臺灣博碩士論文加值系統

本實驗採取鎳鈷錳莫爾比8：1：1之層狀結構，透過高鎳含量達到高電容量之效果，並降低鈷在電池中的占比使材料成本下降。透過微波加熱法讓反應物能快速加熱與均勻的受熱，而形成穩定且均一的前驅化合物。

原料採用三種不同鹽類，分別是鈷錳鎳的醋酸鹽、硝酸鹽、硫酸鹽在微波加熱系統中進行前驅物合成，再藉由高溫段燒得LiNi0.8Co0.1Mn0.1O2粉末進行比較。

探討酸鹽種類、pH值、微波系統反應時間、煅燒溫度對LiNi0.8Co0.1Mn0.1O2的影響。並利用X光繞射儀分析、SEM、ICP-OES、DLS、與電化學分析儀，觀察成品的結晶、表面形貌、元素組成、粒徑大小及電化學性能的測試。

廢電池的回收則為目前的產業趨勢，透過妥善的回收及再生處理可減少對環境的危害並達到資源有效利用的利益。本實驗透過酸溶三種不同的電池廢料樣品，在過程中以氟化氫銨去除雜質鈣、鎂，並透過油萃取的方式去除銅，最後透過再結晶的方式回收電池中的貴重金屬鎳。

In this experiment, the molar ratio of a layered structure was adopted nickel-cobalt-manganese 8:1:1, and the high specific capacity was achieved by rich nickel content, and the lower proportion of cobalt in the battery bring the lower cost. Prepared by microwave heating methods can form a stable and uniform precursor compound because uniform heating.

The Layered LiNi0.8Co0.1Mn0.1O2 cathode materials were synthesized by using three different acidic salts, Cobalt, Manganese, Nickel of acetic acid, nitric acid and sulfuric acid, respectively. And put in the microwave heating system, and then compare the different LiNi0.8Co0.1Mn0.1O2 samples which were obtained by calcination .

Study on some variables: Acid type, pH value, reaction time of microwave, calcined temperature how to influence LiNi0.8Co0.1Mn0.1O2. And observe the crystallization, surface morphology, element composition, particle size, and electrochemical performance by X-ray diffraction analysis, SEM/EDX, ICP-OES, DLS, and Electrochemical analyzer.

Currently, the industry trend in to recycling of waste batteries. Through proper recycling the harm to the environment can be reduced and the benefits of efficient using resources can be realized. Three different kinds of battery waste samples were dissolved by acid in this experiment, Ammonium fluoride was used to remove impurities Calcium and Magnesium, and copper was removed by oil extraction. Finally, precious metal nickel in the battery was recovered by recrystallization.

摘 要.............................................................................................................................. i
Abstract ....................................................................................................................... iii
誌謝............................................................................................................................... v
目錄.............................................................................................................................. vi
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
1.3 論文研究流程 4
第二章 文獻回顧 7
2.1 鋰離子電池簡介 7
2.1.1 鋰電池工作原理 7
2.1.2 鋰電池優點 9
2.1.3 鋰電池缺陷 10
2.1.4 鋰電池各元件介紹 12
2.2 正極材料介紹 15
2.2.1 層狀結構 15
2.2.1.1 LiCoO2 15
2.2.1.2 LiNiO2 17
2.2.2 尖晶石結構 19
2.2.2.1 LiMn2O4 19
2.2.3 橄欖石結構 21
2.2.3.1 LiFePO4 21
2.2.4 LiNi1-x-yCoxMnyO2三元材料 22
2.2.5 過量鋰材料 23
2.3 合成方法與LINI0.8CO0.1MN0.1O2材料 25
2.3.1 高溫固相法 25
2.3.2 共沉澱法 27
2.3.3 溶膠凝膠法 30
2.3.4 噴霧乾燥法 33
2.3.5 水熱法 37
2.3.6 微波加熱法 40
2.3.7 各種合成方法優缺點比較 46
2.4 鋰電池材料造成之污染 47
2.5 鋰電池回收原理技術 49
2.5.1 預處理 49
2.5.2 乾式法 49
2.5.3 濕式法 50
2.5.4 沉澱實驗 52
2.5.5 萃取實驗 53
2.5.6 結晶實驗 53
第三章 實驗設備與方法 54
3.1 實驗藥品及材料 54
3.1.1 合成LiNi0.8Co0.1Mn0.1O2正極材料 54
3.1.2 組裝鈕扣電池 59
3.1.3 廢電池回收 61
3.2 實驗器材與分析儀器 63
3.3 實驗儀器介紹 66
3.3.1 X-光繞射分析儀(X-ray diffraction, XRD) 66
3.3.2 掃描式電子顯微鏡(Scanning electron microscope, SEM) 67
3.3.3 動態光散射儀(Dynamic light scattering, DLS) 68
3.3.4 微波消化器(Microwave reaction system, MRS) 68
3.3.5 感耦合電漿發射光譜分析儀(Inductively coupled plasma-optical emission spectrometry, ICP-OES) 69
3.3.6 恆電位電流儀(Autolab PGSTAT30 Potential) 69
3.4 實驗流程 70
3.4.1 LiNi0.8Co0.1Mn0.1O2正極材料製備 70
3.4.2 確認起始原料濃度 72
3.4.3 確定不連續微波及平衡時功率 72
3.4.4 確定微波功率與反應時間 73
3.4.5 改變煅燒溫度 79
3.4.6 正極材料分析過程 80
3.4.7 正極極片製備 81
3.4.8 手套箱操作流程及檢查表 83
3.4.9 鈕扣型電池組裝 84
3.4.10 廢電池回收流程 86
第四章 結果與討論 88
4.1 SEM分析 88
4.1.1 不同酸鹽合成之LiNi0.8Co0.1Mn0.1O2 SEM分析 88
4.1.2 不同pH值下之LiNi0.8Co0.1Mn0.1O2 SEM分析 90
4.1.3 不同微波時間下之LiNi0.8Co0.1Mn0.1O2 SEM分析 92
4.1.4 不同煅燒溫度下之LiNi0.8Co0.1Mn0.1O2 SEM分析 94
4.2 ICP-OES元素分析 96
4.2.1 不同pH值前驅物之 ICP-OES 分析 96
4.2.2 不同微波時間前驅物之 ICP-OES 分析 97
4.2.3不同煅燒溫度條件 ICP-OES 分析 99
4.3 DLS粒徑分析 101
4.3.1 不同酸鹽合成之LiNi0.8Co0.1Mn0.1O2 DLS分析 101
4.3.2 不同pH值下之LiNi0.8Co0.1Mn0.1O2 DLS分析 103
4.3.3 不同微波時間下之LiNi0.8Co0.1Mn0.1O2 DLS分析 105
4.3.4 不同煅燒溫度下之LiNi0.8Co0.1Mn0.1O2 DLS分析 108
4.4 XRD分析 111
4.4.1 不同酸鹽合成之LiNi0.8Co0.1Mn0.1O2 XRD分析 111
4.4.2 不同pH值下之LiNi0.8Co0.1Mn0.1O2 XRD分析 114
4.4.3 不同微波時間下之LiNi0.8Co0.1Mn0.1O2 XRD分析 117
4.4.4 不同煅燒溫度下之LiNi0.8Co0.1Mn0.1O2 XRD分析 121
4.5 電化學分析 125
4.5.1 LiNi0.8Co0.1Mn0.1O2循環伏安測試 125
4.5.2 不同微波時間所合成材料變速率放電圖 127
4.5.3 不同煅燒溫度所合成材料變速率放電圖 128
4.5.4 改變第二階段煅燒溫度之LiNi0.8Co0.1Mn0.1O2 SEM分析 132
4.5.5 改變第二階段煅燒溫度之LiNi0.8Co0.1Mn0.1O2 ICP-OES分析 133
4.5.6 改變第二階段煅燒溫度之LiNi0.8Co0.1Mn0.1O2 DLS分析 134
4.5.7 改變第二階段煅燒溫度之LiNi0.8Co0.1Mn0.1O2 XRD分析 135
4.5.8 改變第二階段煅燒溫度之LiNi0.8Co0.1Mn0.1O2變速率放電圖 138
4.6 廢電池回收 139
4.6.1 樣品A 139
4.6.1.1 硫酸浸漬結果 140
4.6.1.2 NH4HF2除Ca、Mg結果 141
4.6.1.3 萃取油萃取Cu結果 143
4.6.1.4 結晶之回收率 144
4.6.2 三菱/HANWA樣品 146
4.6.2.1 水溶樣品結果 147
4.6.2.2 NH4HF2除Ca、Mg結果 148
4.6.2.3 萃取油萃取Cu結果 151
4.6.2.4 結晶之回收率 153
4.6.2.5 不同鹼調整pH值之回收率比較 154
4.6.2.6 改變雙氧水和NH4HF2之回收率比較 156
4.6.3 現場樣品-粗硫酸鎳 158
4.6.3.1 浸漬結果 159
4.6.3.2 NaF除Ca、Mg結果 160
4.6.3.3 萃取油萃取Cu結果 161
4.6.3.4 回收率比較 162
第五章 結論 164
參考文獻 169
附錄 - JCPDS標準圖表 179
符號說明 182

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