废旧锂离子电池有机酸湿法冶金回收技术研究进展

doi:10.19799/j.cnki.2095-4239.2020.0199

摘要/Abstract

摘要：

近几年随着电动汽车的普及，废旧锂离子电池的数量也迅速增长，从环境保护和资源利用的角度来说，废旧锂离子电池回收是必然的趋势，然而目前废旧锂离子电池的回收技术由于二次污染、成本高的问题，并未得到广泛的应用，因此寻求更加绿色环保经济高效的回收技术迫在眉睫。湿法冶金回收技术因其能量需求低、回收产物纯度高、成本低而成为废旧锂离子电池回收方法中最具有前景的工艺。本文通过对相关文献的研究，综述了目前湿法冶金回收技术中有机酸对废旧锂离子电池中金属浸出的影响，着重介绍了酸浸过程中苹果酸、柠檬酸、草酸等有机酸的特点，重点比较了各种有机酸在浸出过程中的反应条件以及金属浸出效率，分析了浸出过程中有机酸与活性物质的浸出动力学。综合分析表明，通过对浸出动力学进行探究，能够优化影响金属浸出的因素，提升金属浸出效率，进而提高湿法冶金回收技术的整体回收效率。在未来的发展中，有机酸的浸出动力学有望成为湿法冶金回收工艺研究的重要方向。

关键词: 废旧锂离子电池, 湿法冶金, 有机酸, 反应机理

Abstract:

In the recent years, the number of spent lithium-ion batteries has rapidly increased with the popularity of electric vehicles. Hence, the development of a recycling technology has become an urgent matter from the viewpoint of environmental protection and resource utilization. However, the recycling technology for spent lithium-ion batteries has not been widely used because of secondary pollution and high cost, which has consequently resulted to an urgent call for a green, economical, and efficient recycling technology. The hydrometallurgical technology is the most promising technology in recycling spent lithium-ion batteries because of its low energy demand, high purity, and low cost. This paper reviews the effects of organic acids on the hydrometallurgical recovery technology on metal leaching in spent lithium-ion batteries, introduces the characteristics of malic acid, citric acid, oxalic acid, and other organic acids in the acid leaching process, compares the reaction conditions of various organic acids in the leaching process and the efficiency of metal leaching, and analyzes the leaching kinetics between organic acids and active substances during the leaching process. The comprehensive analysis shows that the factors affecting metal leaching can be optimized; the metal leaching efficiency can be improved; and the overall recovery efficiency of the hydrometallurgical recovery technology can be elevated by exploring the leaching kinetics. In the future, the leaching kinetics of organic acids is expected to become an important research direction in the hydrometallurgical recovery process.

Key words: spent lithium-ion batteries, hydrometallurgy, organic acid, mechanis

中图分类号:

TM 911

李林林, 曹林娟, 麦永雄, 门一飞, 杨伟, 陈胜洲. 废旧锂离子电池有机酸湿法冶金回收技术研究进展[J]. 储能科学与技术, 2020, 9(6): 1641-1650.

Linlin LI, Linjuan CAO, Yongxiong MAI, Yifei MEN, Wei YANG, Shengzhou CHEN. Research progress of the organic acid of the hydrometallurgical recovery technology in spent Li ion batteries[J]. Energy Storage Science and Technology, 2020, 9(6): 1641-1650.

图/表 3

参考文献 62

1	LI Li, LU Jun, REN Yang, et al. Ascorbic-acid-assisted recovery of cobalt and lithium from spent Li-ion batteries[J]. Journal of Power Sources, 2012, 218: 21-27.
2	LIANG Yuhan, SU Jing, XI Beidou, et al. Life cycle assessment of lithium-ion batteries for greenhouse gas emissions[J]. Resources, Conservation and Recycling, 2017, 117: 285-293.
3	李金东, 古月圆, 王路阳, 等. 退役锂离子电池健康状态评估方法综述[J]. 储能科学与技术, 2019, 8(5): 807-812.
	LI Jindong, GU Yueyuan, WANG Luyang, et al. Review on state of health estimation of retired lithium-ion batteries[J]. Energy Storage Science and Technology, 2019, 8(5): 807-812.
4	OR T, GOURLEY S W D, KALIYAPPAN K, et al. Recycling of mixed cathode lithium-ion batteries for electric vehicles: Current status and future outlook[J]. Carbon Energy, 2020, 2(1): 6-43.
5	BIGUM M, DAMGAARD A, SCHEUTZ C, et al. Environmental impacts and resource losses of incinerating misplaced household special wastes (WEEE, batteries, ink cartridges and cables)[J]. Resources, Conservation and Recycling, 2017, 122: 251-260.
6	PUCA Antonio, CARRANO Marco, LIU Gengyuan, et al. Energy and eMergy assessment of the production and operation of a personal computer[J]. Resources, Conservation and Recycling, 2017, 116: 124-136.
7	JAGANNATH Akshaya, Vidya SHETTY K, SAIDUTTA M B. Bioleaching of copper from electronic waste using Acinetobacter sp. Cr B2 in a pulsed plate column operated in batch and sequential batch mode[J]. Journal of Environmental Chemical Engineering, 2017, 5(2): 1599-1607.
8	WEI Jucai, ZHAO Shichang, JI Liangxin, et al. Reuse of Ni-Co-Mn oxides from spent Li-ion batteries to prepare bifunctional air electrodes[J]. Resources, Conservation and Recycling, 2018, 129: 135-142.
9	陈永珍, 黎华玲, 宋文吉, 等. 废旧磷酸铁锂电池回收技术研究进展[J]. 储能科学与技术, 2019, 8(2): 237-247.
	CHEN Yongzhen, LI Hualiang, SONG Wenji, et al. A review on recycling technology of spent lithium iron phosphate battery[J]. Energy Storage Science and Technology, 2019, 8(2): 237-247.
10	卫寿平, 孙杰, 周添, 等. 废旧锂离子电池中金属材料回收技术研究进展[J]. 储能科学与技术, 2017, 6(6): 1196-1207.
	WEI Shouping, SUN Jie, ZHOU Tian, et al. Research development of metals recovery from spent lithium-ion batteries[J]. Energy Storage Science and Technology, 2017, 6(6): 1196-1207.
11	楼平, 徐国华, 岳灵平, 等. 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, et al. Degraded Li_xNi_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.
12	GEORGI-MASCHLER T, FRIEDRICH B, WEYHE R, et al. Development of a recycling process for Li-ion batteries[J]. Journal of Power Sources, 2012, 207: 173-182.
13	GARCIA E M, SANTOS J S, PEREIRA E C, et al. Electrodeposition of cobalt from spent Li-ion battery cathodes by the electrochemistry quartz crystal microbalance technique[J]. Journal of Power Sources, 2008, 185(1): 549-553.
14	BAHALOO-HOREH N, MOUSAVI S M. Enhanced recovery of valuable metals from spent lithium-ion batteries through optimization of organic acids produced by Aspergillus niger[J]. Waste Management, 2017, 60: 666-679.
15	HOREH N B, MOUSAVI S M, SHOJAOSADATI S A. Bioleaching of valuable metals from spent lithium-ion mobile phone batteries using Aspergillus niger[J]. Journal of Power Sources, 2016, 320: 257-266.
16	ZHAO Ling, YANG Dong, ZHU Nanwen. Bioleaching of spent Ni-Cd batteries by continuous flow system: Effect of hydraulic retention time and process load[J]. Journal of Hazardous Materials, 2008, 160(2): 648-654.
17	GOLMOHAMMADZADEH Rabeeh, FARAJI Fariborz, RASHCHI Fereshteh. Recovery of lithium and cobalt from spent lithium ion batteries (LIBs) using organic acids as leaching reagents: A review[J]. Resources, Conservation and Recycling, 2018, 136: 418-435.
18	BARIK S P, PRABAHARAN G, KUMAR L. Leaching and separation of Co and Mn from electrode materials of spent lithium-ion batteries using hydrochloric acid: Laboratory and pilot scale study[J]. Journal of Cleaner Production, 2017, 147: 37-43.
19	MESHRAM Pratima, PANDEY B D, MANKHAND T R. Recovery of valuable metals from cathodic active material of spent lithium ion batteries: Leaching and kinetic aspects[J]. Waste Management, 2015, 45: 306-313.
20	刘小娟, 凌雨轩, 成江涛, 等. 废旧钴酸锂离子电池材料中钴、锂的回收工艺研究[J]. 湖南工程学院学报(自然科学版), 2019, 29(4): 67-71.
	LIU Xiaojuan, LING Yuxuan, CHENG Jiangtao, et al. Study on recycling of spent lithiumion batteries containing cobalt and lithium[J].Journal of Hunan Institute of Engineering, 2019, 29(4): 67-71.
21	TESFAYE Fiseha, LINDBERG Daniel, HAMUYUNI Joseph, et al. Improving urban mining practices for optimal recovery of resources from e-waste[J]. Minerals Engineering, 2017, 111: 209-221.
22	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): 217-228.
	LI Hualing, CHEN Yongzhen, SONG Wenji, et al. Research progress on the recovery of valuable metals in retired LiNi_xCo_yMn_zO₂ batteries by wet process[J]. Chemical Industry and Engineering Progress, 2019, 38(2): 217-228.
23	HE Lipo, SUN Shuying, MU Yanyu, et al. Recovery of lithium, nickel, cobalt, and manganese from spent lithium-ion batteries using l-tartaric acid as a leachant[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(1): 714-721.
24	LI Li, BIAN Yifan, ZHANG Xiaoxiao, et al. Economical recycling process for spent lithium-ion batteries and macro- and micro-scale mechanistic study[J]. Journal of Power Sources, 2018, 377: 70-79.
25	GOLMOHAMMADZADEH Rabeeh, RASHCHI Fereshteh, VAHIDI Ehsan. Recovery of lithium and cobalt from spent lithium-ion batteries using organic acids: Process optimization and kinetic aspects[J]. Waste Management, 2017, 64: 244-254.
26	范二莎, 李丽, 林娇, 等. 低温熔融盐辅助高效回收废旧三元正极材料[J]. 储能科学与技术, 2020, 9(2): 361-367.
	FAN Ersha, LI Li, LIN Jiao, et al. Low-temperature molten-salt-assisted recycling of spent LiNi_1/3Co_1/3Mn_1/3O₂ cathode materials[J]. Energy Storage Science and Technology, 2020, 9(2): 361-367.
27	LI Li, GE Jing, CHEN Renjie, et al. Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries[J]. Waste Management, 2010, 30(12): 2615-2621.
28	LI L, DUNN J B, ZHANG X X, et al. Recovery of metals from spent lithium-ion batteries with organic acids as leaching reagents and environmental assessment[J]. Journal of Power Sources, 2013, 233: 180-189.
29	SUN Conghao, XU Liping, CHEN Xiangping, et al. Sustainable recovery of valuable metals from spent lithium-ion batteries using DL-malic acid: Leaching and kinetics aspect[J]. Waste Management & Research, 2017, 36(2): 113-120.
30	ZHANG Yingjie, MENG Qi, DONG Peng, et al. Use of grape seed as reductant for leaching of cobalt from spent lithium-ion batteries[J]. Journal of Industrial and Engineering Chemistry, 2018, 66: 86-93.
31	JANEIRO P, OLIVEIRA BRETT A M. Catechin electrochemical oxidation mechanisms[J]. Analytica Chimica Acta, 2004, 518(1): 109-115.
32	LI Li, BIAN Yifan, ZHANG Xiaoxiao, et al. Process for recycling mixed-cathode materials from spent lithium-ion batteries and kinetics of leaching[J]. Waste Management, 2018, 71: 362-371.
33	YAO Lu, FENG Yong, XI Guoxi. A new method for the synthesis of LiNi_1/3Co_1/3Mn_1/3O₂ from waste lithium ion batteries[J]. RSC Advances, 2015, 5(55): 44107-44114.
34	LI Li, GE Jing, WU Feng, et al. Recovery of cobalt and lithium from spent lithium ion batteries using organic citric acid as leachant[J]. Journal of Hazardous Materials, 2010, 176(1): 288-293.
35	ZHENG Y, LONG H L, ZHOU L, et al. Leaching procedure and kinetic studies of cobalt in cathode materials from spent lithium ion batteries using organic citric acid as leachant[J]. 2016, 10: 159-168.
36	CHEN Xiangping, FAN Bailin, XU Liping, et al. An atom-economic process for the recovery of high value-added metals from spent lithium-ion batteries[J]. Journal of Cleaner Production, 2015, 112: 3562-3570.
37	CHEN Xiangping, ZHOU Tao. Hydrometallurgical process for the recovery of metal values from spent lithium-ion batteries in citric acid media[J]. Waste Management & Research, 2014, 32(11): 1083-1093.
38	NAYAKA G P, MANJANNA J, PAI K V, et al. Recovery of valuable metal ions from the spent lithium-ion battery using aqueous mixture of mild organic acids as alternative to mineral acids[J]. Hydrometallurgy, 2015, 151: 73-77.
39	SUN Liang, QIU Keqiang. Organic oxalate as leachant and precipitant for the recovery of valuable metals from spent lithium-ion batteries[J]. Waste Management, 2012, 32(8): 1575-1582.
40	ZENG Xianlai, LI Jinhui, SHEN Bingyu. Novel approach to recover cobalt and lithium from spent lithium-ion battery using oxalic acid[J]. Journal of Hazardous Materials, 2015, 295: 112-118.
41	GAO Wenfang, SONG Jiali, CAO Hongbin, et al. Selective recovery of valuable metals from spent lithium-ion batteries—Process development and kinetics evaluation[J]. Journal of Cleaner Production, 2018, 178: 833-845.
42	LI Li, QU Wenjie, ZHANG Xiaoxiao, et al. Succinic acid-based leaching system: A sustainable process for recovery of valuable metals from spent Li-ion batteries[J]. Journal of Power Sources, 2015, 282: 544-551.
43	NAYAKA G P, PAI K V, SANTHOSH G, et al. Dissolution of cathode active material of spent Li-ion batteries using tartaric acid and ascorbic acid mixture to recover Co[J]. Hydrometallurgy, 2016, 161: 54-57.
44	NAYAKA G P, PAI K V, MANJANNA J, et al. Use of mild organic acid reagents to recover the Co and Li from spent Li-ion batteries[J]. Waste Management, 2016, 51: 234-238.
45	MUSARIRI Bruce, AKDOGAN Guven, DORFLING Christie, et al. Evaluating organic acids as alternative leaching reagents for metal recovery from lithium ion batteries[J]. Minerals Engineering, 2019, 137: 108-117.
46	SHIH Yujen, CHIEN Shihkai, JHANG Syuruei, et al. Chemical leaching, precipitation and solvent extraction for sequential separation of valuable metals in cathode material of spent lithium ion batteries[J]. Journal of the Taiwan Institute of Chemical Engineers, 2019, 100: 151-159.
47	AALTONEN Miamari, PENG Chao, Benjamin WILSON P, et al. Leaching of metals from spent lithium-ion batteries[J]. Recycling, 2017, 2(4): doi: 10.3390/recycling2040020.
48	ZHANG Xiaoxiao, BIAN Yifan, XU Siwenyu, et al. Innovative application of acid leaching to regenerate Li(Ni_1/3Co_1/3Mn_1/3)O₂ cathodes from spent lithium-ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(5): 5959-5968.
49	LI L, LU J, ZHAI L, 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.
50	NATARAJAN S, BORICHA A B, BAJAJ H C. Recovery of value-added products from cathode and anode material of spent lithium-ion batteries[J]. Waste Management, 2018, 77: 455-465.
51	HONG Y K, HONG W H. Removal of acetic acid from aqueous solutions containing succinic acid and acetic acid by tri-n-octylamine[J]. Separation and Purification Technology, 2005, 42(2): 151-157.
52	LI Li, FAN Ersha, GUAN Yibiao, et al. Sustainable recovery of cathode materials from spent lithium-ion batteries using lactic acid leaching system[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(6): 5224-5233.
53	LEVENSPIEL Octave. Chemical reaction engineering[J]. John Wiley & Sons, 1972, doi: 10.1021/ie990488g. doi: 10.1021/ie990488g
54	ZHENG Ying, WANG Shiquan, GAO Yinglong, et al. Lithium nickel cobalt manganese oxide recovery via spray pyrolysis directly from the leachate of spent cathode scraps[J]. ACS Applied Energy Materials, 2019, 2(9): 6952-6959.
55	WU Caibin, LI Bensheng, YUAN Chengfang, et al. Recycling valuable metals from spent lithium-ion batteries by ammonium sulfite-reduction ammonia leaching[J]. Waste Management, 2019, 93: 153-161.
56	MENG Fei, LIU Qingcai, KIM Rina, et al. Selective recovery of valuable metals from industrial waste lithium-ion batteries using citric acid under reductive conditions: Leaching optimization and kinetic analysis[J]. Hydrometallurgy, 2020, 191: doi: 10.1016/j.hydromet.2019.105160.
57	GAO Guilan, HE Xin, LOU Xiaoyi, et al. A citric Acid/Na₂S₂O₃ system for the efficient leaching of valuable metals from spent lithium-ion batteries[J]. JOM, 2019, 71(10): 3673-3681.
58	ZHUANG Luqi, SUN Conghao, ZHOU Tao, et al. Recovery of valuable metals from LiNi_0.5Co_0.2Mn_0.3O₂ cathode materials of spent Li-ion batteries using mild mixed acid as leachant[J]. Waste Management, 2019, 85: 175-185.
59	ZHANG Xihua, CAO Hongbin, XIE Yongbing, et al. A closed-loop process for recycling LiNi_1/3Co_1/3Mn_1/3O₂ from the cathode scraps of lithium-ion batteries: Process optimization and kinetics analysis[J]. Separation and Purification Technology, 2015, 150: 186-195.
60	JHA M K, KUMARI A J, JHA A K, et al. Recovery of lithium and cobalt from waste lithium ion batteries of mobile phone[J]. Waste Management, 2013, 33(9): 1890-1897.
61	NAYL A A, ELKHASHAB R A, BADAWY S M, et al. Acid leaching of mixed spent Li-ion batteries[J]. Arabian Journal of Chemistry, 2017, 10: S3632-S3639.
62	DEMIRKıRAN N, KÜNKÜL A. Dissolution kinetics of ulexite in perchloric acid solutions[J]. International Journal of Mineral Processing, 2007, 83(1): 76-80.

[1]	周伟, 符冬菊, 刘伟峰, 陈建军, 胡照, 曾燮榕. 废旧磷酸铁锂动力电池回收利用研究进展[J]. 储能科学与技术, 2022, 11(6): 1854-1864.
[2]	赵志伟, 杨智, 彭章泉. 飞行时间二次离子质谱在锂基二次电池中的应用[J]. 储能科学与技术, 2022, 11(3): 781-794.
[3]	李月霞, 刘全兵. MXene基纳米材料在氧还原电催化中的应用[J]. 储能科学与技术, 2021, 10(6): 1918-1930.
[4]	李林林, 王昱杰, 门一飞, 杨伟, 邹汉波, 陈胜洲. 湿法冶金回收技术中无机酸作为浸出剂的研究进展[J]. 储能科学与技术, 2021, 10(1): 68-76.
[5]	聂雪娇, 郭晋芝, 王美怡, 谷振一, 赵欣欣, 杨旭, 梁皓杰, 吴兴隆. 以废旧锰酸锂正极为原料制备Li_0.25Na_0.6MnO₂钠离子电池正极材料的研究[J]. 储能科学与技术, 2020, 9(5): 1402-1409.
[6]	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.
[7]	陈永珍, 黎华玲, 宋文吉, 涂小琳, 冯自平. 废旧磷酸铁锂电池回收技术研究进展[J]. 储能科学与技术, 2019, 8(2): 237-247.
[8]	卫寿平，孙杰，周添，李吉刚，曹焕露. 废旧锂离子电池中金属材料回收技术研究进展[J]. 储能科学与技术, 2017, 6(6): 1196-.