臺灣博碩士論文加值系統

　　本研究成功以溶膠-凝膠法製備出氧化鎳鈷氣凝膠，未經鍛燒處理已具有normal-spinel結構之晶相，其比表面積達156 m2/g，經200℃鍛燒處理後，表面積仍有134 m2/g，隨著鍛燒溫度增加，比表面積跟著下降，晶相也有轉移變化。當鍛燒至400℃時，NiCo2O4晶相轉移成inverse-spinel，對氧氣產生效率(oxygen evolution reaction, OER)也造成影響。於電解液1 M KOH中，進行線性循環伏安掃描與其他鍛燒溫度進行比較，可知熱處理200℃時，OER有最佳效率，其Tafel slope，b值為59 mV/dec，而電流密度100 mA時過電位η則是0.184 V，相較於其他文獻上所使用之不同結構NiCo2O4，本研究使用的氣凝膠有著相當好的效率。氧化鎳鈷乾凝膠，同氣凝膠，未經鍛燒處理亦具有normal-spinel結構之晶相，經200℃鍛燒處理後，表面積為113 m2/g，與其他鍛燒溫度比較，熱處理200℃之樣品OER有著最佳效率，其b值為62 mV/dec，η為0.227 V。
　　仿效文獻以熱沉積方式製備出具inverse-spinel結構的氧化鎳鈷奈米顆粒，並與氧化鎳鈷氣凝膠及乾凝膠效率最佳兩組做比較分析。由熱沉積法製備出的奈米顆粒，由於經過600℃高溫鍛燒，使得孔洞體積極小，僅有0.097 cc/g，比表面積為13 m2/g，因此其OER效率不如其他兩者佳，其產氧初始電壓為0.47 V，b值為81 mV/dec，η為0.379 V。因此，本研究中，由溶膠-凝膠法製備出的氧化鎳鈷氣凝膠，於鍛燒溫度200℃時，有最佳的OER效率。
　　為了提升改善氧化鎳鈷在超級電容器上的行為表現，本研究使用高導電性及高比表面積的碳氣凝膠做為骨架，製備出氧化鎳鈷/碳氣凝膠複合電極，比電容值於掃描速率25 mV/s、電解液1 M NaOH、操作電位-0.1~0.55 V vs. Ag/AgCl，可達1,696 F/g，經計算得到，能量密度及功率密度分別為67.6 Wh/kg及16 kW/kg，於下世代超級電容器之設計需求，提供了一個低成本，高效能之材料選擇。

總目錄
摘要 I
Abstract II
致謝 IV
總目錄 V
圖目錄 VIII
表目錄 XII
第1章 緒論 1
1.1 電化學原理 1
1.1.1 電化學反應系統 1
1.1.2 影響電化學反應系統的因素 2
1.1.3 電極材料 3
1.2 氣凝膠的介紹 5
1.2.1 氣凝膠簡介 5
1.2.2 氣凝膠之製備 6
1.2.3 二氧化碳超臨界乾燥系統 9
1.3氧氣產生 12
1.3.1 氧氣產生簡介 12
1.3.2 Tafel Equation 14
1.4 電化學電容器 16
1.4.1 電化學電容器簡介 16
1.4.2 擬電容器 18
1.4.3 電容測試原理 19
第2章 文獻回顧 23
2.1氧氣產生 23
2.1.1 貴重金屬氧化物應用於氧氣產生 23
2.1.2 過渡金屬氧化物應用於氧氣產生 25
2.1.3 溶膠-凝膠法製備之鈷氧化物(MxCo3-xO4, M = Ni, Cu; 0≦x≦1)薄膜應用於氧氣產生 27
2.1.4 鎳鈷氧化物複合材料之電化學性質探討 29
2.1.5 探討鈷氧化物其氧氣產生反應機制及等效電路模擬圖 31
2.1.6 探討鹼性溶液中水電解反應 32
2.1.7 以電化學製備六角形奈米層片氧化鎳鈷應用於水電解 33
2.1.8 熱沉積法製備氧化鎳鈷奈米線應用於氧氣產生 35
2.2 氧化鎳鈷應用於超級電容器 36
2.2.1 電化學成長非結晶性水合鎳鈷氫氧化物之擬電容行為 36
2.2.2 溶膠-凝膠法製備氧化鎳鈷氣凝膠應用於超級電容器 37
2.2.3 電化學方式合成尖晶石奈米薄膜應用於超級電容器 39
第3章 實驗方法 42
3.1 實驗藥品 42
3.2 實驗儀器 44
3.3 檢測儀器 45
3.4 實驗動機 47
3.5 實驗流程 48
3.5.1 石墨電極之製備及前處理 48
3.5.2 氧化鎳鈷應用於氧氣產生 49
3.5.3 氧化鎳鈷複合碳氣凝膠應用於超電容 53
3.5.4 電化學分析實驗 56
第4章 結果與討論 58
4.1 氧氣產生 58
4.1.1 氧化鎳鈷氣凝膠結果與討論 58
4.1.2 氧化鎳鈷乾凝膠結果與討論 74
4.1.3 熱裂解氧化鎳鈷奈米粒子結果與討論 82
4.1.4 不同結構氧化鎳鈷於氧氣產生之結果與討論 86
4.1.5 熱裂解沉積氧化鎳鈷奈米線結果與討論 90
4.2 超級電容器 93
第5章 結論 101
第6章 參考資料 103

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