三元前驱体微观形貌结构对LiNi0.85Co0.10Mn0.05O2正极材料性能的影响

doi:10.19799/j.cnki.2095-4239.2019.0291

储能科学与技术 ›› 2020, Vol. 9 ›› Issue (2): 409-414.doi: 10.19799/j.cnki.2095-4239.2019.0291

• 庆祝陈立泉院士八十寿辰专刊 • 上一篇下一篇

三元前驱体微观形貌结构对LiNi_0.85Co_0.10Mn_0.05O₂正极材料性能的影响

陈龙, 张二冬, 李道聪, 杨茂萍, 夏昕()

合肥国轩高科动力能源有限公司工程研究总院，安徽合肥 230012

收稿日期:2019-12-27 修回日期:2020-02-10 出版日期:2020-03-05 发布日期:2020-03-15
通讯作者: 夏昕 E-mail:xiaxin@gotion.com.cn
作者简介:陈龙（1988—），男，博士，工程师，研究方向为锂离子动力电池、三元正极材料及前驱体，E-mail：chenlong@gotion.com.cn；
基金资助:
国家重点研发计划项目(2016YFB0100301)

Effect of precursor microstructure on the performance of LiNi_0.85Co_0.10Mn_0.05O₂ cathode materials

CHEN Long, ZHANG Erdong, IQBAL Azhar, LI Daocong, YANG Maoping, XIA Xin()

Institute of Engineering Research, Hefei Guoxuan High-Tech Power Energy Co. , Ltd. , Hefei 230012, Anhui, China

Received:2019-12-27 Revised:2020-02-10 Online:2020-03-05 Published:2020-03-15
Contact: Xin XIA E-mail:xiaxin@gotion.com.cn

摘要/Abstract

摘要：

通过调节共沉淀制备过程中氨水浓度和pH值控制三元前驱体的成核与长大过程，制备得到团聚态和均一态两种微观结构的Ni_0.85Co_0.10Mn_0.05(OH)₂前驱体。两种前驱体的粒度分布，比表面，振实等理化指标接近。烧结后制备LiNi_0.85Co_0.10Mn_0.05O₂三元正极材料测试电化学性能表明，两种正极的克容量及倍率性能相近，但具有均一态结构的正极材料1C循环50周后容量保持率达到98.3%，高于团聚态结构正极材料的96.9%循环保持率。dQ ·dV ^-1分析表明，具有均一态结构的正极材料循环前后的氧化还原峰位置和压差稳定，显示了较小的极化损失。进一步通过SEM表征，循环前后具有均一态结构的正极材料断面密实，显示出较高的机械强度，因此在充放电循环过程中颗粒无明显破碎，有较稳定的电极/电解液界面，可改善循环性能。

关键词: 锂离子电池, 正极前驱体, 二次球形貌, LiNi_0.85Co_0.10Mn_0.05O₂

Abstract:

In this work, the nucleation and crystal growth processes of the precursor can be controlled by adjusting the ammonia concentration and pH value during the co-precipitation processes, and two types of high-nickel Ni_0.85Co_0.10Mn_0.05(OH)₂ precursors with different particle structures (agglomerated vs. uniform) are synthesized. The as-synthesized precursors show almost similar physical and chemical properties. After sintering process, the obtained LiNi_0.85Co_0.10Mn_0.05O₂ cathodes also showed similar initial charge/discharge capacities and rate performance. However, LiNi_0.85Co_0.10Mn_0.05O₂ cathode resulted from the precursor with uniform structure demonstrates better cycling performance (98.3% capacity retention after 50 cycles at 1 C) than that of the cathode with agglomerated structure (96.9%). The LiNi_0.85Co_0.10Mn_0.05O₂cathode with uniform structure shows stable redox peak position and voltage interval after cycle test by dQ ·dV ^-1 analysis, which indicated the lower polarization loss. Further SEM characterization also revealed the suppression of the microcracks that maintain the mechanical integrity of the particles throughout the cycling process along with the establishment of a stable electrode/electrolyte interface to improved cycling stability.

Key words: lithium ion battery, cathode precursors, secondary particle microstructure, LiNi_0.85Co_0.10Mn_0.05O₂

中图分类号:

TM 912

陈龙, 张二冬, 李道聪, 杨茂萍, 夏昕. 三元前驱体微观形貌结构对LiNi_0.85Co_0.10Mn_0.05O₂正极材料性能的影响[J]. 储能科学与技术, 2020, 9(2): 409-414.

CHEN Long, ZHANG Erdong, IQBAL Azhar, LI Daocong, YANG Maoping, XIA Xin. Effect of precursor microstructure on the performance of LiNi_0.85Co_0.10Mn_0.05O₂ cathode materials[J]. Energy Storage Science and Technology, 2020, 9(2): 409-414.

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参考文献 14

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理化指标			典型值	B1	B2
物理指标	PSD/μm	Dmin	≥3.0	4.6	5.1
		D10	6.0~8.0	7.6	7.4
		D50	9.8~11.0	10.5	10.8
		D90	13.0~17.0	14.4	14.7
		Dmax	≤24	19.5	20.2
	比表面/m².g^-1		6±1.5	5.3	5.1
	振实密度/g·cc^-1		≥2.1	2.1	2.2
	水分/μg.g^-1		≤5000	3400	3800
化学指标	主元素质量含量	Ni/%	52.5±1	52.8	52.6
		Co/%	6.2±0.4	6.4	6.3
		Mn/%	2.8±0.3	2.9	2.8
	杂质含量	Ca/μg.g^-1	≤80	37	53
		Na/μg.g^-1	≤300	140	110
		Mg/μg.g^-1	≤100	46	37
		Cr/μg.g^-1	≤10	ND	ND
		Fe/μg.g^-1	≤30	10	10
		Cu/μg.g^-1	≤5	ND	2.2
		Zn/μg.g^-1	≤10	2	2
		S/μg.g^-1	≤1500	1200	1100
	磁性异物含量	Fe/ng.g^-1	≤50	16	15
		Cr/ng.g^-1		6	4
		Zn/ng.g^-1		2	1

样品	c	a	体积/?³	c/a	Ni²⁺/Li⁺ 混排摩尔百分比
BC1	14.1942	2.8709	33.7722	4.9442	0.03
BC2	14.1876	2.8719	33.7787	4.9401	0

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三元前驱体微观形貌结构对LiNi_0.85Co_0.10Mn_0.05O₂正极材料性能的影响

Effect of precursor microstructure on the performance of LiNi_0.85Co_0.10Mn_0.05O₂ cathode materials

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