1.0 C)	181.6(1.0 C)	循环100次后容量保持率为81.8%(1.0 C)	循环100次后容量保持率为94.6%(1.0 C)	Nb修饰的固体边界表面足以抵抗HF和有害物质对活性物质的毒性作用，减少极化现象	[39]
Na	173.0(0.1 C)	186.0(0.1 C)	循环100次后容量保持率为83.7%(1.0 C)	循环100次后容量保持率为93.5%(1.0 C)	Na⁺的掺杂减少了阳离子的混合，同时稳定了层间结构	[52]
Mg	148.0(0.5 C)	155.0(0.5 C)	循环30次后容量保持率为90.7%(0.5 C)	循环30次后容量保持率为95.8%(0.5 C)	Mg取代Co提高了Li⁺的扩散速率	[58]
B	230.0(0.1 C)	237.0(0.1 C)	循环100次后容量保持率为76.0%(0.1 C)	循环100次后容量保持率为91.0%(0.1 C)	硼离子对可以部分缓解NCM90正极深度充电过程中产生的固有内部应变	[66]
F	179.0(0.5 C)	201.0(0.5 C)	循环50次后容量保持率为63.0%(0.5 C)	循环50次后容量保持率为88.0%(0.5 C)	用F^-取代氧可以在过渡金属和F之间产生较强的键，使晶格参数c增大	[73]

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