因應人類社會對能源的龐大需求，石化燃料的快速消耗與空汙等問題日漸加劇，如何開發環保且永續的儲能裝置亦成為重要議題。而超級電容器作為一種幾乎免維護的儲能設備，具有極長的循環壽命且高功率密度，但受限於較低的能量密度。為此，科學家正在尋找可以突破這極限的方法，而近年來發展出混合式超級電容器，結合兩種材料以拓展電位窗增加能源密度。本研究使用相對無毒且地殼含量豐富的錳和鉬合成了鉬錳氧化物-硫化物複合材料。鉬錳硫化物尚未被學界廣泛研究，本實驗透過電化學分析了解其電容潛力，在5mVs-1時比電容值高達3664 F g-1。鉬錳硫化物透過過渡金屬未填充電子的d軌域，其中多重氧化態的轉換儲存電子；又因硫具有更廣闊的價電子殼層，因此提升電化學活性，進一步提升贋電容值。然而此材料由於活性太強，電容維持率不高。我們以鉬錳氧化物複合此材料，而奈米片狀陣列狀可分散晶體，避免堆積，並使電解質更易到達電極表面進行反應。此材料在1A g-1時比電容值可達2167 F g-1，在高電流密度(10 A g-1)下仍有良好的電容維持率83%。另一方面，透過循環經濟概念，解決農業廢棄物的問題。取環境難以自然降解之菱角殼作為負極材料；通過高溫爐的兩步碳化、活化程序，不需繁瑣的步驟與化學藥品，便合成具有2054 m2 g-1高比表面積之多孔碳材料，而此材料富含的中孔結構輔助微孔，使離子更易儲存在孔洞之中，增加電容應用效果。在5 mVs-1時比電容值可達174 Fg-1。將此兩種材料所組成的混合式超級電極157.31 Wh kg-1時功率密度為584 W kg-1。同時也以有機電解液組成對稱超級電容，在能量密度為110.8 Wh kg-1，功率密度為665 kg-1；在功率密度提升至11700 W kg-1時，能量密度也可維持在48.8 Wh kg-1，此電極材料不僅製作過程環保也具有強大儲能潛能。

In response to the huge energy demand of human society, the issue of environmental protection and green energy has also attracted the attention of scientists. In the development of green energy, how to develop environmentally friendly energy storage devices has also become important issue. Supercapacitor, as an almost maintenance-free energy storage device with extremely long cycle life, was limited to relatively low energy density. Therefore, scientists are looking for a material that can break through this threshold. In recent years, scholars have combined batteries and supercapacitors into hybrid supercapacitors to take advantage of both.
In this study, the core-shell structure of MnMoS4/MnMoO4 transition metal bimetallic sulfide and bimetallic oxide was synthesized using manganese and molybdenum, which are relatively non-toxic and rich in crustal content. Since the transition metal has an unfilled d orbital, which has many valence states; it will greatly increase the pseudocapacitance. The core-shell nanosheet structure separates the metal particles, avoids accumulation, and makes the electrolyte more easily reach the electrode surface to react, thus creating a high specific capacitance value of 3664 F g-1.
On the other hand, using the environmentally friendly agricultural waste - water chestnut as the raw material of the cathode material, the environmentally friendly porous carbon material with a high specific surface area (2054 m2 g-1) is synthesized through one activation process of tube furnace.
Furthermore, an asymmetric supercapacitor is also assembled, exhibiting an energy density of 157.31 Wh kg-1 at a power density of 584 W kg-1.

目錄
摘要 I
Abstract II
誌謝 III
目錄 IV
圖目錄 VII
表目錄 XI
第一章 前言 1
1.1 簡介 1
1.2 研究動機 1
第二章 文獻回顧 3
2.1 電化學分析 3
2.1.1 電極動力學[3][4] 4
2.1.2 極化、過電位[3][4] 5
2.1.3 電化學系統之可逆反應[3] 6
2.2 超級電容器 7
2.2.1 儲能機制及種類 11
2.2.2 電雙層理論(Electric double layer theory) 12
2.2.3 電雙層電容器(Electric double layer capacitor) 14
2.2.4 贋電容電容器(pseudocapacitor) 15
2.2.5 混合式電容器(Battery-Supercapacitor Hybrid Devices, BSHs) 17
2.2.6 電極設計 18
2.3 過渡金屬氧化物(Transition Metal Oxide) 20
2.3.1 過渡金屬三元化合物(Transition Metal Ternary compounds) 21
2.3.2 過渡金屬硫化物(Transition Metal Chalcogenides) 23
2.4 菱角殼生物炭 26
2.4.1 生物炭組成與裂解過程 26
2.4.2 生物炭化學活化 27
第三章 研究方法 30
3.1 藥品 30
3.2 實驗設備 31
3.3 實驗流程 32
3.3.1 核殼狀錳鉬氧化物與硫化物的合成 32
3.3.2 菱角殼多孔生物炭的合成 34
3.3.3 非對稱超級電容的組成 35
3.4 檢測儀器與作用原理 37
3.4.1 高解析熱場發射掃描式電子顯微鏡(High Resolution Thermal Field Emission Scanning Electron Microscope , HRFEG-SEM) 37
3.4.2 穿透式電子顯微鏡(Transmission electron microscope, TEM) 38
3.4.3 X-射線繞射分析儀(X-ray diffraction, XRD ) 39
3.4.4 拉曼光譜儀(Raman spectroscopy) 40
3.4.5 比表面積與孔隙度分析儀 (Specific Surface Area and Porosimetry Analyzer, BET) 41
3.4.6 電化學分析(Electrochemical analysis) 44
第四章 結果與討論 49
4.1 鉬錳氧化物與硫化物之結構分析 49
4.2 鉬錳氧化物與硫化物之電化學分析 55
4.3 菱角殼生物炭之結構分析 63
4.4 菱角殼生物炭之電化學分析 74
4.5 非對稱超級電容 77
4.6 對稱超級電容 81
第五章 結論 89
第六章 未來展望 90
6.1 鉬錳氧化物與硫化物 90
6.2 菱角殼多孔生物炭 90
參考文獻 91

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