School of Environment Science and Spatial Informatics, China University of Mining and Technology, No.1 Daxue Road, Xuzhou, Jiangsu 221116, China.
School of Chemical Engineering and Technology, China University of Mining and Technology, No.1 Daxue Road, Xuzhou, Jiangsu 221116, China.
Waste Manag. 2020 Sep;115:113-120. doi: 10.1016/j.wasman.2020.05.030. Epub 2020 Jul 29.
Liberation and reduction of cathode material are the necessary procedures for improving the recycling efficiency of cathode material derived from spent lithium-ion batteries. In this research work, a pyrolysis technology was utilized to remove the organic binder and enhance liberation of electrode materials. At the same time, pyrolysis treatment can facilitate the thermal-reduction of Co in LiCoO to Co with surface organics, which lays a foundation for the subsequent reductant-free acid leaching. Results indicate that the crystal structure of pure LiCoO is not changed at a pyrolysis temperature of 600 °C, but LiCoO transforms to CoO, LiCO, LiF, and LiO under the reduction action of HF, pyrolytic carbon, and additive carbon black. Water-impact crushing is synchronized with water-leaching to separate electrode materials from aluminum foil and recover Li element. Afterwards, reductant-free acid leaching technology can be utilized to recycle Li and Co from spent LiCoO batteries. Recovery efficiency of Li element in water-leaching process was up to 92.17% while the remaining 7.83% of Li and all Co elements were recovered during reductant-free acid leaching process. Based on the foundation analysis, the green chemical process for recovering valuable metals from spent lithium-ion batteries was proposed.
阴极材料的解放和还原是提高废旧锂离子电池阴极材料回收效率的必要步骤。在这项研究工作中,采用了热解技术去除有机粘结剂并促进电极材料的解放。同时,热解处理可以促进 LiCoO 中的 Co 在表面有机物的作用下进行热还原为 Co,这为后续无还原剂酸浸奠定了基础。结果表明,在 600°C 的热解温度下,纯 LiCoO 的晶体结构不会发生变化,但在 HF、热解碳和添加剂炭黑的还原作用下,LiCoO 转化为 CoO、LiCO、LiF 和 LiO。水冲击破碎与水浸同步进行,以将电极材料从铝箔中分离出来并回收 Li 元素。然后,可以利用无还原剂酸浸技术从废旧 LiCoO 电池中回收 Li 和 Co。水浸过程中 Li 元素的回收率高达 92.17%,而无还原剂酸浸过程中则回收了剩余的 7.83%的 Li 和所有 Co 元素。基于基础分析,提出了从废旧锂离子电池中回收有价金属的绿色化学工艺。