臺灣博碩士論文加值系統

隨著科技發展迅速，人類對於生活品質及需求逐年增長，而現今社會隨處可見與鋰電池相關的產品，因此廢棄鋰電池相關處理及再利用之研究開發有其重要性。本研究以離子交換與化學沉澱法分離鋰、鈷、錳、鎳等有價金屬，以利後續回收高純度的金屬產物。
本實驗分為三階段，第一階段將鋰電池中陰極材料進行前處理及特性分析，了解原料成分及晶相結構，有利於後續研究規劃。第二階段為探討酸浸漬之實驗參數，尋找最佳浸漬參數，其實驗結果顯示使用濃度為6 N 之硫酸、固液比70 g/L、添加5 vol.% H2O2，於反應溫度60 ℃之環境下反應3小時，其鋰、鈷、錳、鎳之浸漬率皆達90 %以上。
第三階段為利用選擇性化學沉澱及離子交換進行有價金屬分離回收。首先，將浸漬液進行硫化沉澱，使鈷、鎳完全沉澱與溶液中有價金屬鋰、錳分離，之後分為兩個部分進行有價金屬回收。第一部分:利用化學沉澱法，以碳酸鈉作為沉澱劑，將鋰、錳分離回收，得到碳酸錳與碳酸鋰之沉澱物，其錳、鋰之產物純度分別為87、70 %；第二部分:先使用鹽酸將硫化沉澱後之產物硫化鈷及硫化鎳溶解，所得之鈷鎳溶液藉由離子交換樹脂進行吸附，以達到鈷、鎳分離。吸附後之樹脂利用濃鹽酸溶液去除殘留液，再以清水進行解析，達成鈷之分離與純化，其回收鈷之純度為99 %。

With the rapid development of science and technology, human beings have grown their quality of life and demand year by year. Nowadays, lithium-ion battery-related products can be seen everywhere in society. Therefore, the research and development of disposal and reuse of waste lithium batteries are of great importance. In this study, ion exchange and chemical precipitation were used to separate valuable metals. The experiment is divided into three stages. In the first stage, the cathode material in the lithium battery is pretreated and characterized to understand the composition of the raw materials and the crystal phase structure. The second stage is to investigate the experimental parameters of acid leaching. The experimental results show that the reaction is carried out for 3 hours at a reaction temperature of 60 °C using a sulfuric acid concentration of 6 N, a solid-liquid ratio of 70 g/L, and addition of 5 vol.% H2O2. The leaching efficiency of lithium, cobalt, manganese, and nickel are all above 90%. The third stage is the separation and recovery of valuable metals by chemical precipitation and ion exchange. Lithium and manganese are separated and recovered by using sodium carbonate as a precipitating agent. The purity of the manganese and lithium products were 87% and 70%, respectively. Finally, adsorption by ion exchange resin to achieve separation of cobalt and nickel. The recovered cobalt has a purity of 99%.

摘要 i
致謝 vii
目錄 viii
表目錄 xi
圖目錄 xii
第一章 緒論 1
1.1 前言 1
1.2 研究目的 2
第二章 理論基礎與文獻回顧 3
2.1 鋰離子電池之介紹 3
2.1.1 鋰離子電池結構 3
2.1.2 鋰電池工作原理 5
2.1.3 鋰電池對環境之危害 6
2.2 冶金技術與資源化 7
2.2.1 火法冶金 7
2.2.2 濕法冶金 8
2.2.2.1 浸漬 ( Leaching ) 8
2.2.2.2 分離與純化 (Separation and Purification) 11
2.2.2.3 金屬析出 14
2.2.3 火法冶金與濕法冶金之差異 14
2.3 實驗反應機制 15
2.3.1 浸漬反應熱力學 15
2.3.2 浸漬反應動力學 17
2.3.3 離子交換熱力學 19
2.3.4 離子交換動力學 22
2.4 文獻回顧 24
2.4.1 浸漬文獻 24
2.4.2 回收文獻 26
第三章 實驗材料及流程 29
3.1實驗材料及設備 29
3.1.1 實驗材料 29
3.1.2 實驗設備 31
3.2 實驗流程 37
3.3 實驗方法及步驟 38
3.3.1 前處理及原料分析 38
3.3.2 浸漬 40
3.3.3 分離回收 41
3.3.3.1 錳沉澱回收 42
3.3.3.2 鋰沉澱回收 42
3.3.3.3 鈷鎳分離回收 43
第四章 結果與討論 44
4.1 鋰電池陰極材料之特性分析 44
4.1.1 粒徑分析 44
4.1.2 成份分析 45
4.1.3 晶相分析 46
4.2 鋰電池陰極材料之浸漬 47
4.2.1 鹽酸浸漬 47
4.2.1.1 固液比 47
4.2.1.2 浸漬劑濃度 48
4.2.1.3 還原劑添加量 49
4.2.1.4 反應溫度 50
4.2.1.5 反應時間 51
4.2.2 硫酸浸漬 52
4.2.2.1 固液比 52
4.2.2.2 浸漬劑濃度 53
4.2.2.3 還原劑添加量 54
4.2.2.4 反應時間 55
4.2.3 浸漬溶出小結 56
4.3 鋰電池陰極材料之分離回收 57
4.3.1 錳沉澱回收 57
4.3.2 鋰沉澱回收 61
4.3.3 離子交換分離鈷鎳 64
第五章 結論與建議 66
5.1 結論 66
5.2 建議 67
參考文獻 68

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