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研究生： 儲涵
Han Chu
論文名稱： 微波輔助萃取廢鋰電池中有價金屬
Microwave-Assisted Leaching of Valuable Metals from Spent Li-ion Batteries
指導教授： 劉志成
Jhy-Chern Liu
口試委員: 陳嘉明
王丞浩
何豐謀
學位類別： 碩士
Master
系所名稱： 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年： 2018
畢業學年度： 106
語文別： 中文
論文頁數： 112
中文關鍵詞： 抗壞血酸 、鈷 、萃取 、鋰 、微波系統 、廢鋰電池
外文關鍵詞： Ascorbic acid, cobalt, leaching, lithium, microwave, spent Li-ion batteries(LIBs)
相關次數： 點閱：229  下載：12 
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    • 鋰電池(LIBs)具有高能量密度、重量輕以及高性能等特性，因此被廣泛應用於可攜式電子設備中。全球鋰電池的使用越來越普遍，如何處理廢鋰電池成為一大課題。鋰電池中含有有價金屬鈷及鋰，將鋰電池拆解分類後再回收提取價值較高的物質是一較經濟且環保的作法。其中，酸萃取法常作為回收廢鋰電池的技術，但此技術較耗時。因此，本研究利用微波輔助萃取法回收廢鋰電池中的鈷、鋰、錳，此技術較環境友善且具成本效益，其中比較鹽酸、硫酸、醋酸和抗壞血酸在不同濃度(0.5-1.5 N)、固液比(10-40 g/L)以及微波功率(100-300 W)下之萃取效果，結果顯示使用抗壞血酸進行萃取最能有效溶解正極材料。抗壞血酸具有強還原性，因此可以有效提升鈷和錳的萃取效果。關於酸強度的影響，可得知萃取效果隨著濃度增加而提升，當鹽酸為0.5 N、固液比為10 g/L、微波功率為300 W時，在5分鐘內鈷、鋰、錳的萃取效果分別可達44.74%、87.92%、47.57%。當鹽酸濃度提升為1.5 N時，鈷、鋰、錳的萃取效果提升至80.09%、102.81%、69.80%。而使用0.5 N抗壞血酸時，鈷、鋰、錳的萃取效果分別可達113.03%、101.13%、111.13%。從實驗中也證實在萃取過程中，氫離子濃度及錯合物的形成也會影響萃取效果。相較於傳統萃取法，微波輔助萃取法可在短時間獲得較高的萃取效果。因此，微波輔助萃取法可作為回收廢鋰電池中有價金屬最有潛力的技術之一。

    Lithium-ion batteries (LIBs) have been widely used for energy storage because of their high energy density, lightweight, and durability. The amount of spent LIBs increased rapidly recently. Recovery of metals from spent lithium-ion batteries (LIBs) is essential for sustainable utilization of resources. Acid leaching is commonly used for leaching of metals from spent LIBs. However, it could be time-consuming. Microwave-assisted leaching is studied for leaching of cobalt (Co), lithium (Li), and manganese (Mn) from spent LIBs as a cost-effective, green, and environmentally friendly method.
    Effects of parameters such as acid types (HCl, H2SO4, CH3COOH, and ascorbic acid), acid concentration (0.5-1.5 N), solid to liquid ratio (10-40 g/L), and microwave power (100-300 W) were investigated. When at 10 g/L solid to liquid ratio, microwave power of 300 W, and 5 min of reaction time, the leaching efficiency of Co, Li, and Mn were 44.74, 87.92%, and 47.57%, respectively using 0.5 N of HCl. It increased to 80.09% for Co, 102.81% for Li, and 69.80% for Mn as HCl concentration increased to 1.5 M. And the leaching efficiency of Co, Li, and Mn were 113.03, 101.13%, and 111.13%, respectively using 0.5 N of ascorbic acid. It was found that the leaching of Co and Mn were significantly dependent on the reducibility of acid. Ascorbic acid has high reducibility which can leach Co, Li, and Mn effectively. The hydrogen ion concentration and complex formation between metals and acid are also involved in the leaching process. Compared with conventional leaching, microwave-assisted leaching was more efficient and required shorter reaction time. This method offers high potential to be applied for recycling of spent LIBs.

    內容 摘要 I Abstract II Acknowledgment III Contents IV List of Figures VI List of Tables VIII CHAPTER 1 1-1 1.1 Background 1-1 1.1 Objectives 1-2 CHAPTER 2 2-1 2.1 Lithium-ion batteries 2-1 2.1.1 Cathode material of lithium-ion batteries 2-3 2.2 Lithium………………………………………………………………………………..2-4 2.2.1 Application of lithium 2-4 2.2.2 Resources of lithium 2-5 2.2.2.1 Primary resources 2-5 2.2.2.2 Secondary resources 2-5 2.3 Cobalt………………………………………………………….………………………2-7 2.3.1 Application of Cobalt 2-7 2.3.2 Resources of cobalt 2-7 2.4 Recovery of lithium and cobalt from spent LIBs…………………………..2-8 2.5 Microwave-assisted leaching…………………………………………….…….2-14 2.5.1 Fundamentals of microwave irradiation 2-14 2.5.2 Principles of microwave heating 2-15 CHAPTER 3 3-1 3.1 Materials and reagents ……………………………………………………………3-1 3.2 Instruments…………………………………………………..………………………3-2 3.3 Source of spent LIBs…………………………………………...………………….3-3 3.4 Methods ………………………………………………………………………………3-4 3.4.1 Experimental framework and procedures 3-4 3.4.2 Characterization of cathode powder from spent LIBs 3-6 3.4.2.1 FESEM-EDS analysis 3-6 3.4.2.2 X-ray diffraction (XRD) 3-6 3.4.2.3 Aqua-regia digestion (NIEA S321.63B) 3-6 3.4.2.4 Water content-weight method (NIEA S280.61C) 3-7 3.4.2.5 ICP-AES analysis 3-8 3.4.3 Microwave-assisted leaching 3-8 3.4.4 Conventional leaching 3-10 3.4.5 Chemical equilibrium diagram software (HYDRA/MEDUSA) 3-10 CHAPTER 4 4-1 4.1 Characterization of cathode powder from spent LIBs…………………..4-1 4.2 Microwave-assisted leaching…………………………………………………….4-6 4.2.1 Effect of acid type 4-6 4.2.2 Effect of acid concentration 4-13 4.2.3 Effect of solid to liquid ratio (S/L) 4-15 4.2.3 Effect of microwave power 4-17 4.2.4 Characterization of leaching residue 4-23 4.3 Conventional leaching……………………………………………………………4-26 4.3.1 Kinetic study……………………………………….………………………………4-27 CHAPTER 5 5-1 5.1 Conclusions……………………………………………………………………………..5-1 5.2 Recommendations…………………………………………….………………………5-2 REFERENCE R-1 APPENDIX A A-1 APPENDIX B B-1 APPENDIX C C-1

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