臺灣博碩士論文加值系統

本研究主要是要探討製備鈷/錳氧化物核/殼奈米結構的製程參數及電化學特性。以石墨塊作為基材，將製程分成三個階段，並改變其參數進行比較：第一階段以水熱法不同濃度與時間製備鈷氧化物作為模板，製備出雪花狀層級式堆疊之結構提升其反應面積；第二階段進行不同溫度與持溫時間之煆燒熱處理，比較其結晶性及表面結構，取出最佳煆燒參數；第三階段進行第二次水熱法，隨著水熱時間之改變來沉積錳氧化物，在每個階段取出最佳參數之後，製備出鈷/錳氧化物電極材料，進行XRD、SEM、TEM、EDS、XPS與電容特性分析。
在濃度Co 0.1 M沉積4 h之參數下長寬比適中，其具有優異之反應面積。在煆燒溫度300°C持溫4 h，其結晶性有明顯增加，有利於電子傳遞，在SEM分析中可以觀察到其表面有毛邊與孔洞，有助於反應面積之提升。而在錳氧化物沉積時間2 h，展現其優異之電容特性。
吾人將在三種階段取最佳參數進行不同掃描速率之分析及其他電性測試。在掃描速率25 mV/s下，其電容值可以達到196 F/g，經過10次充放電測試，雖然有些微的電壓降產生，但是其整體圖形接近對稱等腰三角形，說明其具有良好的電化學可逆性；在經過1200圈循環伏安分析後，其電容量還維持著94%左右之電容量，也可以說明其具有良好的循環穩定性。顯示鈷/錳氧化物為具有潛力與發展性之電極活性材料。

In the present study, the preparation of Co/Mn (cobalt/manganese) oxide electrode was mainly based on three steps. First, Co-oxide nanostructure was prepared on a graphite substrate by hydrothermal process as a function of hydrothermal time. Experimental results showed that the hydrothermal synthesized Co-oxide exhibited a snowflake-like morphology with a hierarchical structure. Second, the snowflake-like Co-oxide was post heated at 300°C and 350°C in an ambient atmosphere. Subsequently, the Mn-oxide was deposited onto the surface of the Co-oxide nanostructure to form a Co/Mn oxide core-shell structure by a secondary hydrothermal process. The resulting Co/Mn oxide core-shell structures were characterized using XRD, SEM, TEM, XPS and electrochemical analyses.
The effect of post heat treatment on the material characteristics and pseudocapacitive performance of the core-shell structure were investigated. The dimension of hydrothermal synthesized Co-oxide with a snowflake-like morphology varied with the post heat treatment conditions. The Co-oxide nanostructure served as a template for the growth of Mn-oxide films. A highest specific capacitance (SC) of 196 F/g and a relatively good electrochemical reversibility can be obtained when the composite electrode was calcined at 300ºC for 4 h. More than 90% capacitance retained after 1200 CV (cyclic voltammetry) cycles. The Co/Mn oxide core/shell structure exhibited a better electrochemical stability, being one of the promising active materials in pseudocapacitor applications.

誌 謝 I
中文摘要 II
Abstract III
總 目 錄 IV
圖 目 錄 VI
表 目 錄 VIII
第一章 前言 1
第二章 文獻回顧 4
2.1 超級電容器的介紹 4
2.2 超級電容器的種類 7
2.2.1 電雙層電容器 7
2.2.2 擬電容器 8
2.3 鈷氧化物之介紹與應用 11
2.3.1 鈷氧化物之簡介 11
2.3.2 鈷氧化物應用於超級電容器 13
2.4 錳氧化物的介紹與應用 17
2.4.1 錳氧化物之簡介 17
2.4.2 錳氧化物應用於超級電容器 18
2.5 水熱法的介紹 22
2.5.1 水熱法之簡介 22
2.5.2 水熱法之原理及應用 23
2.6 超級電容器設備介紹 26
2.6.1 電解液 26
2.6.2 電極 27
2.6.3 電極材料 27
第三章 研究方法 29
3.1 電極材料製備 29
3.1.1 石墨基材前處理 29
3.1.2 水熱法沉積氧化物薄膜 30
3.2 電極材料分析 32
3.2.1 X光繞射晶體結構分析 32
3.2.2 冷場發射掃描式電子顯微鏡表面型態分析 33
3.2.3 高解析穿透式電子顯微鏡粉體結構分析 33
3.2.4 電子能譜儀鍵結分析 34
3.3 電化學電性分析 34
3.3.1 循環伏安法 34
3.3.2 計時電位法 36
第四章 結果與討論 37
4.1 鈷氧化物電極製備之檢測 37
4.1.1 鈷氧化物電極之SEM表面形態分析 37
4.1.2 鈷氧化物電極之TEM顯微結構觀察 41
4.2 鈷/錳氧化物電極隨鈷氧化物煆燒條件改變之比較 42
4.2.1 鈷/錳氧化物電極隨鈷氧化物煆燒條件改變之TGA熱重分析 43
4.2.2 鈷/錳氧化物電極隨鈷氧化物煆燒條件改變之XRD晶體結構分析 44
4.2.3 鈷/錳氧化物電極隨鈷氧化物煆燒條件改變之SEM表面形態分析 48
4.2.4 鈷/錳氧化物電極隨鈷氧化物煆燒條件改變之電性測試 51
4.3 鈷/錳氧化物複合粉體電極製備之檢測 58
4.3.1 鈷/錳氧化物複合粉體電極之XRD晶體結構分析 59
4.3.2 鈷/錳氧化物複合粉體電極之SEM表面形貌分析 60
4.3.3 鈷/錳氧化物複合粉體電極之TEM顯微結構之觀察 60
4.3.4 鈷/錳氧化物複合粉體電極之電性測試 62
4.4 鈷/錳氧化物電極材料在不同階段之分析比較 68
4.4.1 鈷/錳氧化物電極材料在不同階段之XRD晶體結構分析 68
4.4.2 鈷/錳氧化物電極材料在不同階段之SEM表面形態分析 69
4.4.3 鈷/錳氧化物電極材料在不同階段之XPS之化學組成分析 71
第五章 結論 76
參考文獻 77

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