(1. 北京工業(yè)大學(xué) 材料與制造學(xué)部，北京 100124；
2. 工業(yè)大數(shù)據(jù)應(yīng)用技術(shù)國家工程實(shí)驗(yàn)室，北京 100124；
3. 荊門市格林美新材料有限公司，荊門 448124；
4. 國家電子廢棄物循環(huán)利用工程技術(shù)研究中心，荊門 448124；
5. 格林美股份有限公司，深圳 518101)
摘 要: 通過高溫氫還原和濕法冶金聯(lián)用的方法回收報(bào)廢動力電池鎳鈷錳酸鋰三元正極材料中的鎳、鈷、錳以及鋰金屬，并對其回收機(jī)理及工藝進(jìn)行研究。結(jié)果表明：報(bào)廢三元正極材料經(jīng)過高溫氫氣還原后，在層狀鎳鈷錳酸鋰結(jié)構(gòu)中的鋰遷移到表面，變成LiOH、LiOH？H2O和少量的Li2CO3；鎳鈷錳由之前的Co2+、Ni3+和Mn4+分別還原成了Co0、Ni0和 MnO，其在還原水洗后物料的表面相分別為Ni(OH)2和Co(OH)2及MnO；還原后的LiOH、LiOH？H2O和少量的Li2CO3經(jīng)過水浸、酸洗、沉淀后，可得純度為99.5%的Li2CO3，實(shí)現(xiàn)了鋰與鎳、鈷、錳的分離；還原后的鎳、鈷和MnO經(jīng)過硫酸酸浸后，鎳、鈷和錳浸出率分別為96.88%、97.23%和99.78%。浸出后溶液經(jīng)氧化沉淀及萃取分離，錳沉淀分離率為98.46%，萃取分離后氯化鈷和氯化鎳溶液雜質(zhì)含量低于10 mg/L。
關(guān)鍵字: 鎳鈷錳酸鋰；三元正極材料；報(bào)廢；氫氣還原；回收；機(jī)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
