Resource recovery technology of spent lithium iron phosphate cathode material

doi:10.19799/j.cnki.2095-4239.2021.0388

Abstract

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

CLC Number:

X 773

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.

Figures/Tables 9

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References 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.