熔盐法再生修复退役三元动力电池正极材料

doi:10.19799/j.cnki.2095-4239.2019.0258

储能科学与技术 ›› 2020, Vol. 9 ›› Issue (3): 848-855.doi: 10.19799/j.cnki.2095-4239.2019.0258

熔盐法再生修复退役三元动力电池正极材料

楼平¹, 徐国华¹, 岳灵平¹, 李首顶², 程琦², 曹元成²(), 邓鹤鸣³

^1. 国网浙江省电力公司湖州供电公司，浙江湖州 313000
^2. 华中科技大学电气与电子工程学院，湖北武汉 430074
^3. 国网电力科学研究院，湖北武汉 430074

收稿日期:2019-11-13 修回日期:2019-12-03 出版日期:2020-05-05 发布日期:2020-05-11
通讯作者: 曹元成 E-mail:yccao@hust.edu.cn
作者简介:楼平（1967—），男，硕士，主要研究方向为配网及储能技术，E-mail：louping2005@126.com；
基金资助:
国家重点研发计划项目(2018YFB0905300)

Degraded Li _x Ni_0.5Co_0.2Mn_0.3O₂ (0 < x < 1) via eutectic solutions for direct regeneration of spent lithium ion battery cathodes

LOU Ping¹, XU Guohua¹, YUE Lingping¹, LI Shouding², CHENG Qi², CAO Yuancheng²(), DENG Heming³

^1. State Grid Huzhou Electric Power Supply Company, Huzhou 313000, Zhejiang, China
^2. School of Electrical and Electronic Engineering, Huazhong University of Science and Technology, Wuhan 430000, Hubei, China
^3. State Grid Electric Power Research Institute, Wuhan 430074, Hubei, China

Received:2019-11-13 Revised:2019-12-03 Online:2020-05-05 Published:2020-05-11
Contact: Yuancheng CAO E-mail:yccao@hust.edu.cn

摘要/Abstract

摘要：

本文主要针对普遍使用的废弃锂离子电池正极材料NCM523进行绿色回收，工艺极富创新性，且简单可行，直接对废弃三元正极材料进行NCM523再生修复。在空气气氛中，采用低共熔混合物LiNO₃-LiOH为锂盐进行补锂修复再生，从而把废弃失效的NCM523重新修复成初始比容量的材料。X射线衍射（XRD）、电感耦合等离子光谱发生仪（ICP）、扫描电子显微镜（SEM）结果表明通过熔融的锂盐为失效正极材料补锂，并加以短暂煅烧过程可以将失效的正极材料组分和晶体结构都恢复至原始状态，电化学结果显示，在0.1 C的充放电电流密度和2.8～4. 25 V的电压范围内，300 ℃/3 h-850 ℃/4 h修复再生后的LiNi_{0. 5}Co_{0. 2}Mn_0.3O₂首次放电比容量为161. 2 mA·h/g（0.1 C），充放电库仑效率为87. 8%。1 C条件下循环100次后,放电比容量为132. 6 mA·h/g，相比于未处理的废弃三元正极材料，倍率性能和循环性能得到大幅度提高，与商业NCM523材料相差无几。本研究有助于推动废旧三元正极材料回收产业化推广，也为回收再生其它的锂电池正极材料，例如锰酸锂、磷酸铁锂等材料的绿色回收提供了独特的思路，此方法在锂电池回收领域有良好的应用前景。

关键词: 废旧锂离子电池, 正极材料, 低温共熔盐, 修复再生, 镍钴锰酸锂

Abstract:

Spent NCM523 was regenerated by a green method which is simple, feasible, and innovative. A low-eutectic mixture (LiNO₃-LiOH) was used as the lithium salt for regeneration in an air atmosphere. The regenerated product was characterized by X-ray diffraction, inductively coupled plasma spectroscopy, and scanning electron microscopy. The composition and crystal structure confirmed that the spent cathode was restored to its original state. Moreover, electrochemical results show that under the condition 300 ℃/3 h～850 ℃/4 h, the specific capacity of the regenerated material reached 161.2 mA·h/g(0.1 C, 2.8～4. 25 V) in the first discharge, and the coulomb efficiency was 87.8%. After 100 cycles at 1 C, the specific discharge capacity was 133.6 mA·h/g, confirming the high electrochemical performance of the rejuvenated material. The rate and recycling performance were much improved from those of untreated cathode materials and were similar to those of commercial anode materials. This research can promote the industrialization of cathode material recovery and provides a unique idea for the green recovery of other cathode materials such as LiMn₂O₄ and LiFePO₄. This method has good application prospects in lithium battery recovery.

Key words: spent lithium ion battery, anode material, eutectic, regenerate, lithium nickel cobalt manganese oxide

中图分类号:

TM 912.8

楼平, 徐国华, 岳灵平, 李首顶, 程琦, 曹元成, 邓鹤鸣. 熔盐法再生修复退役三元动力电池正极材料[J]. 储能科学与技术, 2020, 9(3): 848-855.

LOU Ping, XU Guohua, YUE Lingping, LI Shouding, CHENG Qi, CAO Yuancheng, DENG Heming. Degraded Li _x Ni_0.5Co_0.2Mn_0.3O₂ (0 < x < 1) via eutectic solutions for direct regeneration of spent lithium ion battery cathodes[J]. Energy Storage Science and Technology, 2020, 9(3): 848-855.

图/表 8

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参考文献 21

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编号	n(Li)/%	n(Ni)/%	n(Co)/%	n(Mn)/%
失效三元NCM523	0.6601	0.5027	0.2009	0.2964
300 ℃/4 h	0.9795	0.5133	0.2052	0.2815
300 ℃/3 h	0.9996	0.5073	0.2041	0.2887
300 ℃/2 h	0.9951	0.5116	0.2050	0.2834
300 ℃/4 h-850 ℃/4 h	1.0252	0.5110	0.2051	0.2839
300 ℃/3 h-850 ℃/4 h	1.0452	0.5107	0.2065	0.2829
300℃/2 h-850 ℃/4 h	1.0238	0.5108	0.2050	0.2842

处理条件	I ₀₀₃	I ₁₀₁	I ₁₀₄	I ₀₀₃/I ₁₀₄	M1	I ₁₀₁/I ₁₀₄	M2	a	c	c/a
300 ℃/4 h	540	258	640	0.84	12.41%	0.40	6.78%	2.87249	14.23298	4.955
300 ℃/3 h	2812	1082	2087	1.35	1.65%	0.52	1.60%	2.87244	14.246	4.960
300 ℃/2 h	2879	1151	2145	1.34	1.75%	0.54	0.84%	2.87247	14.2428	4.958
300 ℃/4 h-850 ℃/4 h	3964	1516	3162	1.25	3.48%	0.48	3.28%	2.87532	14.21978	4.945
300 ℃/3 h-850 ℃/4 h	3976	1529	3057	1.30	2.56%	0.50	2.38%	2.87122	14.23814	4.959
300 ℃/2 h-850 ℃/4 h	3030	1382	2937	1.03	8.10%	0.47	3.67%	2.87499	14.25395	4.958

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熔盐法再生修复退役三元动力电池正极材料

Degraded Li _x Ni_0.5Co_0.2Mn_0.3O₂ (0 < x < 1) via eutectic solutions for direct regeneration of spent lithium ion battery cathodes

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熔盐法再生修复退役三元动力电池正极材料

Degraded Li x Ni0.5Co0.2Mn0.3O2 (0 < x < 1) via eutectic solutions for direct regeneration of spent lithium ion battery cathodes

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Degraded Li _x Ni_0.5Co_0.2Mn_0.3O₂ (0 < x < 1) via eutectic solutions for direct regeneration of spent lithium ion battery cathodes