(此文档为word格式，下载后您可任意编辑修改！)
南京大学
从废旧锂电池中分离回收钴的工艺研究
学院名称： 化学与环境工程学院 专 业： 应用化学 班 级： 学 号： 姓 名： 指导教师姓名： 指导教师职称：
二〇一三 年 六 月
从废旧锂电池中分离回收钴的工艺研究
摘要：随着锂离子电池产量和应用的增多，废弃锂离子电池的处置己经成为一
个日益迫切的问题。在众多处置方案中，再生处理是目前的研究热点，同时也是最具发展前途的方案,它不仅可以解决报废锂离子电池所带来的一系列环境问题，而且对电池中有价金属进行回收并循环利用，有效的缓解了资源的紧张。本课题对从废旧锂电池中分离回收钴的工艺进行了研究，提出了以 H2SO4溶液为介质,以硫代硫酸钠固体为还原剂,于80 ℃搅拌2.5 h ,溶解锂离子电池中的LiCoO2’ 溶解液中的Li+ 和Co2+ 用NaOH溶液为沉淀剂进行分离; Co (OH) 2沉淀先经过提纯,提纯后的试样在800 ℃下煅烧4 h ,可回收得到Co3O4。Co的纯度达到91.23 %。母液中Li+加固体Na2CO3处理,沉淀后重结晶,得到Li2CO3。Li的纯度达93.5 %。
关键词：锂离子电池; 钴酸锂; 硫代硫酸钠; 回收; 浸出
Research of recycling cobalt from the waste Lithium-ion batteries
Abstract: Disposal of spent lithium-ion batteries(LIBS) has becoming more and
more important with the growth of production and use of LIBS. Recycling treatment has attracted more and more attentions. Compared to other methods of treatment, recycling can not only resolves environmental problems, but also slows the lack of resource effectively by recovering and reusing of valued metals from LIBS. This project study the craft from the waste separation and recovery of cobalt in lithium battery.The process of dissolving LiCoO2 in Li-ion battery made by Na2S2O3 solution under 80 ℃milled for 2.5 h with H2SO4 solution was studied. The separation of Li+ and Co2+ in solution could be realized by adopting NaOH solution as precipitator , Co3O4 was obtained after Co (OH)
2 had been purified and calcined for 4h under 800℃, its purity was 94.2 %. The Li
+
in
pregnant liquor was concentrated by adding solid Na2CO3 and Li2CO3 was collected after serious of crystallization, the purity was 93.5 %.
Key words: Li-ion battery ; LiCoO2 ; Na2S2O3 ; recovery ; leach
目 录
第一章 前 言 ........................................... 1
1.1 研究本课题的意义和目的 .................................................................... 1 1.2 国内外本领域科技创新发展概况和最新发展趋势 ..................................... 1
1.2.1锂离子电池的发展概况 ..................................................................... 1 1.2.2 锂离子电池的结构及材料组成 ............................................................. 2 1.2.3 废锂离子电池回收利用的必要性 .......................................................... 3 1.2.4 国家相关法规政策 .......................................................................... 5 1.2.5废锂离子电池资源化技术 ................................................................... 5 1.2.6 电极材料的浸出 ............................................................................. 9 1.2.7 浸出液中金属的提取和分离 ............................................................... 9
1.3 废锂离子电池中金属回收研究开发现状的国内外比较 .............................. 12
1.3.1 废锂离子电池重金属回收研究开发现状 ................................................ 12 1.3.2 国内外技术比较 ........................................................................... 13
1.4 本课题的研究内容和方案 ................................................................... 14
1.4.1主要研究内容 .............................................................................. 14 1.4.2 研究方案 ................................................................................... 15
第二章 实验材料与方法 ................................... 16
2.1 实验工艺流程及原理 ......................................................................... 16
2.1.1 实验工艺流程图 ........................................................................... 16 2.1.2工艺流程及原理 ........................................................................... 16
2.2 试剂和仪器 ..................................................................................... 18 2.3 实验步骤 ........................................................................................ 19
2.3.1 预处理 ..................................................................................... 19 2.3.2 浸出及其它实验步骤 ..................................................................... 19
2.3.3 铜离子的定性分析 ........................................................................ 20 2.3.4 四氧化三钴中钴含量的定量分析 ........................................................ 20
第三章 实验结果与讨论 .................................. 22
3.1 用硫代硫酸钠还原钴酸锂 ................................................................... 22
3.1.1 试样化学成分 ............................................................................. 22 3.1.2 酸性条件下Na2S2O3对试样的还原 ...................................................... 22 3.1.3 Co2+与Li+ 的分离与回收 ................................................................. 23 3.1.4 溶解的酸度及硫代硫酸钠代替双氧水 ................................................... 23 3.1.5 结论 ........................................................................................ 23
3.2 四氧化三钴中钴含量的测定—EDTA滴定法 .......................................... 24 3.3 清洁回收生产工艺的研究 ................................................................... 24 3.4 Co3O4的XRD分析 ........................................................................... 25 3.5 Li2CO3的XRD分析 .......................................................................... 25
第四章 总 结 ......................................... 26
4.1钴的回收与四氧化三钴的制备 ............................................................. 26 4.2碳酸锂的回收与制备 ......................................................................... 26 4.3结论 ............................................................................................... 26
参考文献 .............................................. 27
附录 ....................................................................................................... 31
致谢 ....................................................................................................... 32