非水系溶剂溶胶-凝胶法制备高性能LiNi0.8Co0.15Al0.05O2正极材料

doi:10.15541/jim20140579

摘要/Abstract

摘要：

采用溶胶-凝胶法制备锂离子电池正极材料LiNi_0.8Co_0.15Al_0.05O₂, 溶剂分别采用水、乙醇、乙二醇和丙三醇。通过TG/DSC进行样品的热性能分析, 确定样品的烧结条件为550℃预处理6 h, 750℃烧结24 h。XRD分析结果显示, 采用有机溶剂制备的样品, 018/110峰分裂明显, 但向小角度偏移, 说明样品的晶间距增大。SEM结果表明, 采用有机溶剂制备的样品, 平均颗粒尺寸0.4 μm, 小于采用水溶剂制备的样品颗粒尺寸0.5 μm。采用乙醇与乙二醇为溶剂制备的样品出现了部分大尺寸的单晶颗粒。电化学性能测试结果表明, 采用有机溶剂制备的样品的充放电性能要低于水作为溶剂的样品性能, 但是采用乙醇作为溶剂制备的样品, 首次放电容量(197.33 mAh/g)与水作为溶剂(200.66 mAh/g)制备的样品相当, 并且在1C倍率下50次循环, 容量保持率由水溶剂制备样品的87.1%增大至94.4%。大尺寸单晶颗粒的存在有利于NCA材料循环性能的提高。

关键词: 乙醇, 溶胶-凝胶, 有机溶剂, 单晶

Abstract:

Lithium ion battery cathode material LiNi_0.8Co_0.15Al_0.05O₂ was prepared by Sol-Gel, respectively, using water, ethanol, ethylene glycol, glycerol as a solvents. Through TG / DSC analysis of the thermodynamic properties, the sintered condition of the sample was selected as pre-treatment at 550℃for 6 h and then ??sintering at 750℃ for 24 h. XRD patterns show that the 018/110 peak of the samples prepared by organic solvent is splitted obviously, but the peak shifts to a small angle, which indicates that the lattice spacing increases. SEM results show that the average particle size of the samples prepared by organic solvent is 0.4 μm, which is smaller than that of the sample (0.5 μm) prepared by using water. Some of the single crystals present in the sample prepared by using ethanol and ethylene glycol as solvent. The electrochemical performance test results show that the charge-discharge performance of samples prepared in the organic solvent is lower than that of the sample prepared in the water. However, the initial discharge capacity (197.33 mAh/g) of the samples prepared using ethanol as a solvent (200.66 mAh/g) is closed to that of the sample prepared by using water as solvent, and cycle performance has greatly improved at 1C rate. After 50 cycles at 1C rate, the capacity retention rate of the sample prepared by using water is increased from 87.1% to 94.4% as compared with the sample prepared by using ethanol. The presence of large crystal particle is beneficial to improve the cycle performance of the NCA material.

Key words: ethanol, Sol-Gel, organic solvent, single crystal

中图分类号:

TQ174

夏书标, 张英杰, 董鹏, 徐明丽, 姚遥. 非水系溶剂溶胶-凝胶法制备高性能LiNi_0.8Co_0.15Al_0.05O₂正极材料[J]. 无机材料学报, 2015, 30(7): 732-738.

XIA Shu-Biao, ZHANG Ying-Jie, DONG Peng, XU Ming-Li, YAO Yao. High-performance LiNi_0.8Co_0.15Al_0.05O₂ Cathode Material Prepared by Sol-Gel Method in Non-aqueous Solvent[J]. Journal of Inorganic Materials, 2015, 30(7): 732-738.

图/表 9

表1 几种溶剂的物理性能[13]

Table 1 Physical properties of several solvents[13]

	Ethanol	Ethylene glycol	Glycerol	Water
Molecular formula	C₂H₆O	C₂H₆O₂	C₃H₈O₃	H₂O
Structural formula	CH₃CH₂-OH	HO-CH₂CH₂-OH	HOCH₂-CHOH-CH₂OH	H-O-H
Viscosity (20℃)/(mPa·s)	1.21	22.15	1412.00	1.01
Relative density(20℃, H₂O)	0.79	1.12	1.26	1.00

图1 采用乙醇为溶剂制备所得正极材料的热性能分析

Fig. 1 Thermal property analyses of cathode materials prepared using by ethanol as solvent

图2 不同溶剂制备所得NCA材料的XRD图谱

Fig. 2 XRD patterns of NCA material prepared by using different solvents

表2 不同溶剂制备所得NCA材料的晶格参数

Table 2 Lattice parameters of NCA material prepared by using different solvents

	a/nm	c/nm	c/a	I₀₀₃/I₁₀₄	V/nm³
H₂O	0.28653	1.41835	4.944	1.845	0.10084
Ethanol	0.28648	1.41726	4.947	1. 669	0.10073
Ethylene glycol	0.28652	1.41820	4.950	1. 712	0.10083
Glycerol	0.28634	1.41755	4.950	1. 783	0.10063

图3 采用不同溶剂制备NCA材料的SEM照片

Fig. 3 SEM images of NCA material prepared by using different solvents (a) H2O; (b) Ethanol; (c) Ethylene glycol: (d) Glycerol

图4 几种溶剂对阳离子吸引力示意图

Fig. 4 Schematic of several solvents on cation attractive

图5 不同溶剂制备所得NCA材料的CV曲线图

Fig. 5 CV performance of NCA material prepared by using different solvents

图6 不同溶剂制备所得NCA材料的首次充放电曲线图

Fig. 6 Initial charge-discharge curves of NCA material prepared by using different solvents

图7 不同溶剂制备所得NCA材料的循环性能

Fig. 7 Cycle capability of NCA material prepared by using different solvents

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非水系溶剂溶胶-凝胶法制备高性能LiNi_0.8Co_0.15Al_0.05O₂正极材料

High-performance LiNi_0.8Co_0.15Al_0.05O₂ Cathode Material Prepared by Sol-Gel Method in Non-aqueous Solvent

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