以海底多金属锰结核制备三元正极材料前驱体Ni0.5Co0.2Mn0.3(OH)2  

Preparation of ternary cathode material precursor Ni0.5Co0.2Mn0.3(OH)2 from seafloor polymetallic nodules

作　　者：钟志杰 徐徽 杨喜云 王小弟 伍玲龙 陈志鑫 ZHONG Zhi-jie;XU Hui;YANG Xi-yun;WANG Xiao-di;WU Ling-long(School of Metallurgy and Environment,Central South University,Changsha 410083,China)

机构地区：[1]中南大学冶金与环境学院,长沙410083

出　　处：《中国有色金属学报》2020年第11期2605-2615,共11页The Chinese Journal of Nonferrous Metals

基　　金：国家自然科学基金资助项目(51574286)。

摘　　要：以海底多金属结核资源为原料,采用硫酸浸出−净化除杂−配合沉淀的工艺制备三元正极材料前驱体Ni0.5Co0.2Mn0.3(OH)2。在硫酸浸出过程中,考察温度、液固比、硫酸浓度、浸出时间对镍、钴、锰浸出率的影响,探究镍、钴、锰元素浸出动力学。结果表明:在温度200℃、液固比6:1、硫酸浓度350 g/L、浸出时间90 min条件下,镍、钴浸出率达到95%以上,锰浸出率仅为6.43%,实现镍、钴与少部分锰的浸出。当温度在120~200℃之间时,锰浸出过程受扩散控制,表观活化能为10.64 kJ/mol;镍、钴浸出过程受混合控制,表观活化能分别为27.60和38.16 kJ/mol。浸出液经黄钠铁矾法除铁、硫化锰除铜、碳酸氢铵水解沉淀除铝、P204萃取除钙后,采用P204萃取镍、钴、锰,得到硫酸镍、硫酸钴和硫酸锰的混合液,经调节镍钴锰比例后,用氨水−氢氧化钠配合共沉淀法制备得到球形的Ni0.5Co0.2Mn0.3(OH)2,可用于制备三元正极材料。With seafloor polymetallic nodules as raw materials,ternary cathode material precursor Ni0.5Co0.2Mn0.3(OH)2 was prepared through a process of sulfuric acid leaching-purification-precipitation.In the process of sulfuric acid leaching,the effects of temperature,liquid-solid ratio,sulfuric acid concentration and leaching time on the leaching efficiency of nickel,cobalt and manganese were investigated.The leaching kinetics of nickel,cobalt and manganese were explored.The results show that the leaching efficiencies of nickel and cobalt are greater than 95%,and that for manganese is only 6.43%under the conditions of temperature of 200℃,liquid-solid ratio of 6:1,sulfuric acid concentration of 350 g/L,and leaching time of 90 min.Nickel and cobalt are selective leaching.At 120−200℃,the leaching process of Mn is controlled by diffusion with apparent activation energy of 10.64 kJ/mol.The leaching processes of Ni and Co are controlled by both diffusion and chemical reaction with apparent activation energy of 27.60 and 38.16 kJ/mol,respectively.Fe3+ion in the leaching liquor is removed using sodium jarosite,copper is removed with manganese sulfide,and aluminum is precipitated as aluminum hydroxide as well as calcium is extracted by P204.A mixture of pure nickel sulfate,cobalt sulfate and manganese sulfate is then obtained through solvent extraction.The spherical Ni0.5Co0.2Mn0.3(OH)2,ternary cathode material precursor,is prepared by ammonia-sodium hydroxide coprecipitation after adjusting the molar ratio of nickel sulfate,cobalt sulfate and manganese sulfate.

关 键 词：三元前驱体 正极材料 海底多金属锰结核 浸出 除杂 

分 类 号：P744.3[天文地球—海洋科学]