臺灣博碩士論文加值系統

本實驗第一部分為利用簡單的回流方法合成表面具有花瓣狀之二氧化錳（CNC@MnO2）。並使用掃描電子顯微鏡（SEM）、X-射線光電子能譜儀（XPS）、拉曼光譜（Raman spectra）做特性分析，可以得到所合成之材料為birnessite-type的二氧化錳。將CNC@MnO2混合CNT後，其電子轉移數高達3.94；在進行鋅空氣電池全電池測試後，發現在電流密度50 mA/cm2，其放電可達1.1 V、比電容量為804 mAh/g；在電流密度為200 mA/cm2，有最大功率密度138 mW/cm2；在循環充放電300圈後，CNC@MnO2擁有92.7 %的放電保留率，高於市售白金之85.8 %。
第二部分為利用靜電紡絲法合成表面具有觸媒之奈米碳纖維，並利用描電子顯微鏡（SEM）、X-射線光電子能譜儀（XPS）、拉曼光譜（Raman spectra）、電子能譜儀（AES）、mapping做為其特性分析，可以得到所合成之奈米碳纖維其表面顆粒為Co3O4。藉由碳化溫度與不同前驅物比例之旋轉電極測試，可以得到在碳化溫度為900 oC、PAN系高分子與醋酸鈷比例為1：1時，擁有最大電子轉移數3.94；經由全電池測試後，電流密度固定在50 mA/cm2，放電電壓為1.13 V、比電容量為802 mAh/g。由極化曲線可得知在電流密度為175 mA/cm2，有最大功率密度127 mW/cm2。經由循環充放電測試後，可觀察其放電電壓與市售白金相同。

Carbon nanocapsele (CNC) is employed as substrates for petal-like MnO2 nanostructures on surface (CNC@MnO2) by reflux synthesis. The characterization of the materials were conducted with scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), Raman analysis. The results confirm that the birnessite-type MnO2 was formed. The number of electrons transferred is calculated as 3.94 by rotating ring-disk electrode (RRDE). The discharge voltage of 1.1 V and specific capacity of 804 mAhg-1 are obtained at 50 mAcm-2. A maximum power density is 138 mWcm-2 at 200 mAcm-2. After cycling test (300 cycles), the discharge potential retention of cell was about 92.7 %.
Formation of catalyst-nanoparticles-embeded were achieved by electrospinning technology. The characterization of the materials were conducted with scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), Raman analysis, mapping and Auger electron spectroscopy(AES). The results confirms that the nanoparticles on carbon fiber is Co3O4,The number of electrons transferred is calculated as 3.94 by rotating ring-disk electrode (RRDE). By full cell test, The discharge voltage of 1.13 V and specific capacity of 802 mAhg-1 are obtained at 50 mAcm-2. A maximum power density is 127 mWcm-2 at 175 mAcm-2. After cycling test(300cycles), the discharge potential is the same as 20 wt% Pt/C.

誌謝 I
中文摘要 II
Abstract III
目錄 V
表目錄 IX
圖目錄 X
第一章 緒論 1
1-1 前言 1
1-2 鋅空氣電池之簡介 2
1-3 靜電紡絲之簡介 7
第二章 文獻回顧 8
2-1 鋅空氣電池的發展史 8
2-2 鋅空氣電池之基本電化學原理 11
2-2-1 鋅空氣電池放電過程 11
2-2-1-1 空氣電極之還原半反應 12
2-2-2 鋅空氣電池充電過程 15
2-2-3 鋅陽極反應 17
2-2-4 其他反應 18
2-3 鋅空氣電池之構造 19
2-3-1 鋅陽極 19
2-3-1-1 鋅陽極材料 20
2-3-1-2 鋅陽極種類 24
2-3-1-3 鋅陽極之鈍化 24
2-3-1-4 鋅陽極之腐蝕 26
2-3-2 空氣陰極 27
2-3-2-1 觸媒材料 29
2-4 鋅空氣電池空氣陰極之相關文獻回顧整理 41
2-5 研究動機及目標 65
第三章 實驗步驟與研究方法 66
3-1 實驗架構 66
3-2 二氧化錳-奈米碳球殼核材料之製備 68
3-2-1 實驗材料與藥品 68
3-2-2 實驗裝置 68
3-2-3 實驗步驟 69
3-2-4 實驗檢測儀器 71
3-3 利用靜電紡絲法製備金屬碳纖維觸媒 72
3-3-1 實驗材料與藥品 72
3-3-2 實驗裝置 73
3-3-3 實驗步驟 74
3-3-4 實驗檢測儀器 77
3-4 鋅空氣電池-電化學測試 78
3-4-1 實驗材料與藥品 78
3-4-2 實驗裝置 79
3-4-3 實驗步驟 80
3-4-3-1 旋轉電極漿料配製 80
3-4-3-2 空氣陰極製作 82
3-4-3-3 電化學測試 87
3-4-4 實驗檢測儀器 89
第四章 結果與討論 90
4-1合成表面具有花瓣狀二氧化錳之CNC@MnO2 91
4-1-1 CNC@MnO2之特性分析 93
4-1-1-1 CNC@MnO2之XPS分析 93
4-1-1-2 CNC@MnO2之Raman分析 96
4-1-1-3實驗小節 98
4-1-2 CNC@MnO2於鋅空氣電池上之應用 99
4-1-2-1 旋轉電極測試 99
4-1-2-2 鋅空氣電池全電池測試 116
4-1-2-3 實驗小節 121
4-2合成表面具有觸媒之奈米碳纖維 122
4-2-1 不同金屬觸媒前驅物 123
4-2-2 不同碳化溫度 132
4-2-3 不同比例之PAN系高分子與醋酸鈷 142
4-2-4 表面具有觸媒之奈米碳纖維特性分析 157
4-2-4-1 表面具有觸媒之奈米碳纖維之TE-mapping分析 157
4-2-4-2 表面具有觸媒之奈米碳纖維之AES分析 158
4-2-4-3 表面具有觸媒之奈米碳纖維之XPS分析 160
4-2-4-4 表面具有觸媒之奈米碳纖維之Raman分析 162
4-2-5 表面具有觸媒之奈米碳纖維之成長機制 163
4-2-6 表面具有觸媒之奈米碳纖維於鋅空氣電池上的應用 164
4-2-7 實驗小節 169
第五章 總結與未來展望 170
5-1 總結 170
5-2 未來展望 172
參考文獻 173
附錄 182
附錄A ORR起始電位與半波電位的值之取得方法 182
附錄B OER起始電位的值之取得方法 183
附錄C XC-72@MnO2與20 wt%Pt/C之SEM圖 184
附錄D 不同金屬前驅物穩定化之SEM圖 185
附錄E 不同比例之PAN系高分子與醋酸鈷穩定化之SEM圖 186

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