Xu Meiling, Kang Shumei, Jiang Feng, Yan Xinyong, Zhu Zhongbo, Zhao Qingping, Teng Yingxue, Wang Yu
School of Materials and Metallurgy, University of Science and Technology Liaoning Anshan 114051 China
Department of Materials Science and Engineering, Southern University of Science and Technology Shenzhen 518055 China.
RSC Adv. 2021 Aug 16;11(44):27689-27700. doi: 10.1039/d1ra04979h. eCollection 2021 Aug 9.
There is great economic and environmental value in recovering valuable metal ions from spent lithium-ion batteries (LIBs). A novel method that employs organic acid recovery using citric acid and salicylic acid was used to enhance the leaching of metal ions from the cathode materials of spent LIBs. The effects of the acid concentration, reducing agent content, solid to liquid (S : L) ratio, temperature, and leaching time were systematically analyzed and the optimal acid leaching process condition was determined through the results. The kinetics of the leaching process with different temperatures was analyzed to explore and verify the relationship between the leaching mechanism and temperature. The results of TG/DSC analysis showed that the optimum calcination temperature was 500 °C for 1 h and 600 °C for 3 h. The XRD and micromorphology analysis results showed that cathode material powders without impurities were obtained after pretreatment. The experimental results demonstrated that the optimal leaching efficiencies of the metals ions were 99.5% Co and 97% Li and the optimal corresponding condition was 1.5 M citric acid, 0.2 M salicylic acid, a 15 g L S : L ratio, 6 vol% HO, 90 °C, and 90 min. Afterward, the infrared tests and SEM morphologies results indicated that only salicylic acid was present in the residue after filtration because of the microsolubility of the salicylic acid. Finally, it was obvious that the temperature had a great influence on the leaching process as observed through the kinetics and thermodynamics analyses, while the values for Co and Li were obtained as 37.96 kJ mol and 25.82 kJ mol through the kinetics model. The whole process was found to be efficient and reasonable for recovering valuable metals from the industrial electrodes of spent LIBs.
从废旧锂离子电池(LIBs)中回收有价值的金属离子具有巨大的经济和环境价值。一种采用柠檬酸和水杨酸进行有机酸回收的新方法被用于提高废旧LIBs正极材料中金属离子的浸出率。系统分析了酸浓度、还原剂含量、固液比(S : L)、温度和浸出时间的影响,并根据结果确定了最佳酸浸工艺条件。分析了不同温度下浸出过程的动力学,以探索和验证浸出机理与温度之间的关系。热重/差示扫描量热分析(TG/DSC)结果表明,最佳煅烧温度为500℃ 1小时和600℃ 3小时。X射线衍射(XRD)和微观形貌分析结果表明,预处理后得到了无杂质的正极材料粉末。实验结果表明,金属离子的最佳浸出效率为钴99.5%、锂97%,最佳相应条件为1.5 M柠檬酸、0.2 M水杨酸、15 g/L固液比、6 vol%过氧化氢、90℃和90分钟。随后,红外测试和扫描电子显微镜(SEM)形貌结果表明,由于水杨酸的微溶性,过滤后的残渣中仅存在水杨酸。最后,通过动力学和热力学分析可以明显看出温度对浸出过程有很大影响,而通过动力学模型得到钴和锂的值分别为37.96 kJ/mol和25.82 kJ/mol。结果表明,整个过程对于从废旧LIBs的工业电极中回收有价值的金属是高效且合理的。