(1. 北京工业大学 材料与制造学部，北京 100124；
2. 工业大数据应用技术国家工程实验室，北京 100124；
3. 荆门市格林美新材料有限公司，荆门 448124；
4. 国家电子废弃物循环利用工程技术研究中心，荆门 448124；
5. 格林美股份有限公司，深圳 518101)
摘 要: 通过高温氢还原和湿法冶金联用的方法回收报废动力电池镍钴锰酸锂三元正极材料中的镍、钴、锰以及锂金属，并对其回收机理及工艺进行研究。结果表明：报废三元正极材料经过高温氢气还原后，在层状镍钴锰酸锂结构中的锂迁移到表面，变成LiOH、LiOH？H2O和少量的Li2CO3；镍钴锰由之前的Co2+、Ni3+和Mn4+分别还原成了Co0、Ni0和 MnO，其在还原水洗后物料的表面相分别为Ni(OH)2和Co(OH)2及MnO；还原后的LiOH、LiOH？H2O和少量的Li2CO3经过水浸、酸洗、沉淀后，可得纯度为99.5%的Li2CO3，实现了锂与镍、钴、锰的分离；还原后的镍、钴和MnO经过硫酸酸浸后，镍、钴和锰浸出率分别为96.88%、97.23%和99.78%。浸出后溶液经氧化沉淀及萃取分离，锰沉淀分离率为98.46%，萃取分离后氯化钴和氯化镍溶液杂质含量低于10 mg/L。
关键字: 镍钴锰酸锂；三元正极材料；报废；氢气还原；回收；机理
（1. College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China;
2. National Engineering Laboratory for Industrial Big-data Application Technology, Beijing 100124, China;
3. GEM Jingmen New Material Co., Ltd., Jingmen 448124, China;
4. Chinese National WEEE Recycling Engineering Research Center, Jingmen 448124, China;
5. GEM Co., Ltd., Shenzhen 518101, China）
Abstract:The nickel, cobalt, manganese and lithium metals in the ternary cathode material of scrapped power battery were recovered by high temperature hydrogen reduction and hydrometallurgical method, and the recovery mechanism and process were studied. The results show that the Li in the layered Ni-Co-Mn oxide migrates to the surface and becomes LiOH, LiOH？H2O and a small amount of Li2CO3 after high temperature reduction. The Co2+, Ni3+ and Mn4+ are reduced to Co0, Ni0 and MnO, respectively. And the surface phases of the reduced materials are referred as Ni(OH)2, Co(OH)2 and MnO after Li leaching. The Li2CO3 with 99.5% in purity is obtained from the water leaching, acid washing, and precipitation processes of LiOH, LiOH？H2O and a small amount of Li2CO3, which realizes the separation of Li from Co-Ni-Mn. After the sulfuric acid leaching of the reduced Ni, Co and MnO, the leaching rates of Ni, Co and Mn are 96.88%, 97.23% and 99.78%, respectively. The precipitation and separation rate of Mn is 98.46% after the oxidizing precipitation and extraction separation of the leached solution, and the impurity contents in CoCl2 and NiCl2 solutions are less than 10 mg/L after the extraction separation.
Key words: LiNi1/3Co1/3Mn1/3O2; ternary cathode materials; waste; hydrogen reduction; recovery; mechanism
