Mg-Cr共掺LiNi0.5Mn1.5O4包覆LiNi0.8Co0.1Mn0.1O2锂离子电池正极材料

doi:10.15541/jim20250320

摘要/Abstract

摘要：

LiNi_0.8Co_0.1Mn_0.1O₂(NCM811)因其高理论比容量, 已成为动力电池领域中重要的正极材料之一。然而, 当充电电压超过4.3 V时, 材料易发生结构相变并与电解液产生剧烈界面副反应, 导致界面阻抗增大和容量快速衰减, 制约其能量密度进一步提升。本研究提出一种协同改性策略, 在采用同步锂化工艺的同时, 制备Mg-Cr共掺杂的LiNi_0.5Mn_1.5O₄(LNMO)包覆层。该包覆层继承了LNMO的高工作电压、三维锂离子传输通道以及良好的电化学稳定性, 同时Mg-Cr共掺杂提高了LNMO的离子/电子电导率并抑制了Mn元素的溶解。结果表明, Mg-Cr共掺杂LNMO包覆改性降低了NCM811正极材料中Li⁺/Ni²⁺阳离子混排程度, 改性后正极材料在2.7~4.5 V电压区间表现出优异性能, 在0.1C (1C=200 mA·g^-1)下的首圈放电比容量达到212.74 mAh·g^-1, 5C高倍率下的放电比容量达到182.32 mAh·g^-1, 1C倍率下循环100圈后容量保持率为77.09%, 性能显著优于未改性及分步包覆样品。该策略通过抑制界面副反应、降低电荷转移电阻, 提升了NCM811的稳定性与电化学性能, 为高电压高镍正极材料优化提供了有效途径。

关键词: NCM811, LNMO包覆, Mg-Cr共掺杂, 同步锂化

Abstract:

LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) emerged as one of the crucial cathode materials in the field of power batteries owing to its high theoretical specific capacity. However, when the charging voltage exceeds 4.3 V, the material is prone to structural phase transitions and severe interfacial side reactions with the electrolyte, leading to increased interfacial impedance and rapid capacity fading, which restricts the further improvement of its energy density. In this study, a synergistic modification strategy is proposed: a synchronous lithiation process is adopted to prepare Mg-Cr co-doped LiNi_0.5Mn_1.5O₄ (LNMO) as the coating layer. This coating layer inherits the high operating voltage, three-dimensional lithium ion transport channels, and excellent electrochemical stability of LNMO. Meanwhile, Mg-Cr co-doping enhances the ionic/electronic conductivity of LNMO and inhibits the dissolution of Mn elements. The results demonstrate that the Mg-Cr co-doped LNMO coating modification reduces the degree of Li⁺/Ni²⁺ cation mixing in the NCM811 cathode material. The modified cathode material exhibits outstanding performance in the voltage range of 2.7-4.5 V. It delivers an initial discharge specific capacity of 212.74 mAh·g^-1 at 0.1C (1C= 200 mA·g^-1), a discharge specific capacity of 182.32 mAh·g^-1 at a high rate of 5C, and a capacity retention rate of 77.09% after 100 cycles at 1C. Its electrochemical performance is significantly superior to that of the unmodified and stepwise-coated samples. This strategy improves the stability and electrochemical performance of NCM811 by suppressing interfacial side reactions and reducing charge transfer resistance, thereby providing an effective approach for the optimization of high-voltage and high-nickel cathodes.

Key words: NCM811, LNMO coating, Mg-Cr co-doping, synchronous lithiation

中图分类号:

O646

刘博宇, 王腾飞, 庞青, 李秀芬, 望红玉. Mg-Cr共掺LiNi_0.5Mn_1.5O₄包覆LiNi_0.8Co_0.1Mn_0.1O₂锂离子电池正极材料[J]. 无机材料学报, 2026, 41(8): 1069-1077.

LIU Boyu, WANG Tengfei, PANG Qing, LI Xiufen, WANG Hongyu. LiNi_0.8Co_0.1Mn_0.1O₂ Coated with Mg-Cr Co-doped LiNi_0.5Mn_1.5O₄ as Cathode Material for Li-ion Battery[J]. Journal of Inorganic Materials, 2026, 41(8): 1069-1077.

图/表 12

图1 同步锂化与分步包覆工艺流程图

Fig. 1 Process flow diagram of synchronous lithiation and stepwise coating

图2 NCM811、NCM811-LNMO和NCM811-LNMO-Mg-Cr的XRD图谱

Fig. 2 XRD patterns of NCM811, NCM811-LNMO and NCM811-LNMO-Mg-Cr

图3 (a, b) NCM811、(c, d) NCM811-LNMO和(e, f) NCM811- LNMO-Mg-Cr的SEM照片; (g) NCM811-LNMO-Mg-Cr的EDS元素分布图

Fig. 3 (a-f) SEM images of (a, b) NCM811, (c, d) NCM811- LNMO and (e, f) NCM811-LNMO-Mg-Cr; (g) EDS elemental mappings of NCM811-LNMO-Mg-Cr

图4 (a, b) NCM811-LNMO和(c, d) NCM811-LNMO-Mg-Cr的(a, c) TEM和(b, d) HRTEM照片

Fig. 4 (a, c) TEM and (b, d) HRTEM images of (a, b) NCM811-LNMO and (c, d) NCM811-LNMO-Mg-Cr

图5 (a) NCM811、(b) NCM811-LNMO和(c) NCM811-LNMO-Mg-Cr的(a~c) Ni2p XPS谱图和(d) Ni2+/Ni3+占比; (e, f) NCM811-LNMO-Mg-Cr的(e) Cr2p和(f) Mg1s XPS谱图

Fig. 5 (a-c) Ni2p XPS spectra and (d) Ni2+/Ni3+ ratios of (a) NCM811, (b) NCM811-LNMO and (c) NCM811-LNMO-Mg-Cr; (e) Cr2p and (f) Mg1s XPS spectra of NCM811-LNMO-Mg-Cr Colorful figures are available on website

图6 NCM811、NCM811-LNMO和NCM811-LNMO-Mg-Cr电池的电化学性能

Fig. 6 Electrochemical performances of NCM811, NCM811-LNMO and NCM811-LNMO-Mg-Cr cells (a) Charge-discharge curves; (b) Rate capability; (c) Lithium ion diffusion coefficient; (d) Cycling performance Colorful figures are available on website

图7 (a, b) 100圈循环(a)前、(b)后NCM811、NCM811-LNMO和NCM811-LNMO-Mg-Cr电池的EIS谱图; (c) NCM811和(d) NCM811-LNMO-Mg-Cr电池的dQ/dV曲线

Fig. 7 (a, b) EIS spectra of NCM811, NCM811-LNMO and NCM811-LNMO-Mg-Cr cells (a) before and (b) after 100 cycling; (c, d) dQ/dV curves of (c) NCM811 and (d) NCM811-LNMO-Mg-Cr cells Colorful figures are available on website

图8 100圈循环后NCM811、NCM811-LNMO和NCM811- LNMO-Mg-Cr的XRD谱图

Fig. 8 XRD patterns of NCM811, NCM811-LNMO and NCM811-LNMO-Mg-Cr after 100 cycling

图9 100圈循环后(a, b) NCM811、(c, d) NCM811-LNMO和(e, f) NCM811-LNMO-Mg-Cr的SEM照片

Fig. 9 SEM images of (a, b) NCM811, (c, d) NCM811- LNMO and (e, f) NCM811-LNMO-Mg-Cr after 100 cycling

图S1 NCM811-LNMO-1和NCM811-LNMO-Mg-Cr-1的XRD图谱

Fig. S1 XRD patterns of NCM811-LNMO-1 and NCM811-LNMO-Mg-Cr-1

图S2 (a, b) NCM811-LNMO-1和(c, d) NCM811-LNMO-Mg-Cr-1的SEM照片; (e) NCM811-LNMO-Mg-Cr-1的EDS元素分布图

Fig. S2 (a-d) SEM images of (a, b) NCM811-LNMO-1 and (c, d) NCM811-LNMO-Mg-Cr-1; (e) EDS elemental mappings of NCM811-LNMO-Mg-Cr-1

图S3 NCM811-LNMO-1和NCM811-LNMO-Mg-Cr-1电池的电化学性能

Fig. S3 Electrochemical performances of NCM811-LNMO-1 and NCM811-LNMO-Mg-Cr-1 cells (a) Charge-discharge curves; (b) Rate capability; (c) Lithium ion diffusion coefficients; (d) Cycling performances

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Mg-Cr共掺LiNi_0.5Mn_1.5O₄包覆LiNi_0.8Co_0.1Mn_0.1O₂锂离子电池正极材料

LiNi_0.8Co_0.1Mn_0.1O₂ Coated with Mg-Cr Co-doped LiNi_0.5Mn_1.5O₄ as Cathode Material for Li-ion Battery

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