摘要
短流程回收废旧锂离子电池中的有价金属是保障新能源产业原料供给的重点挑战方向。本工作基于硫化法基本原理,采用Factsage 7.3热力学软件,对三类典型硫化剂[S_(8)、SO_(2)、硫化矿(FeS,CuFeS_(2),ZnS)]硫化正极材料LiCoO_(2)的过程开展热力学分析,系统研究了硫化温度、硫化剂用量对硫化产物的影响。结果表明,上述硫化剂在热力学上均可实现对LiCoO_(2)的硫化,Li被硫化成水溶性的Li_(2)S或Li_(2)SO_(4),Co则生成难溶于水的硫化物或氧化物,结合浸出分离实验可实现Li与Co的高效分离。硫化回收实验研究表明,三类硫化剂对LiCoO_(2)均可实现不同程度的硫化,其中S_(8)受反应动力学影响,硫化效果最差,硫化率仅为2.51%;SO_(2)单独作为硫化剂时硫化效果较差,硫化率为34.07%,而与还原剂C协同作用时,硫化率显著提升至72.03%;硫化矿中,ZnS的硫化效果最优,硫化率达96.14%,CuFeS_(2)和FeS的硫化效果则相对较差。本研究可为短流程回收废旧锂离子电池中的有价金属提供新思路。
The short-process recycling of valuable metals in waste lithium-ion batteries is a key challenge for ensuring the supply of raw materials for the new energy industry.With the development of the new energy industry,achieving the short-process recycling of valuable metals in waste lithium-ion batteries is an important link in the new energy industry chain.Based on the basic principle of the sulfurization method,the thermodynamic analysis of the sulfurization of LiCoO_(2)positive electrode materials with three typical sulfurizing agents[S_(8),SO_(2),sulfide minerals(FeS,CuFeS_(2),ZnS)]was carried out using Factsage 7.3 thermodynamic software.The effects of sulfurization temperature and sulfurizing agent dosage on the sulfurization products were studied.Through software simulation calculations,it was proved that all sulfurizing agents can thermodynamically sulfurize LiCoO_(2).Li in LiCoO_(2)was sulfurized into water-soluble Li_(2)S or Li_(2)SO_(4),while Co generates sulfides or oxides that were insoluble in water.Through leaching separation experiments,efficient separation of Li and Co was achieved.The results of the sulfurization recovery experiment showed that the three types of sulfurizing agents can achieve different degrees of sulfurization on LiCoO_(2).Among them,S_(8)was affected by reaction kinetics and had the worst sulfurization effect,with a sulfurization rate of only 2.51%;SO_(2)had a poor sulfurization effect when used as a sulfurizing agent,with a sulfurization rate of 34.07%,while when SO_(2)and the reducing agent C synergistically sulfurize,the sulfurization rate increased significantly to 72.03%.When sulfide minerals were used as sulfurizing agents,ZnS showed the best sulfurization effect,with a sulfurization rate of 96.14%,while the sulfurization effects of both CuFeS_(2)and FeS were quite poor.This study can provide new ideas for the short-process recovery of valuable metals in waste Li-ion batteries.
作者
陈世梁
管修涛
樊友奇
王鑫
郭志鹏
李虎
谭文龙
丁超
吴健
赵森
姚永林
Shiliang CHEN;Xiutao GUAN;Youqi FAN;Xin WANG;Zhipeng GUO;Hu LI;Wenlong TAN;Chao DING;Jian WU;Sen ZHAO;Yonglin YAO(School of Metallurgical Engineering,Anhui University of Technology,Ma'anshan,Anhui 243002,China;Anhui Province Joint Construction Key Laboratory of Green and Low-carbon Copper Smelting and Resource Recycling Technology,Tongling Nonferrous Metals Group Co.,Ltd.,Tongling,Anhui 244000,China;Green Development of Copper Industry Chain Anhui Industrial Innovation Research Institute,Tongling Nonferrous Metals Group Co.,Ltd.,Tongling,Anhui 244000,China)
出处
《过程工程学报》
北大核心
2025年第7期717-727,共11页
The Chinese Journal of Process Engineering
基金
安徽省自然科学基金资助项目(编号:2308085QE155,2308085ME151)
安徽省教育厅高校自然科学研究项目(编号:KJ2020A0224)。
