臺灣博碩士論文加值系統

摘 要
本實驗採用水溶液法之一的「直接生成法」合成氫氧化鎳粉末，藉由改變反應時間、鎳鹽種類以及添加界面活性劑等方式，得到在5 ~ 30 mm分佈範圍內6種氫氧化鎳粉末，分別為樣品A（硫酸鎳為鎳鹽；反應時間12小時）、樣品A-1（硫酸鎳為鎳鹽；反應時間12小時並老化(aging)處理）、樣品A-2（硫酸鎳為鎳鹽；反應時間2小時）、樣品A-3（硫酸鎳為鎳鹽；反應時間2小時並老化處理）、樣品B（草酸鎳為鎳鹽；反應時間12小時）以及樣品C（硫酸鎳為鎳鹽；反應時間12小時並加入界面活性劑）。經FT-IR、XRD等結構鑑定後，除樣品A-2為bbc（badly-crystallized b）結構外，其餘5種樣品均為b型態之氫氧化鎳。
由充放電的實驗可知，此5種樣品之放電電容量值均約為160 mAh/g。雖然文獻中指出粒子較小之電極有較好的電化學活性，但顆粒小則容易由極板上脫落，造成活性物質利用率下降。故樣品B雖有較小的平均粒徑，但充放電約3次後則放電電容量減少；樣品C則因添加界面活性劑使得晶粒間的阻抗增加，因此較慢才達到放電電容量值。而樣品A-2的放電電容量只有140 mAh/g左右，由交流阻抗分析及循環伏安實驗可看到其反應不易進行，推測是由於樣品A-2的結晶狀態較差，質子傳遞不易，故其放電電容量比其他組樣品小。根據此實驗結果我們發現，在5 ~ 30 mm的分佈範圍內，顆粒大小並非影響氫氧化鎳電極性能的關鍵因素，氫氧化鎳本身的結構型態才是影響其性質之主因。
另外，由熱分析實驗可知，經老化處理後得之氫氧化鎳粉末的起始分解溫度及熔點有提高的現象，表示其熱安定性較佳。且縮短反應時間為2小時並老化處理後所得的氫氧化鎳粉末，亦為b之型態，其放電電容量與反應時間12小時所得的氫氧化鎳相當。因此多了老化處理步驟，可以減少合成反應的時間，便可得到熱性質及電化學性質兼具之正極活性材料。

目 錄
摘要……………………………………………………………………….i
謝誌……………………………………………………………………...iii
目錄……………………………………………………………………...iv
表目錄…………………………………………………………………..vii
圖目錄………………………………………………………………….viii
第一章 緒論 1
1-1 前言 1
1-2 研究動機 3
第二章 文獻回顧 5
2-1 鎳氫電池簡介 5
2-1-1 鎳氫電池之一般反應 5
2-1-2 鎳氫電池之組件 6
2-1-3 鎳氫電池之自放電 7
2-1-4 鎳氫電池之高速放電 9
2-2 正極材料 9
2-2-1 a-Ni(OH)2為活性材料的正極反應 11
2-2-2 b-Ni(OH)2為活性材料的正極反應 12
2-2-3 正極材料之合成 12
2-3 Ni(OH)2正極性能之改進 16
2-3-1 添加劑 16
2-3-2 添加法 19
2-3-3 無電鍍處理 20
2-4 正極表面行為 21
2-4-1 交流阻抗應用於鎳氫電池正極之分析 21
2-4-2 質子擴散行為 24
第三章 實驗 25
3-1 實驗藥品及儀器 25
3-2 材料製備 26
3-3 材料鑑定 28
3-4 電池製作及組裝 30
3-5 電池性能測試 31
3-5-1 充放電測試 31
3-5-2 交流阻抗分析 32
3-5-2-1 交流阻抗分析原理 32
3-5-2-2 交流阻抗分析實驗 33
3-5-3 循環伏安實驗 34
第四章 實驗結果與討論 35
4-1 基本結構形貌分析 36
4-1-1 粒徑分析（LPA） 36
4-1-2 氫氧化鎳表面形態分析（SEM） 37
4-1-3 氫氧化鎳結構組織分析 40
4-1-4 熱性質分析 44
4-2 電化學性質測試 52
4-2-1 鎳極充放電測試 52
4-2-2 鎳極交流阻抗分析 56
4-2-3 循環伏安實驗 58
4-3 鎳極電容量與其物性之關係 59
第五章 結論 64
第六章 參考文獻 66
表目錄
表1.1 市售電池比較對照表 1
表1.2 市售氫氧化鎳產品品質分析 2
表2.1 鎳電極充放電體積變化比 12
表4.1 不同氫氧化鎳樣品之晶格常數 41
表4.2 不同氫氧化鎳樣品之TGA及DTA實驗結果 45
表4.3 不同氫氧化鎳樣品之分解起始、結束溫度結果 52
表4.4 不同氫氧化鎳樣品之DSC實驗結果 52
表4.5 氫氧化鎳粉末之放電電容量（mAh/g） 44
表4.6 不同氫氧化鎳樣品之電荷轉移阻抗值，RCT（W g） 57
表4.7 不同氫氧化鎳樣品之循環伏安實驗結果 59
圖目錄
圖1.1 整體實驗之流程圖 4
圖2.1 圓柱形鎳氫電池結構圖 7
圖2.2 電容量與放電電流之關係圖 9
圖2.3 Ni(OH)2結構示意圖 10
圖2.4 Bode圖 11
圖2.5 添加鈷之反應假想模型圖 17
圖2.6 氫氧化鎳充放電反應機制圖 22
圖2.7 Barton鎳電極等效電路圖 22
圖2.8 Zhang實驗之交流阻抗分析圖 23
圖2.9 Zhang實驗之等效電路圖 23
圖3.1 草酸鎳之紅外線光譜圖 28
圖3.2 電池組裝圖 31
圖3.3 電池充放電裝置圖 31
圖3.4 (a)一個簡單RC電路及其(b)標準之阻抗圖 33
圖3.5 交流阻抗分析實驗裝置圖 34
圖3.6 循環伏安實驗裝置圖 34
圖4.1 不同氫氧化鎳樣品之粒徑分佈圖 38
圖4.2 不同氫氧化鎳樣品之SEM圖 39
圖4.3 不同氫氧化鎳樣品之紅外線光譜圖 42
圖4.4 不同氫氧化鎳樣品之XRD光譜圖 43
圖4.5 不同氫氧化鎳樣品之熱重損失TGA及微導數熱重量
測定DTG分析圖 46
圖4.6 不同之氫氧化鎳樣品之熱差掃描卡計DSC圖 49
圖4.7 不同氫氧化鎳樣品正極之放電電容量與循環次數
間的關係圖 56
圖4.8 不同氫氧化鎳樣品充放電前之交流阻抗分析圖 58
圖4.9 不同氫氧化鎳樣品正極之循環伏安圖 61

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