大孔高镍LiNi0.8Co0.1Mn0.1O2正极材料的制备及其电化学性能研究

doi:10.6023/A21010019

摘要/Abstract

本工作以聚甲基丙烯酸甲酯(PMMA)微球组装成的胶晶模板作为铸模, 溶胶-凝胶法辅助获得大孔LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811)正极材料. 结果表明, 利用PMMA作为造孔剂, 形成了由100 nm的颗粒堆积而成的大孔结构, 这种结构有效地提高了材料的倍率性能和循环稳定性. 大孔NCM811在0.1C的首次放电比容量为190.3 mAh∙g^-1. 2C倍率下NCM811纳米颗粒的放电比容量仅为129.3 mAh∙g^-1, 而大孔NCM811的放电比容量为149.8 mAh∙g^-1. 0.5C倍率下循环400次后大孔NCM811的容量保持率为83.02%, 明显高于纳米颗粒材料的38.59%.

关键词: 锂离子电池, 正极材料, 胶晶模板, 大孔, LiNi_0.8Co_0.1Mn_0.1O₂

High-performance rechargeable lithium-ion batteries (LIBs) have been widely applied in electrochemical energy storage fields. In recent years, Ni-rich ternary cathode materials have received considerable attention due to their low cost and high theoretical specific capacity, and they are regarded as promising candidates for the next-generation lithium-ion batteries. In this paper, macroporous Ni-rich LiNi_0.8Co_0.1Mn_0.1O₂(NCM811) cathode material has been successfully prepared by using a poly(methyl methacrylate) (PMMA) colloidal crystal template and sol-gel method. The typical experimental procedure for the synthesis of macroporous LiNi_0.8Co_0.1Mn_0.1O₂ is as follows: Firstly, a stoichiometric mixture of LiNO₃, (CH₃COO)₂Mn∙4H₂O, (CH₃COO)₂Co∙4H₂O, and (CH₃COO)₂Ni∙4H₂O were dissolved together in ethanol for 1 h. Acetylacetone was then drop by drop into the prepared solution under continuous stirring for 1.5 h (a molar ratio of acetylacetone to transition metal ions was 1∶1). Then, the LiNi_0.8Co_0.1Mn_0.1O₂sol was infiltrated completely into PMMA template under vacuum. After that, the as-prepared product was filtrated and dried at 50 ℃, followed by a heat treatment at 450 ℃ for 2 h for removing the PMMA template, and then calcined at 700 ℃ under a flowing oxygen atmosphere. These results suggest that the macroporous architecture stacked by the 100 nm particles is obtained by using the pore-forming agent PMMA, and this structure is beneficial to improve the rate capability and cycling stability of the Ni-rich cathode materials. Specifically, macroporous NCM811 delivers an initial discharge capacity of 190.3 mAh∙g^-1 between 2.7 V and 4.3 V at 0.1C rate. The discharge specific capacity of the nanoparticle NCM811 is only 129.3 mAh∙g^-1 at 2C rate, whereas the macroporous NCM811 is 149.8 mAh∙g^-1 at the same rate. In addition, macroporous NCM811 can still delivers a high discharge specific capacity of 111.7 mAh∙g^-1 at 10C rate. Macroporous NCM811 also exhibits superior capacity retention of 83.02% after 400 cycles at 0.5C rate, surpassing the 38.59% of nanoparticle NCM811 obviously. The macroporous architecture is conducive to shorten the transport distance of lithium ions and electrons, suppress the phase transition and structural deterioration resulting from the frequent Li⁺ insertion/deinsertion, reduce polarization, and thus improving the electrochemical performances, which provides new insights for the development of high-energy-density lithium-ion batteries.

Key words: lithium-ion batteries, cathode material, colloidal crystal template, macroporous, LiNi_0.8Co_0.1Mn_0.1O₂

引用此文

李童心, 李东林, 张清波, 高建行, 孔祥泽, 樊小勇, 苟蕾. 大孔高镍LiNi_0.8Co_0.1Mn_0.1O₂正极材料的制备及其电化学性能研究[J]. 化学学报, 2021, 79(5): 678-684.

Tongxin Li, Donglin Li, Qingbo Zhang, Jianhang Gao, Xiangze Kong, Xiaoyong Fan, Lei Gou. Preparation and Electrochemical Performance of Macroporous Ni-rich LiNi_0.8Co_0.1Mn_0.1O₂ Cathode Material[J]. Acta Chimica Sinica, 2021, 79(5): 678-684.

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图/表 11

图1. (a) NCM811前驱体在450 ℃热处理后的XRD图谱; (b) 纳米颗粒和大孔NCM811样品的XRD图谱; (c) 纳米颗粒和(d) 大孔NCM811样品的XRD精修结果

Figure 1. XRD patterns of (a) the precursor of NCM811 after calcination at 450 ℃ and (b) nanoparticle and macroporous NCM811 samples; XRD Rietveld refinement results of (c) nanoparticle and (d) macroporous NCM811 samples

样品	a/nm	c/nm	c/a	I₍₀₀₃₎/I₍₁₀₄₎
NCM811纳米颗粒	0.28735	1.42109	4.9455	1.227
大孔NCM811	0.28741	1.42237	4.9489	1.426

表1. 纳米颗粒和大孔NCM811样品的晶格常数

Table 1. The lattice parameters of nanoparticle and macroporous NCM811 samples

Parameter	NCM811纳米颗粒	大孔NCM811
Li1(3a)	0.9468	0.9611
Ni1(3a)	0.0532	0.0389
Li2(3b)	0.0532	0.0389
Ni2(3b)	0.7468	0.7611
Co1(3b)	0.1000	0.1000
Mn1(3b)	0.1000	0.1000
O1(6c)	1.0000	1.0000
Ni在Li位的占比/%	5.32	3.89
R_p/%	6.21	6.25
R_wp/%	7.94	7.92
χ²	1.144	1.130

表2. 纳米颗粒和大孔NCM811样品的XRD精修结果

Table 2. XRD Rietveld refinement results of nanoparticle and macroporous NCM811 samples

图2. (a, b) 纳米颗粒和(c, d) 大孔NCM811材料在不同放大倍数下的SEM图

Figure 2. SEM images of (a, b) nanoparticle and (c, d) macroporous NCM811 material at different magnifications

图3. NCM811纳米颗粒的EDS元素分布图

Figure 3. EDS elemental mapping of nanoparticle NCM811

图4. 纳米颗粒和大孔NCM811在0.1C倍率下的首次充放电曲线

Figure 4. Initial charge-discharge curves of nanoparticle and macroporous NCM811 at 0.1C

图5. (a) 倍率性能对比, (b) 纳米颗粒和(c) 大孔NCM811在不同倍率下的充放电曲线

Figure 5. (a) Rate performance comparison, charge-discharge curves of (b) nanoparticle and (c) macroporous NCM811 at different rates

图6. (a) 纳米颗粒和(b) 大孔NCM811电极的CV曲线

Figure 6. CV curves of (a) nanoparticle and (b) macroporous NCM811 electrodes

图7. (a) 0.5C倍率下的循环性能, (b) 纳米颗粒和(c) 大孔NCM811在不同循环次数下的dQ/dV曲线

Figure 7. (a) Cycling performance at 0.5C rate, dQ/dV curves of (b) nanoparticle and (c) macroporous NCM811 at different cycles

图8. 纳米颗粒和大孔NCM811电极(a) 循环115次后的电化学阻抗图谱(内嵌图为等效电路图)和(b) Z′和ω-1/2的关系曲线

Figure 8. (a) Nyquist plots after 115 cycles with an equivalent circuit (inset) and (b) the relationship plots between Z′ and ω-1/2 of nanoparticle and macroporous NCM811 electrodes

样品	Cycle	R_s/Ω	R_ct/Ω
NCM811纳米颗粒	115	2.246	66.52
大孔NCM811	115	3.621	10.94

表3. 纳米颗粒和大孔NCM811电极拟合后的阻抗参数

Table 3. Impedance parameters of the nanoparticle and macroporous NCM811 electrodes after fitting

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大孔高镍LiNi_0.8Co_0.1Mn_0.1O₂正极材料的制备及其电化学性能研究

Preparation and Electrochemical Performance of Macroporous Ni-rich LiNi_0.8Co_0.1Mn_0.1O₂ Cathode Material

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