Mg2+掺杂对富锂层状氧化物材料Li1.2Mn0.54Ni0.13Co0.13O2的影响

doi:10.12422/j.issn.1672-6952.2024.02.004

摘要/Abstract

摘要：

Mg²⁺作为一种电化学惰性的阳离子，由于其离子半径(0.072 nm)与Li⁺的离子半径（0.076 nm）相近，因此被广泛应用于取代富锂层状氧化物(LLOs)材料中Li⁺的位置。然而，Mg²⁺对LLOs材料晶体结构的影响还存在争议。利用溶胶凝胶法成功制备了一系列Mg²⁺掺杂富锂正极材料Li_1.2-_x Mg _x Mn_0.54Ni_0.13Co_0.13O₂，通过X射线衍射仪和X射线光电子能谱等对其晶体结构和元素价态进行了系统的研究。结果表明，Mg²⁺掺杂导致LLOs材料晶胞参数的增加。通过与Li_1.2Mn_0.54Ni_0.13Co_0.13O₂材料的电化学性能对比发现，Mg²⁺掺杂有效地提高了LLOs材料的电化学性能。经过优化后，Mg?0.03样品展现出最优异的电化学性能，在0.1 C倍率下的初始放电比容量为291.9 mA?h/g，首圈库伦效率为78.40%。

关键词: 锂离子电池, 富锂层状氧化物, 正极材料, 溶胶凝胶法, Mg²⁺掺杂

Abstract:

As an electrochemical inert cation, Mg²⁺ has an ionic radius (0.072 nm) similar to that of Li⁺ (0.076 nm), which is widely used to replace Li⁺ in Li?rich layered oxides (LLOs) materials. However, the influence of Mg²⁺ on the crystal structure of LLOs materials is still controversial. In this work, the Mg?doped Li?rich cathode materials Li_1.2-_x Mg _x Mn_0.54Ni_0.13Co_0.13O₂ were synthesized by a sol?gel and high?temperature calcination method. The crystal structure, and valence state of elements in synthesized materials were systematically studied via X?ray diffraction, and X?ray photoelectron spectroscopy. These results indicated that Mg²⁺ doping can increase the cell parameters of LLOs materials. At the same time, compared with Li_1.2Mn_0.54Ni_0.13Co_0.13O₂, Mg?doping can effectively improve the electrochemical performance of LLOs materials. After optimization, the Mg?0.03 sample exhibits anomalous electrochemical performance, that is, the initial discharge?specific capacity is 291.9 mA?h/g and the initial coulomb efficiency is 78.40%.

Key words: Lithium?ion battery, Li?rich layered oxides, Cathode materials, Sol?gel method, Mg²⁺ doping

中图分类号:

TQ131.11

解自奇, 谭玉婷, 赵妮, 周明东, 颜文超. Mg²⁺掺杂对富锂层状氧化物材料Li_1.2Mn_0.54Ni_0.13Co_0.13O₂的影响[J]. 辽宁石油化工大学学报, 2024, 44(2): 22-28.

Ziqi XIE, Yuting TAN, Ni ZHAO, Mingdong ZHOU, Wenchao YAN. Effect of Mg²⁺ Doping on Li⁃Rich Layered Oxides Materials Li_1.2Mn_0.54Ni_0.13Co_0.13O₂[J]. Journal of Liaoning Petrochemical University, 2024, 44(2): 22-28.

图/表 11

表1 样品的ICP?OES分析结果

Table 1 ICP?OES results of as?prepared samples

样品	w/%
样品	Li	Mg	Ni	Co	Mn
Mg⁃0	1.201 9	0	0.131 5	0.129 9	0.540 4
Mg⁃0.01	1.190 7	0.009 9	0.128 8	0.130 5	0.542 8
Mg⁃0.03	1.168 7	0.029 6	0.130 9	0.128 1	0.539 6
Mg⁃0.05	1.149 4	0.050 5	0.129 4	0.127 9	0.542 2

图1 样品粉末的XRD谱图

Fig.1 Powder XRD patterns of the samples

表2 样品的晶胞参数

Table 2 The lattice parameters of the as?papered samples

样品	a/nm	c/nm	c/a	V/nm³
Mg⁃0	0.284 79	1.420 61	4.988 27	0.099 79
Mg⁃0.01	0.284 87	1.421 09	4.988 56	0.099 88
Mg⁃0.03	0.284 98	1.421 77	4.989 02	0.100 01
Mg⁃0.05	0.285 09	1.422 94	4.991 20	0.100 17

图2 样品的SEM图

Fig.2 SEM images of as-samples

图3 样品的XPS图谱

Fig.3 XPS survey spectra for as-prepared materials

图4 样品的电化学性能

Fig.4 The electrochemical performance of as?prepared materials

图5 样品的倍率性能和循环性能

Fig.5 The rate performance and the cycle performance of as?prepared materials

图6 样品的平均放电中压和能量密度

Fig.6 Average discharge potential and energy density of as?prepared samples

图7 Mg?0样品和Mg?0.03样品的放电微分曲线

Fig.7 The differential capacity (dQ/dU) plots of the Mg?0 sample and the Mg?0.03 sample

图8 样品的奈奎斯特图

Fig.8 Nyquist plots of samples

表3 样品奈奎斯特图等效电路拟合结果

Table 3 Fitting result of the equivalent circuit from Nyquist profiles for samples

样品	R_e/Ω		R_ct/Ω
样品	第2圈	第200圈	第2圈	第200圈
Mg⁃0	1.2	4.0	240.0	368.1
Mg⁃0.01	1.3	3.4	93.7	145.2
Mg⁃0.03	1.8	3.5	48.5	85.4
Mg⁃0.05	3.4	5.1	120.4	285.2

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Mg²⁺掺杂对富锂层状氧化物材料Li_1.2Mn_0.54Ni_0.13Co_0.13O₂的影响

Effect of Mg²⁺ Doping on Li⁃Rich Layered Oxides Materials Li_1.2Mn_0.54Ni_0.13Co_0.13O₂

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