废磷酸铁锂正极材料资源化回收工艺

doi:10.19799/j.cnki.2095-4239.2021.0388

储能科学与技术 ›› 2022, Vol. 11 ›› Issue (1): 45-52.doi: 10.19799/j.cnki.2095-4239.2021.0388

废磷酸铁锂正极材料资源化回收工艺

王子璇¹(), 李俊成¹(), 李金东¹, 易娟², 石霖², 吴旭¹()

^1.华中科技大学环境科学与工程学院，湖北武汉 430074
^2.湖北华德莱节能减排科技有限公司，湖北武汉 430070

收稿日期:2021-08-02 修回日期:2021-08-09 出版日期:2022-01-05 发布日期:2022-01-10
通讯作者: 吴旭 E-mail:m202073929@hust.edu.cn;profxuwu@hust.edu.cn
作者简介:王子璇（1997—），女，硕士研究生，研究方向为废旧锂离子电池处理与资源化，E-mail：m202073929@hust.edu.cn；共同第一作者：李俊成（1997—），男，硕士研究生，研究方向为固体废物处理与资源化，E-mail：juncheng87@foxmail.com|王子璇（1997—），女，硕士研究生，研究方向为废旧锂离子电池处理与资源化，E-mail：m202073929@hust.edu.cn；共同第一作者：李俊成（1997—），男，硕士研究生，研究方向为固体废物处理与资源化，E-mail：juncheng87@foxmail.com|吴旭，博士，教授，研究方向为电化学环境工程，E-mail：profxuwu@hust.edu.cn。
基金资助:
国家“千人计划”青年人才项目

Resource recovery technology of spent lithium iron phosphate cathode material

Zixuan WANG¹(), Juncheng LI¹(), Jindong LI¹, Juan YI², Lin SHI², Xu WU¹()

^1.School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China
^2.Hubei Hua Delai Energy Saving and Emission Reduction Technology Co. Ltd. , Wuhan 430070, Hubei, China

Received:2021-08-02 Revised:2021-08-09 Online:2022-01-05 Published:2022-01-10
Contact: Xu WU E-mail:m202073929@hust.edu.cn;profxuwu@hust.edu.cn

摘要/Abstract

摘要：

废磷酸铁锂电池的回收处理是目前的行业焦点。针对废磷酸铁锂电池回收工艺过程复杂、二次废料过多、成本高等问题，提出了一条基于固相电解技术的电化学法回收工艺路线，降低了次生污染的风险，实现了废磷酸铁锂电池高产率低成本回收。工艺采用磷酸体系电解和分步沉淀的方法，制备二水合磷酸铁和磷酸锂。开展了电解过程中的参数优化和沉淀分离的因素研究，重点分析了电解电压、磷酸电解液浓度及电解前浸泡时间等参数对铁、锂浸出率的影响规律。研究结果表明，电解电压为2.5 V，磷酸电解液浓度为0.6 mol/L，先浸泡60 min后电解30 min处理过后，锂离子浸出率为95.6%，铁离子浸出率为91.3%。通过氨水控制溶液pH分步沉淀二水合磷酸铁和磷酸锂，二水合磷酸铁的回收率可达98.8%，锂离子的回收率可达99.4%。

关键词: 废磷酸铁锂, 固相电解, 磷酸电解液, 分步沉淀

Abstract:

Spent lithium iron phosphate (SLFP) batteries recycling is increasingly being researched. In this study, an electrochemical recycling method for SLFP is proposed based on solid-phase electrolysis; in reference to that, the technology exhibits complex procedures, extra secondary wastes, and high cost, resulting in reduced risk of secondary pollution and improved yield, and lower price. Phosphoric acid electrolysis system and stepwise precipitation method were adopted to prepare FePO₄·2H₂O and Li₃PO₄. The study covers parameter optimization in the electrolysis process and factor analysis for the precipitation separation. It analyzes the effect of parameters such as cell voltage, H₃PO₄ electrolyte concentration, and soaking time before electrolysis on Fe and Li leaching rates. After 60 min of soaking, with 30 min electrolysis in 0.6 mol/L H₃PO₄ electrolyte at 2.5 V, the Fe and Li leaching rates were 91.3% and 95.6%, respectively. The solution pH was controlled by stepwise addition of ammonia water to precipitate FePO₄·2H₂O and Li₃PO₄, of which a corresponding 98.8% and 99.4% recovery rates were achieved. respectively.

Key words: spent lithium iron phosphate, solid phase electrolysis, phosphoric acid electrolyte, step precipitation

中图分类号:

X 773

王子璇, 李俊成, 李金东, 易娟, 石霖, 吴旭. 废磷酸铁锂正极材料资源化回收工艺[J]. 储能科学与技术, 2022, 11(1): 45-52.

Zixuan WANG, Juncheng LI, Jindong LI, Juan YI, Lin SHI, Xu WU. Resource recovery technology of spent lithium iron phosphate cathode material[J]. Energy Storage Science and Technology, 2022, 11(1): 45-52.

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参考文献 30

1	PADHI A K, NANJUNDASWAMY K S, GOODENOUGH J B. Phospho-olivines as positive-electrode materials for rechargeable lithium batteries[J]. Journal of the Electrochemical Society, 1997, 144(4): 1188-1194.
2	DELACOURT C, POIZOT P, TARASCON J M, et al, The existence of a temperature-driven solid solution in LixFePO₄ for 0≤x≤1[J]. Nature Materials, 2005, 4(3): 254-260.
3	ANDERSSON A S. Thermal stability of LiFePO₄-based cathodes[J]. Electrochemical and Solid-State Letters, 1999, 3(2): 66-68.
4	朱国才. 废旧动力锂离子电池回收再利用产业化进展[J]. 新材料产业, 2018(3): 31-33.
	ZHU G C. Progress in industrialization of recycling and reuse of spent power lithium ion batteries[J]. Advanced Materials Industry, 2018(3): 31-33.
5	WANG W, WU Y F. An overview of recycling and treatment of spent LiFePO₄ batteries in China[J]. Resources, Conservation and Recycling, 2017, 127: 233-243.
6	吴越, 裴锋, 贾蕗路, 等. 从废旧磷酸铁锂电池中回收铝、铁和锂[J]. 电源技术, 2014, 38(4): 629-631.
	WU Y, PEI F, JIA L L, et al. Recovery of aluminum, iron and lithium from spent lithium iron phosphate batteries[J]. Chinese Journal of Power Sources, 2014, 38(4): 629-631.
7	PALACIN M R, DE GUIBERT A. Why do batteries fail?[J] Science, 2016, 351(6273): 1253292-1253292.
8	王天雅, 宋端梅, 贺文智, 等. 废弃动力锂电池回收再利用技术及经济效益分析[J]. 上海节能, 2019(10): 814-820.
	WANG T Y, SONG D M, HE W Z, et al. Recycling strategies and economic efficiency analysis of waste electric vehicle lithium-ion batteries[J]. Shanghai Energy Conservation, 2019(10): 814-820.
9	OMAR H, ROHANI S. Treatment of landfill waste, leachate and landfill gas: A review[J]. Frontiers of Chemical Science and Engineering, 2015, 9(1): 15-32.
10	KANG D H P, CHEN M, OGUNSEITAN O A. Potential environmental and human health impacts of rechargeable lithium batteries in electronic waste[J]. Environmental Science & Technology, 2013, 47(10): 5495-5503.
11	赵光金, 何睦, 唐国鹏, 等. 废旧磷酸铁锂电池正极材料浸取及回收研究[J]. 电源技术, 2019, 43(3): 442-444, 452.
	ZHAO G J, HE M, TANG G P, et al. Study on leaching and recovery of cathode material for spent lithium iron phosphate battery[J]. Chinese Journal of Power Sources, 2019, 43(3): 442-444, 452.
12	CAI G Q, FUNG K Y, NG K M, et al. Process development for the recycle of spent lithium ion batteries by chemical precipitation[J]. Industrial & Engineering Chemistry Research, 2014, 53(47): 18245-18259.
13	伍德佑, 刘志强, 饶帅, 等. 废旧磷酸铁锂电池正极材料回收利用技术的研究进展[J]. 有色金属(冶炼部分), 2020(10): 70-78.
	WU D Y, LIU Z Q, RAO S, et al. Research progress in recycling technology of cathode materials for spent lithium iron phosphate batteries[J]. Nonferrous Metals (Extractive Metallurgy), 2020(10): 70-78.
14	LÜ W, WANG Z H, CAO H B, et al. A critical review and analysis on the recycling of spent lithium-ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(2): 1504-1521.
15	LIU C W, LIN J, CAO H B, et al, Recycling of spent lithium-ion batteries in view of lithium recovery: A critical review[J]. Journal of Cleaner Production, 2019, 228: 801-813.
16	LI H Y, YE H, SUN M C, et al. Process for recycle of spent lithium iron phosphate battery via a selective leaching-precipitation method[J]. Journal of Central South University, 2020, 27(11): 3239-3248.
17	韩小云, 徐金球. 沉淀法回收废旧磷酸铁锂电池中的铁和锂[J]. 广东化工, 2017, 44(4): 12-16.
	HAN X Y, XU J Q. Recover of iron and lithium from spent lithium iron phosphate batteries by precipitation process[J]. Guangdong Chemical Industry, 2017, 44(4): 12-16.
18	王百年, 王宇, 刘京, 等. 废旧磷酸铁锂电池中锂元素的回收技术[J]. 电源技术, 2019, 43(1): 57-59+116.
	WANG B N, WANG Y, LIU J, et al. Recovery technology of lithium in waste lithium iron phosphate battery[J]. Chinese Journal of Power Sources, 2019, 43(1): 57-59+116.
19	LI H, XING S Z, LIU Y, et al. Recovery of lithium, iron, and phosphorus from spent LiFePO₄ batteries using stoichiometric sulfuric acid leaching system[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(9): 8017-8024.
20	WANG X, WANG X, ZHANG R, et al. Hydrothermal preparation and performance of LiFePO₄ by using Li₃PO₄ recovered from spent cathode scraps as Li source[J]. Waste Management, 2018, 78: 208-216.
21	YANG Y X, MENG X Q, CAO H B, et al. Selective recovery of lithium from spent lithium iron phosphate batteries: a sustainable process[J]. Green Chemistry, 2018, 20(13): 3121-3133.
22	LI L, LU J, ZHAI L Y, et al, A facile recovery process for cathodes from spent lithium iron phosphate batteries by using oxalic acid[J]. CSEE Journal of Power and Energy Systems, 2018, 4(2): 219-225.
23	LI L, BIAN Y F, ZHANG X X, et al. A green and effective room-temperature recycling process of LiFePO₄ cathode materials for lithium-ion batteries[J]. Waste Management, 2019, 85: 437-444.
24	YADAV P, JIE C J, TAN S, et al. Recycling of cathode from spent lithium iron phosphate batteries[J]. Journal of Hazardous Materials, 2020, 399: doi: 10.1016/j.jhazmat.2020.123068.
25	LAROUCHE F, TEDJAR F, AMOUZEGAR K, et al, Progress and status of hydrometallurgical and direct recycling of Li-ion batteries and beyond[J]. Materials, 2020, 13(3): doi: 10.3390/ma13030801.
26	祝宏帅, 孙金峰, 胡启阳, 等. 磷酸体系应用于失效磷酸铁锂电池正极材料回收的研究[J]. 高校化学工程学报, 2017, 31(5): 1238-1244.
	ZHU H S, SUN J F, HU Q Y, et al. Application of phosphoric acid system in positive electrode material recovery from invalid lithium iron phosphate batteries[J]. Journal of Chemical Engineering of Chinese Universities, 2017, 31(5): 1238-1244.
27	YANG Y X, ZHENG X H, CAO H B, et al. A closed-loop process for selective metal recovery from spent lithium iron phosphate batteries through mechanochemical activation[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(11): 9972-9980.
28	BI H J, ZHU H B, ZU L, et al. Combined mechanical process recycling technology for recovering copper and aluminium components of spent lithium-iron phosphate batteries[J]. Waste Management & Research, 2019, 37(8): 767-780.
29	LI Z, LIU D F, XIONG J C, et al. Selective recovery of lithium and iron phosphate/carbon from spent lithium iron phosphate cathode material by anionic membrane slurry electrolysis[J]. Waste Management, 2020, 107: 1-8.
30	BAE H, KIM Y. Technologies of lithium recycling from waste lithium ion batteries: A review[J]. Materials Advances, 2021, 2(10): 3234-3250.

废磷酸铁锂正极材料资源化回收工艺

Resource recovery technology of spent lithium iron phosphate cathode material

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