废旧三元电池材料酸浸液除铝铁工艺优化与试产评估

doi:10.16085/j.issn.1000-6613.2024-1317

摘要/Abstract

摘要：

随着新能源产业的快速发展，废旧三元锂离子电池的回收处理问题变得日益重要。废旧三元正极粉料的酸浸液中通常含有Al、Fe、Cu等杂质离子，高效去除这些杂质离子是提升回收工艺质量的关键问题之一。本文通过热力学分析，采用磷酸盐分步去除酸浸液中铝和铁的除杂工艺，系统研究了温度、时间、初始pH及磷酸盐用量等因素对铝、铁去除的影响规律，并根据处理40m³酸浸液的试产数据分析了该工艺放大应用的可行性。实验结果显示，酸浸液中99.0%以上的铜以Cu和Cu₂O的混合物形式被回收，Al和Fe的去除率分别为98.88%和99.81%，去除效果显著，主元素Ni、Co、Li的损失较少。本文为废旧三元粉料酸浸液除杂提供了一种有效的解决方案，对提升废旧三元粉料的回收效率具有重要意义。

关键词: 废旧三元粉料, 酸浸液, 净化, 回收, 效益评估

Abstract:

With the rapid development of the new energy industry, the recycling and treatment of spent ternary lithium-ion batteries have become increasingly urgent. The acid leachate from spent ternary powders typically contains impurity ions such as Al, Fe and Cu. Efficient removal of these impurities is critical for enhancing the quality of the recycling process. This work investigated a stepwise impurity removal process using phosphates to eliminate Al and Fe from the acid leachate based on thermodynamic analysis. Systematic investigations assessed the effects of reaction temperature, reaction time, initial solution pH and NaH₂PO₄ dosage on the removal efficiencies of Al and Fe. The feasibility of scaling up this process was evaluated using pilot production data from the treatment of 40m³ of acid leachate. The results indicated that over 99% of the copper was recovered as a mixture of Cu and Cu₂O. The removal efficiencies of Al and Fe were 98.88% and 99.81%, respectively, with minimal loss of Ni, Co and Li, demonstrating excellent impurity removal performance. This work provided an effective solution for Al/Fe removal from the acid leachate of spent ternary powders, offering significant potential for improving recycling efficiency.

Key words: spent ternary powders, leachate, purification, recovery, benefit assessment

中图分类号:

TQ153.2

江洋, 陈伟, 周康根, 李洪博, 赖其洲, 农润桥, 彭长宏. 废旧三元电池材料酸浸液除铝铁工艺优化与试产评估[J]. 化工进展, 2025, 44(10): 6016-6022.

JIANG Yang, CHEN Wei, ZHOU Kanggen, LI Hongbo, LAI Qizhou, NONG Runqiao, PENG Changhong. Optimization and pilot testing of Al/Fe removal processes for acid leachate from spent ternary lithium-ion battery powders[J]. Chemical Industry and Engineering Progress, 2025, 44(10): 6016-6022.

图/表 7

参考文献 37

[1]	CHEN Yongming, LIU Nannan, Yafei JIE, et al. Toxicity identification and evolution mechanism of thermolysis-driven gas emissions from cathodes of spent lithium-ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(22): 18228-18235.
[2]	江洋, 彭长宏, 陈伟, 等. 废旧磷酸铁锂粉料综合回收中试研究[J]. 化工学报, 2024, 75(6): 2353-2361.
	JIANG Yang, PENG Changhong, CHEN Wei, et al. Pilot-scale comprehensive recovery of spent LiFePO₄/C materials[J]. CIESC Journal, 2024, 75(6): 2353-2361.
[3]	LIU Jianhua, MENG Zhan. Innovation model analysis of new energy vehicles: Taking Toyota, tesla and BYD as an example[J]. Procedia Engineering, 2017, 174: 965-972.
[4]	LI Kunpeng, WANG Lan. Optimal electric vehicle subsidy and pricing decisions with consideration of EV anxiety and EV preference in green and non-green consumers[J]. Transportation Research Part E: Logistics and Transportation Review, 2023, 170: 103010.
[5]	WANG Yu, XU Zhiqiang, ZHANG Xi, et al. A green process to recover valuable metals from the spent ternary lithium-ion batteries[J]. Separation and Purification Technology, 2022, 299: 121782.
[6]	ZHOU Miaomiao, SHEN Ji, DUAN Yang, et al. The Le Chatelier’s principle enables closed loop regenerating ternary cathode materials for spent lithium-ion batteries[J]. Energy Storage Materials, 2024, 67: 103250.
[7]	LI Chunyan, DAI Guofu, LIU Runyu, et al. Separation and recovery of nickel cobalt manganese lithium from waste ternary lithium-ion batteries[J]. Separation and Purification Technology, 2023, 306: 122559.
[8]	YANG Cheng, ZHANG Jialiang, CHEN Yongqiang, et al. Pollutant reduction and closed-loop process for recovering high value-added products from spent lithium-ion batteries[J]. Journal of Power Sources, 2023, 584: 233611.
[9]	YUAN Haoran, WANG Houran, ZHAO Yunxing, et al. An effective tandem leaching method for recovering precious metals from depleted ternary lithium-ion batteries[J]. Sustainable Chemistry and Pharmacy, 2024, 41: 101694.
[10]	SHI Gongchu, ZHANG Ning, CHENG Jian, et al. Full closed-loop green regeneration and recycling technology for spent ternary lithium batteries: Hydrogen reduction with sulfuric acid cycle-leaching process[J]. Journal of Environmental Chemical Engineering, 2023, 11(6): 111207.
[11]	HAN Yaxing, CHEN Ji, LI Hailian, et al. Comprehensive recovery process of impurities removal and valuable metals co-extraction from simulated leaching solution of spent LIBs with CA12-TBP system[J]. Separation and Purification Technology, 2023, 326: 124773.
[12]	ZHU Xiangnan, JIANG Siqi, LI Xinlong, et al. Review on the sustainable recycling of spent ternary lithium-ion batteries: From an eco-friendly and efficient perspective[J]. Separation and Purification Technology, 2024, 348: 127777.
[13]	张笑笑, 王鸯鸯, 刘媛, 等. 废旧锂离子电池回收处理技术与资源化再生技术进展[J]. 化工进展, 2016, 35(12): 4026-4032.
	ZHANG Xiaoxiao, WANG Yangyang, LIU Yuan, et al. Recent progress in disposal and recycling of spent lithium-ion batteries[J]. Chemical Industry and Engineering Progress, 2016, 35(12): 4026-4032.
[14]	黎华玲, 陈永珍, 宋文吉, 等. 湿法回收退役三元锂离子电池有价金属的研究进展[J]. 化工进展, 2019, 38(2): 921-932.
	LI Hualing, CHEN Yongzhen, SONG Wenji, et al. Research progress on the recovery of valuable metals in retired LiNi _x Co _y Mn _z O₂ batteries by wet process[J]. Chemical Industry and Engineering Progress, 2019, 38(2): 921-932.
[15]	GONG Siyu, DONG Enhua, LIU Bingguo, et al. Eco-friendly closed-loop recycling of nickel, cobalt, manganese, and lithium from spent ternary lithium-ion battery cathodes[J]. Separation and Purification Technology, 2024, 348: 127771.
[16]	ASADI DALINI E, KARIMI Gh, ZANDEVAKILI S. Treatment of valuable metals from leaching solution of spent lithium-ion batteries[J]. Minerals Engineering, 2021, 173: 107226.
[17]	ZHOU Jiahui, ZHOU Xia, YU Wenhao, et al. Towards greener recycling: Direct repair of cathode materials in spent lithium-ion batteries[J]. Electrochemical Energy Reviews, 2024, 7(1): 13.
[18]	WU Juan, XIAO Li, SHEN Li, et al. Recent advancements in hydrometallurgical recycling technologies of spent lithium-ion battery cathode materials[J]. Rare Metals, 2024, 43(3): 879-899.
[19]	张英杰, 宁培超, 杨轩, 等. 废旧三元锂离子电池回收技术研究新进展[J]. 化工进展, 2020, 39(7): 2828-2840.
	ZHANG Yingjie, NING Peichao, YANG Xuan, et al. Research progess on the recycling technology of spent ternary lithium ion battery[J]. Chemical Industry and Engineering Progess, 2020, 39(7): 2828-2840.
[20]	WANG Yu, TU Yanan, XU Zhiqiang, et al. Separating metal impurities from spent ternary Li-ion batteries materials based on the roasting characteristics[J]. Ionics, 2022, 28(4): 1833-1844.
[21]	YU Jiancheng, MA Baozhong, QIU Zhijun, et al. Separation and recovery of valuable metals from ammonia leaching solution of spent lithium-ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2023, 11(26): 9738-9750.
[22]	YANG Cheng, ZHANG Jialiang, LIANG Guoqiang, et al. An advanced strategy of “metallurgy before sorting” for recycling spent entire ternary lithium-ion batteries[J]. Journal of Cleaner Production, 2022, 361: 132268.
[23]	ZHENG Ying, YANG Zhe, LI Zhaoyang, et al. Environmentally friendly recovery of Li₂CO₃ from spent lithium-ion batteries by oxidation and selective leaching process[J]. ACS ES & T Engineering, 2024, 4(8): 1927-1936.
[24]	WANG Hui, WU Zejia, WANG Mengmeng, et al. “Acid + oxidant” treatment enables selective extraction of lithium from spent NCM523 positive electrode[J]. Batteries, 2024, 10(6): 179.
[25]	LI Guidong, CHEN Ye, WU Mingkun, et al. High-efficiency leaching process for selective leaching of lithium from spent lithium iron phosphate[J]. Waste Management, 2024, 190: 141-148.
[26]	LEI Shuya, SUN Wei, YANG Yue. Solvent extraction for recycling of spent lithium-ion batteries[J]. Journal of Hazardous Materials, 2022, 424: 127654.
[27]	SRIVASTAVA Varsha, RANTALA Venla, MEHDIPOUR Parisa, et al. A comprehensive review of the reclamation of resources from spent lithium-ion batteries[J]. Chemical Engineering Journal, 2023, 474: 145822.
[28]	YAO Yonglin, ZHU Meiying, ZHAO Zhuo, et al. Hydrometallurgical processes for recycling spent lithium-ion batteries: A critical review[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(11): 13611-13627.
[29]	WENG Yaqing, XU Shengming, HUANG Guoyong, et al. Synthesis and performance of Li[(Ni_1/3Co_1/3Mn_1/3)_1- _x Mg _x ]O₂ prepared from spent lithium ion batteries[J]. Journal of Hazardous Materials, 2013, 246: 163-172.
[30]	KANG Jingu, SOHN Jeongsoo, CHANG Hankwon, et al. Preparation of cobalt oxide from concentrated cathode material of spent lithium ion batteries by hydrometallurgical method[J]. Advanced Powder Technology, 2010, 21(2): 175-179.
[31]	WEI Yun, ZHOU Lei, HU Wenbin, et al. Recovery of cathode copper and ternary precursors from CuS slag derived by waste lithium-ion batteries: Process analysis and evaluation[J]. Chinese Chemical Letters, 2024, 35(7): 109172.
[32]	Weiguang LYU, WANG Zhonghang, CAO Hongbin, 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.
[33]	GRATZ Eric, Qina SA, APELIAN Diran, et al. A closed loop process for recycling spent lithium ion batteries[J]. Journal of Power Sources, 2014, 262: 255-262.
[34]	黎伟杰, 路蕾蕾, 李得科, 等. 锂离子电池拆解回收技术及进展[J]. 化工进展, 2024, 43(8): 4601-4613.
	LI Weijie, LU Leilei, LI Deke, et al. Lithium-ion battery disassembly and recycling technology and process[J]. Chemical Industry and Engineering Process, 2024, 43(8): 4601-4613.
[35]	JIANG Yang, PENG Changhong, ZHOU Kanggen, et al. Recovery of iron from titanium white waste for the preparation of LiFePO₄ battery[J]. Journal of Cleaner Production, 2023, 415: 137817.
[36]	HAO Jiacheng, HAO Jiayu, LIU Dongfu, et al. Maximizing resource recovery: A green and economic strategy for lithium extraction from spent ternary batteries[J]. Journal of Hazardous Materials, 2024, 472: 134472.
[37]	JIANG Yang, ZHANG Guopeng, ZHOU Kanggen, et al. Sequential separation and recovery of phosphorus and lithium from lithium phosphate slag by selective extraction-precipitation[J]. Separation and Purification Technology, 2024, 333: 125907.

除杂渣	Ni	Co	Mn	Li	Al	Fe	Cu	P
富铜渣	0.17	0.02	0.04	0.02	0.11	2.33	89.14	—
预除杂渣	0.21	0.05	0.13	0.04	14.87	1.69	0.004	19.16
净化渣	0.69	0.28	0.25	0.07	0.30	27.40	—	10.38
沉降率	1.12	1.31	2.08	0.39	98.88	99.81	99.03	98.96

除杂渣	Ni	Co	Mn	Li	Al	Fe	Cu	P
富铜渣	0.17	0.02	0.04	0.02	0.11	2.33	89.14	—
预除杂渣	0.21	0.05	0.13	0.04	14.87	1.69	0.004	19.16
净化渣	0.69	0.28	0.25	0.07	0.30	27.40	—	10.38
沉降率	1.12	1.31	2.08	0.39	98.88	99.81	99.03	98.96

分类	物料名称	单价	消耗量	成本/CNY
辅料	磷酸二氢钠	6900CNY·t^-1	-0.9t	-6210
	32%液碱	1100CNY·m^-3	-0.3m³	-330
	双氧水	1290CNY·m^-3	-0.33m³	-426
	工业铁粉	2500CNY·t^-1	-0.125t	-313
其他	蒸汽	230CNY·t^-1	—	-270
	电力	0.7CNY·kW·h^-1	—	-130
	人工	—	—	-500
	固废处理	300CNY·t^-1	-1.75t	-525
产物	富铜渣	62500CNY·t^-1	+0.14t	+8750
收支		+46CNY

分类	物料名称	单价	消耗量	成本/CNY
辅料	磷酸二氢钠	6900CNY·t^-1	-0.9t	-6210
	32%液碱	1100CNY·m^-3	-0.3m³	-330
	双氧水	1290CNY·m^-3	-0.33m³	-426
	工业铁粉	2500CNY·t^-1	-0.125t	-313
其他	蒸汽	230CNY·t^-1	—	-270
	电力	0.7CNY·kW·h^-1	—	-130
	人工	—	—	-500
	固废处理	300CNY·t^-1	-1.75t	-525
产物	富铜渣	62500CNY·t^-1	+0.14t	+8750
收支		+46CNY