Li-Ni共掺尖晶石型LiMn<sub>2</sub>O<sub>4</sub>单晶多面体材料的制备及电化学性能

李萌; 刘红雷; 郭俊明; 向明武; 刘晓芳; 白红丽; 白玮

doi:10.13801/j.cnki.fhclxb.20201215.002

Li-Ni共掺尖晶石型LiMn₂O₄单晶多面体材料的制备及电化学性能

doi: 10.13801/j.cnki.fhclxb.20201215.002

云南民族大学　化学与环境学院，昆明 650500

基金项目: 国家自然科学基金(51972282；U1602273)；云南省基础研究计划项目青年项目(202001AU070008)

详细信息

通讯作者:
郭俊明，硕士，教授，博士生导师，研究方向为锂离子电池正极材料　E-mail：guojunming@tsinghua.org.cn

中图分类号: TM912
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出版历程
- 收稿日期: 2020-10-30
- 录用日期: 2020-12-10
- 网络出版日期: 2020-12-15
- 刊出日期: 2021-10-01

Preparation and electrochemical properties of Li-Ni co-doping spinel LiMn₂O₄ single crystal polyhedron material

School of Chemistry and Environment, Yunnan Minzu University, Kunming 650500, China

摘要

摘要: 采用无焰燃烧法在500℃反应3 h，然后分别在600、650、700和750℃二次焙烧6 h制备了尖晶石型Li_1.02Ni_0.05Mn_1.93O₄正极材料。结果表明，不同焙烧温度制备的Li-Ni共掺材料没有改变LiMn₂O₄的立方尖晶石结构，且随着焙烧温度的升高，颗粒尺寸变大，结晶性提高。二次焙烧温度为700℃的Li_1.02Ni_0.05Mn_1.93O₄单晶多面体晶粒正极材料具有{111}、{110}和{100}面，且电化学性能较优，在1 C倍率下初始放电比容量为108.2 mA·h·g⁻¹，循环500次后的容量保持率为76.8%；在5 C下首次放电比容量可达到99.0 mA·h·g⁻¹，1000次循环后，仍能维持72.1%的容量保持率；在10 C下仍显示出71.3 mA·h·g⁻¹的首次放电比容量及经500次循环后86.4%的容量保持率。并且其具有较大的Li⁺扩散系数和较小的表观活化能。Li-Ni共掺LiMn₂O₄单晶多面体材料能够有效抑制Jahn-Teller效应，减小Mn的溶解及增加Li⁺扩散通道，使材料的晶体结构稳定，提高倍率性能和循环性能。
- 尖晶石型LiMn₂O₄ /
- Li-Ni共掺 /
- 单晶多面体 /
- 无焰燃烧法 /
- 焙烧温度 /
- 正极材料 /
- 锂离子电池
Abstract: Spinel Li_1.02Ni_0.05Mn_1.93O₄ cathode material was synthesized via a flameless combustion method at 500℃ for 3 h followed by calcination at 600、650、700 and 750℃ for 6 h, respectively. The results show that Li-Ni co-doping material at different calcination temperatures does not change the cubic spinel structure of LiMn₂O₄. With the increase of calcination temperature, the particle size increases and the crystallinity is enhanced. At the secondary calcination temperature of 700℃, the cathode material of Li_1.02Ni_0.05Mn_1.93O₄ single crystal polyhedron possess {111}, {110} and {100} surfaces. It exhibits an excellent electrochemical performance. The Li_1.02Ni_0.05Mn_1.93O₄ cathode material shows the first-discharge specific capacity of 108.2 mA·h·g⁻¹ and maintains the capacity retention of 76.8% after 500 cycles at 1 C. Moreover, it displays an initial discharge capacity of 99.0 and 71.3 mA·h·g⁻¹, while provides a capacity retention rate of 72.1 and 86.4% after 1000 cycles at 5 C and 500 cycles at 10 C, respectively. The optimized electrode has a large Li⁺ diffusion coefficient and low apparent activation energy. The Li-Ni co-doping material of LiMn₂O₄ single crystal polyhedron can inhibit the Jahn-Teller effect effectively and alleviate Mn dissolution as well as increase Li⁺ ions expressing channels. Hence, the crystal structure of material is stabilized, the rate and cycle performance are enhanced.
- spinel LiMn₂O₄ /
- Li-Ni co-doping /
- single crystal polyhedron /
- flameless combustion method /
- calcination temperature /
- cathode material /
- lithium-ion battery

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图 1 不同二次焙烧温度Li_1.02Ni_0.05Mn_1.93O₄-x样品的XRD图谱

Figure 1. XRD patterns of samples Li_1.02Ni_0.05Mn_1.93O₄-x at different secondary calcination temperatures(a. Li_1.02Ni_0.05Mn_1.93O₄-600; b. Li_1.02Ni_0.05Mn_1.93O₄-650; c. Li_1.02Ni_0.05Mn_1.93O₄-700; d. Li_1.02Ni_0.05Mn_1.93O₄-750)

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图 2 Li_1.02Ni_0.05Mn_1.93O₄-x样品的SEM图像：(a) 500℃燃烧反应3 h产物；(b) Li_1.02Ni_0.05Mn_1.93O₄-600；(c) Li_1.02Ni_0.05Mn_1.93O₄-650；(d) Li_1.02Ni_0.05Mn_1.93O₄-700；(e) Li_1.02Ni_0.05Mn_1.93O₄-750；(f) 八面体及多面体示意图

Figure 2. SEM images of Li_1.02Ni_0.05Mn_1.93O₄-x: (a) Combustion at 500℃ for 3 h; (b) Li_1.02Ni_0.05Mn_1.93O₄-600; (c) Li_1.02Ni_0.05Mn_1.93O₄-650; (d) Li_1.02Ni_0.05Mn_1.93O₄-700; (e) Li_1.02Ni_0.05Mn_1.93O₄-750; (f) Schematic diagram of octahedron and polyhedron

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图 3 Li_1.02Ni_0.05Mn_1.93O₄-700样品的XPS图谱((a) 全图谱；(b) Mn 2p_3/2拟合图谱；(c) Ni 2p图谱)

Figure 3. XPS spectra of Li_1.02Ni_0.05Mn_1.93O₄-700((a) Survey; (b) Mn 2p_3/2; (c) Ni 2p)

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图 4 不同二次焙烧温度Li_1.02Ni_0.05Mn_1.93O₄-x样品1 C首次充放电曲线 (a) 、1 C循环性能图(b)、5 C循环性能图(c)、10 C循环性能图 (d)

Figure 4. Different secondary calcination temperatures of Li_1.02Ni_0.05Mn_1.93O₄-x: initial charge-discharge curves at 1 C (a), cycle performances diagrams at 1 C (b), 5 C (c) and 10 C (d)

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图 5 不同二次焙烧温度Li_1.02Ni_0.05Mn_1.93O₄-x样品的倍率性能

Figure 5. Rate capability of Li_1.02Ni_0.05Mn_1.93O₄-x at different secondary calcination temperatures

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图 6 不同二次焙烧温度Li_1.02Ni_0.05Mn_1.93O₄-x样品的CV曲线

Figure 6. CV curves of Li_1.02Ni_0.05Mn_1.93O₄-x at different secondary calcination temperatures

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图 7 不同二次焙烧温度Li_1.02Ni_0.05Mn_1.93O₄−x样品：(a) 循环前EIS图；(b) 1 C循环500次的EIS图；(c) 实部阻抗Z'与ω^−1/2的关系

Figure 7. Nyquist plots of Li_1.02Ni_0.05Mn_1.93O₄−x at different secondary calcination temperatures: (a) Before cycles at 1 C; (b) After 500 cycles at 1 C; (c) Relationship of real impedance Z' vs. ω^−1/2

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图 8 不同二次焙烧温度Li_1.02Ni_0.05Mn_1.93O₄-x样品在不同温度下的EIS图(插图为相应曲线的lgi₀与1000 T⁻¹的Arrhenius关系)

Figure 8. Nyquist plots of Li_1.02Ni_0.05Mn_1.93O₄-x at different secondary calcination temperatures at different temperatures (Insets are the Arrhenius plots of lgi₀ vs. 1000 T⁻¹)

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表 1 样品的命名

Table 1. Naming of samples

Sample	Secondary calcination temperature/℃
Li_1.02Ni_0.05Mn_1.93O₄-600	600
Li_1.02Ni_0.05Mn_1.93O₄-650	650
Li_1.02Ni_0.05Mn_1.93O₄-700	700
Li_1.02Ni_0.05Mn_1.93O₄-750	750

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表 2 不同二次焙烧温度Li_1.02Ni_0.05Mn_1.93O₄-x样品在循环前和500次循环后的电荷转移阻抗R_ct

Table 2. Charge transfer impedance R_ct of Li_1.02Ni_0.05Mn_1.93O₄-x at different secondary calcination temperatures before and after 500 cycles

Sample	Before cycles		After 500 cycles
Sample	R_s/Ω	R_ct/Ω	R_s/Ω	R_ct/Ω
Li_1.02Ni_0.05Mn_1.93O₄-600	4.02	184.98	7.31	260.69
Li_1.02Ni_0.05Mn_1.93O₄-650	2.78	178.22	10.40	242.60
Li_1.02Ni_0.05Mn_1.93O₄-700	2.63	160.37	7.92	225.08
Li_1.02Ni_0.05Mn_1.93O₄-750	3.18	229.82	14.70	331.30
Note: R_s—Electrolyte impedanc.

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