邹小刚,马文君,牛国平,梁志远,周飞,赵钦新,李文锋

• 1:西安西热锅炉环保工程有限公司
• 2:西安交通大学热流科学与工程教育部重点实验室

摘要(Abstract)：

传统湿法冶金回收锂电池的过程不仅消耗腐蚀性强酸、反应时间长，且产生二次污染物。使用微波辅助的低共熔溶剂（DES）浸取回收正极材料钴酸锂LiCoO_2(LCO)中有价金属，浸取回收过程不仅绿色低污染，且反应速率快、有价金属溶解稳定性好、回收产物纯度较高。同时采用FT-IR、XRD、ICP-MS、SEM和电化学分析方法探究微波辅助DES浸取LCO中有价金属的机理。通过正交实验法得到各个实验因素对有价金属浸取效率的影响程度为DES种类>温度>液固比>时间。根据影响程度采用单因素实验法获得最佳浸取条件为：采用氯化胆碱-草酸在液固比为60 mL/g、温度为180℃、时间为10 min条件下可浸取99.86%Li和99.05%Co，此时Co以更稳定的甲酸钴形式存在。最后，提出一条绿色高效的微波辅助DES回收LCO技术路线，为废旧锂电池中有价金属的回收提供重要的参考方法。

关键词(KeyWords)： 锂电池;低共熔溶剂;微波;湿法回收;钴酸锂

Abstract:

Keywords:

基金项目(Foundation): 中国华能集团有限公司总部科技项目（HNKJ21-HF58）;; 国家重点研发计划项目（2021YFC3001803）;; 陕西省青年科技新星项目（2022KJXX-51） ~~

作者(Author): 邹小刚,马文君,牛国平,梁志远,周飞,赵钦新,李文锋

DOI: 10.19666/j.rlfd.202212209

参考文献(References)：

• [1] HUANG X. Research on short process recycling of ternary cathode materials for waste Lithium ion power battery[D]. Beijing:General Research Institute for Nonferrous Metals, 2019:1.
• [2] LI L, LIANG Y, CHEN L, et al. Research progress on recovery of Cobalt and nickel from waste batteries[J].China Nonferrous Metallurgy, 2008, 4(3):57-60.
• [3] ZHANG X, LI L, FAN E, et al. Toward sustainable and systematic recycling of spent rechargeable batteries[J].Chemical Society Reviews, 2018, 47(19):7239-7302.
• [4] FAN E, LI L, WANG Z, et al. Sustainable recycling technology for Li-ion batteries and beyond:challenges and future prospects[J]. Chemical Reviews, 2020,120(14):7020-7063.
• [5] LIU C, LIN J, CAO H, et al. Recycling of spent lithiumion batteries in view of lithium recovery:a critical review[J]. Journal of Cleaner Production, 2019, 228:801-813.
• [6] HARPER G, SOMMERVILLE R, KENDRICK E, et al.Recycling lithium-ion batteries from electric vehicles[J].Nature, 2019, 575(7781):75-86.
• [7] ZHANG X, CAO H, XIE Y, et al. A closed-loop process for recycling LiNi1/3Co1/3Mn1/3O2 from the cathode scraps of lithium-ion batteries:process optimization and kinetics analysis[J]. Separation and Purification Technology, 2015, 150:186-195.
• [8] LI L, GE J, WU F, 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.
• [9] SANTOS C D, ALVES J C, SILVA S, et al. A closed-loop process to recover Li and Co compounds and to resynthesize LiCoO2 from spent mobile phone batteries[J]. Journal of Hazardous Materials, 2019, 362:458-466.
• [10] TRAN M K, RODRIGUES M-T F, KATO K, et al. Deep eutectic solvents for cathode recycling of Li-ion batteries[J]. Nature Energy, 2019, 4(4):339-345.
• [11] CHEN Y, LU Y, LIU Z, et al. Efficient dissolution of lithium-ion batteries cathode LiCoO2 by polyethylene glycol-based deep eutectic solvents at mild temperature[J]. ACS Sustainable Chemistry&Engineering, 2020,8(31):11713-11720.
• [12] LU B, DU R, WANG G, et al. High-efficiency leaching of valuable metals from waste Li-ion batteries using deep eutectic solvents[J]. Environmental Research, 2022, 212:113286.
• [13] SCHIAVI P G, ALTIMARI P, BRANCHI M, et al.Selective recovery of cobalt from mixed lithium ion battery wastes using deep eutectic solvent[J]. Chemical Engineering Journal, 2021, 417:129249-129258.
• [14] LU Q, CHEN L, LI X, et al. Sustainable and convenient recovery of valuable metals from spent Li-ion batteries by a one-pot extraction process[J]. ACS Sustainable Chemistry&Engineering, 2021, 9(41):13851-13861.
• [15] XU Z, SHAO H, ZHAO Q, et al. Use of microwaveassisted deep eutectic solvents to recycle lithium manganese oxide from Li-ion batteries[J]. The Minerals,Metals&Materials Society, 2021, 73(7):2104-2110.
• [16] LIU M, MA W, ZHANG X, et al. Recycling lithium and cobalt from LIBs using microwave-assisted deep eutectic solvent leaching technology at low-temperature[J].Materials Chemistry and Physics, 2022, 289:126466-126475.
• [17]张盈盈,陆小华,冯新,等.胆碱类低共熔溶剂的物性及应用[J].化学进展, 2013, 25(6):881-892.ZHANG Yingying, LU Xiaohua, FENG Xin, et al.Properties and applications of choline based deep eutectic solvents[J]. Chemistry Progress, 2013, 25(6):881-892.
• [18] SMITH E L, ABBOTT A P, RYDER K S. Deep eutectic solvents(DESs)and their applications[J]. Chemical Reviews, 2014, 114(21):11060-11082.
• [19] CHEN W, XUE Z, WANG J, et al. Investigation on the Thermal stability of deep eutectic solvents[J]. Acta Physico-Chimica Sinica 2018, 34(8):904-911.
• [20] CHANG X, FAN M, GU C F, et al. Selective extraction of transition metals from spent LiNixCoyMn1-x-yO2cathode via regulation of coordination environment[J].Angewandte Chemie International Edition, 2022, 61(24):e202202558.
• [21] CHEN L, CHAO Y, LI X, et al. Engineering a tandem leaching system for the highly selective recycling of valuable metals from spent Li-ion batteries[J]. Green Chemistry, 2021, 23(5):2177-2184.
• [22] YUE D, JIA Y, YAO Y, et al. Structure and electrochemical behavior of ionic liquid analogue based on choline chloride and urea[J]. Electrochimica Acta,2012, 65:30-36.
• [23] CAO X, XU L, SHI Y, et al. Electrochemical behavior and electrodeposition of cobalt from choline chloride-urea deep eutectic solvent[J]. Electrochimica Acta, 2019, 295:550-557.
• [24] WANG S, ZHANG Z, LU Z, et al. A novel method for screening deep eutectic solvent to recycle the cathode of Li-ion batteries[J]. Green Chemistry, 2020, 22(14):4473-4482.
• [25]许溢群. GL/IL复配增塑PVA纤维的熔纺制备及其结构性能研究[D].上海:东华大学, 2020:1.XU Yiqun. Preparation and structure properties of GLIL compound plasticized PVA fiber by melt-spinning[D].Shanghai:Donghua University, 2020:1.
• [26] GONG S, WU T, WANG G, et al. Selection of deep eutectic solvent based on high efficiency recovery of cathode material of waste lithium ion battery[J]. Chinese Journal of Chemistry, 2021, 42(10):3151-3159.
• [27] CHANG J, WANG J, LIU Y, et al. Preparation of plasticizer by epoxidation of soybean oil catalyzed by deep eutectic ionic liquid[J]. Journal of South China University of Technology(Natural Science Edition),2018, 46(2):94-101.
• [28] MORINA R, CALLEGARI D, MERLI D, et al. Cathode active material recycling from spent lithium batteries:a green(circular)approach based on deep eutectic solvents[J]. Chemsuschem, 2021, 15(2):e202102080.
• [29] STEFANESCU M, STOIA M, STEFANESCU O.Thermal and FT-IR study of the hybrid ethylene-glycol–silica matrix[J]. Journal of Sol-Gel Science and Technology, 2006, 41(1):71-78.
• [30] BARAN E J. Review:natural oxalates and their analogous synthetic complexes[J]. Journal of Coordination Chemistry, 2014, 67(23/24):3734-3768.
• [31] PEETERS N, BINNEMANS K, RIA?O S.Solvometallurgical recovery of cobalt from lithium-ion battery cathode materials using deep-eutectic solvents[J].Green Chemistry, 2020, 22(13):4210-4221.
• [32] CHEN K, LI Y, ZHANG C, et al. Experimental study of the hydrothermal reactivity of oxalic acid under high pressure[C]. IOP Conference Series:Earth and Environmental Science, 2020.
• [33]关颖,郭西华,邸立杰,等.太空育种中药材防风的FTIR分析与表征[J].光谱学与光谱分析, 2008, 28(6):1283-1285.GUAN Ying, GUO Xihua, DI Lijie, et al. FTIR analysis and characterization of Chinese medicinal materials for space breeding[J]. Spectroscopy and Spectral Analysis,2008, 28(6):1283-1285.
• [34]伍德佑,刘志强,饶帅,等.不同沉淀剂对废旧锂离子电池中锂回收的对比研究[J].有色金属(冶炼部分),2022, 8(7):36-40.WU Deyou, LIU Zhiqiang, RAO Shuai, et al.Comparative study on recovery of lithium from waste lithium ion batteries with different precipitators[J]. Nonferrous Metals(Smelting Part), 2022, 8(7):36-40.