臺灣博碩士論文加值系統

近年來3C產品蓬勃發展，使全球鋰電池的使用越來越普遍，但如何處理鋰電池電子廢棄物是一大課題。因鋰電池中含有稀少金屬鈷，所以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。本研究蒐集廢手機電池中鈷酸鋰及鎳錳鈷酸鋰等正極材料，以硫酸與檸檬酸兩種酸液比較傳統加熱浸漬、微波輔助浸漬與超音波輔助浸漬溶出鋰電池正極材料中金屬鈷之差異性。實驗結果證明微波浸漬與超音波浸漬皆可有效提升金屬鈷之溶出率，其中以微波搭配硫酸輔助溶鈷效果最佳，其條件為利用2M之硫酸並添加2 vol%之雙氧水作為還原劑，在固液比為25g/L、溫度80℃之條件下浸漬5分鐘，溶出率可達100%。微波相較傳統浸漬可減少12倍的時間，且固液比可由20g/L提升至25g/L，有效節省時間及成本。後續經由添加過錳酸鉀去除溶液中雜質錳，於最佳條件pH=2、Mn2+與KMnO4之莫爾比(MRMK ratio)=1.5、反應時間60分鐘下錳之去除率可達97.7%。萃取部分利用二(2-乙基己基)磷酸 (D2EHPA)作為萃取劑萃取酸液中之鈷離子，最佳條件在pH=5、有機相水相比例(O:A ratio)=1及萃取劑濃度0.25M反應60分鐘，鈷萃取率為93.5%。以5M鹽酸反萃取40分鐘，經反萃後之反萃液中鈷含量可高達96.0 %。最後於最佳條件下進行電解，金屬鈷之回收率可接近98%，純度可達98.2%，顯示本研究之技術，可提升廢二次鋰離子電池回收鈷金屬的純度與價值。

In recent years, the widespread usage of lithium batteries had led to a large amount of waste. Therefore, recovery of cobalt from waste ithium batteries was the most economic benefits. The purpose of this study was to compare three different methods which were conventional, microwave heating and ultrasonic heating on leaching process. Using 2M sulfuric acid, reducing agent proportion of 2 vol%, temperature of 80 ℃, reaction time of 5 minutes and the ratio of solid-liquid was 25g/L. The cobalt cobalt was up to 100% from the leaching liquor under microwave heating system and reaction time would be greatly reduced about 12 times, compared to traditional methods. For the separation of manganese, 0.5 mol L−1 KMnO4 solution was drop-wise added to the leaching liquor to selectively precipitate Mn2+ under optimized experimental conditions. And about 97.7% Mn2+ is precipitated at equilibrium pH = 2.0, molar ratio of Mn2+ to KMnO4 (MRMK) = 1.5 and reaction time of 60 minute. Therefore, the advisable equilibrium pH would be 5, O:A=1 at room temperature, the Co2+ was extracted by D2EHPA and then about 93.5% Co2+ can be extracted. The stripping was carried out at the 5M of hydrochloric acid, reaction time of 10 minute. The solution that contained the cobalt was metalized by electrolytic refining, and the final purity of the cobalt metal was up to 98.2%.

學位論文審定書 i
論文公開授權書 ii
謝誌 iii
摘要 iv
ABSTRACT v
目錄 vi
圖目錄 x
表目錄 xiv
第一章 前言 1
1-1研究緣起 1
1-2研究目的 3
第二章 文獻探討 4
2-1鋰電池基本簡介 4
2-1-1鋰電池 4
2-1-2鋰電池反應原理 6
2-1-3鋰電池的組成與污染 7
2-1-4鋰電池產業近況 10
2-2鋰電池回收現況 14
2-3冶鍊回收金屬 15
2-3-1濕法冶金 17
2-3-2廢鋰電池回收有價金屬 19
2-4鋰電池中各金屬之性質 21
2-5金屬溶出 25
2-5-1酸溶液 25
2-5-2還原劑 27
2-5-3超音波震盪輔助酸溶 27
2-5-4溶出效率 27
2-5-5微波輔助酸溶 28
第三章 研究方法與流程 30
3-1研究方法 30
3-2進行步驟 30
3-3實驗流程圖 36
3-4實驗使用之檢測方法及儀器 37
3-4-1土壤中重金屬檢測方法－王水消化法 37
3-4-2感應耦合電漿光譜法 37
3-4-3環境掃描式電子顯微鏡 39
3-4-4超音波清洗機 39
3-4-5微波反應裝置 40
3-4-6電化學儀器 41
3-5實驗材料與藥品 42
第四章 結果與討論 43
4-1鋰電池拆解分析 43
4-2鋰電池正極材料全量分析 44
4-3傳統浸漬 45
4-3-1硫酸傳統浸漬 45
4-3-2檸檬酸傳統浸漬 48
4-3-3傳統浸漬硫酸及檸檬酸之最佳浸漬條件 51
4-4微波浸漬 52
4-4-1硫酸微波浸漬 52
4-4-2檸檬酸微波浸漬 57
4-4-3微波浸漬硫酸及檸檬酸之最佳浸漬條件 61
4-5超音波浸漬 62
4-5-1硫酸超音波浸漬 62
4-5-2檸檬酸超音波浸漬 66
4-5-3超音波浸漬硫酸及檸檬酸之最佳浸漬條件 70
4-6微波浸漬、超音波浸漬與傳統浸漬之差異性 70
4-6-1微波浸漬對於各酸液溶出率之影響 70
4-6-2超音波浸漬對於各酸液溶出率之影響 70
4-7各條件下鈷與其他金屬之溶出量 71
4-7-1硫酸傳統浸漬最佳條件下金屬之溶出量 71
4-7-2硫酸微波浸漬最佳條件下金屬之溶出量 72
4-7-3硫酸超音波浸漬最佳條件下金屬之溶出量 73
4-7-4檸檬酸傳統浸漬最佳條件下金屬之溶出量 74
4-7-5檸檬酸微波浸漬最佳條件下金屬之溶出量 75
4-7-6檸檬酸超音波浸漬最佳條件下金屬之溶出量 76
4-8不同微波功率及超音波頻率對溶出效率之影響 77
4-8-1硫酸與檸檬酸於不同微波功率之溶出率 77
4-8-2硫酸與檸檬酸於不同超音波頻率之溶出率 79
4-9正極材料反應前後SEM分析 81
4-10溶出液錳分離效率實驗 84
4-10-1 pH環境對於錳沉澱之效率 84
4-10-2錳沉澱結果 87
4-11萃取分離鈷實驗 88
4-11-1 pH值對各金屬萃取率影響之實驗 88
4-11-2 O:A比對各金屬萃取率影響之實驗 89
4-11-3 萃取劑濃度對各金屬萃取率影響之實驗 90
4-11-4 萃取時間對各金屬萃取率影響之實驗 91
4-11-5最佳條件下萃取前、後各金屬含量 92
4-12反萃取實驗 93
4-13電解回收實驗 96
4-13-1電流0.1A於各電壓下之電解回收率 96
4-13-2電流0.3A於各電壓下之電解回收率 97
4-13-3電流0.5A於各電壓下之電解回收率 98
4-13-4電流0.7A於各電壓下之電解回收率 99
4-13-5電流0.9A於各電壓下之電解回收率 100
4-13-6電壓3V下各電流之鈷回收率差異 101
4-14電解精煉實驗 103
4-15最佳條件之質量平衡圖 104
4-16成本效益分析 105
4-16-1設備成本估算 105
4-16-2每年操作之成本效益分析 105
4-17污染量化分析與處理方式 108
第五章 結論與建議 109
5-1結論 109
5-2建議 111
第六章 參考文獻 112

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