臺灣博碩士論文加值系統

超電容器由於可以提供比傳統電池更高的瞬間功率，在電池之研
究與應用已經成為熱門的研究主題，其中非對稱超電容器是由兩個不
同之材質為基底的電極組合而成，藉由這種方法可以使整個電池系統
的操作電壓提高，進而提升系統的比電容值以及能量密度，是目前最
具有潛力的儲能元件。本研究利用石墨烯之電學性質優點，結合紙漿
纖維易成型性與可撓性特點，製備成可撓式複合電極，最後組裝成對
稱與非對稱性超電容器。
研究中將石墨烯與紙漿纖維均勻混和，乾燥後形成石墨烯複合電
極，再利用無電鍍的方式將金屬鎳鍍在電極表面，以不同電鍍時間的
樣品鍛燒氧化後，得到不同比例的金屬鎳/氧化鎳/石墨烯作為超電容
器之正極，電極材料將以TGA、XRD、SEM 及BET 等儀器做檢測與
分析。電化學分析方面，利用以KOH 做為電解液製備成非對稱超級
電容器，另外以高分子複合物作為膠態電解質，製備出可撓式非對稱
超級電容器進行比較，測試其彎曲之機械完整性、比電容值、充放電
穩定度以及能量密度等，以找出製備可撓式非對稱性超電容器電極之
最適化條件。
此非對稱超級電容器以KOH 做為電解溶液，在電流密度0.5A g-1
時，具有比電容值77.5 F g-1；使用高分子膠態電解質組成可撓式非對
稱型超電容器後，改變不同的彎曲程度，對其本身的性質沒有特別影
響，展現出良好的撓曲性，在電流密度0.2A g-1 時，具有比電容值34.61
F g-1，在充放電循環圈數500 圈進行穩定度測試後，電容值幾乎沒有
下降的跡象，具有優異的穩定性質。

As the supercapacitors can provide a higher power density than conventional batteries, it has become a potential application in the energy storage device. Asymmetric supercapacitor is assembled by two slightly different electrode's materials, and the operating voltage can be enhanced and the capacities and energy densities also be dramatically improved. In this study, we have combined the excellent electric properties of graphene with the flexibility of the plant fibers into a flexible composite electrode, and finally assembled into symmetric and asymmetric supercapacitor.
Graphene are uniformly mixed with plant fibers and dried to form a graphene composite electrode.Using electroless plating method to plate nickel on the surface of graphene sheets composites. By controlling the plating time, we can obtain different ratios of Ni/Graphene. Nickel was partially oxidized to nickel oxide because of high-temperature calcinations. The different ratios of Ni/NiO/Graphene composites then formed as a positive electrode of asymmetric supercapacitor.
These composite materials will be tested with TGA, XRD andSEM equipments. With KOH and polymer gel as the electrolyte, we assembled the positive and negative electrodes into asymmetric supercapacitors. By the electrochemical test, the electrochemical properties could be obtained to identify optimal conditions for the preparation of flexible asymmetric supercapacitor.
By using KOH as electrolyte, the asymmetric supercapacitor has a capacitance value 77.5 F g-1 at a current density of 0.5A g-1. On the other hand, the flexible asymmetric supercapacitor still maintain its own characteristic during bending, showing good flexibility. It has a capacitance value 34.61 F g-1 at a current density of 0.2A g-1. The supercapacitor exhibits excellent stability with nearly no decrease after 500 cycles.

摘要-----ii
Abstract-----iii
目錄-----v
表目錄-----viii
圖目錄-----ix
第一章緒論-----1
1-1 前言 -----1
1-2 研究動機與目的-----2
第二章文獻回顧-----3
2-1 超級電容器-----3
2-1-1 超級電容器簡介-----3
2-1-2 電極材料儲能機構的影響 -----6
2-1-3 超級電容器組裝結構-----7
2-1-4 電解質的影響-----12
2-2 無電鍍鎳-----13
2-2-1 無電鍍液的組成-----14
2-2-2 敏化與活化-----15
2-2-3 無電鍍鎳機制 -----15
2-3 造紙技術-----16
2-4 石墨烯-----18
2-5電化學測試原理-----20
2-5-1 循環伏安法-----20
2-5-2恆電流充放電法-----21
第三章實驗方法及步驟-----22
3-1 實驗藥品-----22
3-2 實驗分析儀器-----23
3-3 實驗流程-----24
3-4 實驗方法-----25
3-4-1 氧化石墨烯製備-----25
3-4-2 石墨烯紙漿複材製備-----25
3-4-3無電鍍鎳製備-----25
3-4-4 電化學測試-----26
3-5 分析儀器簡介-----27
3-5-1掃描式電子顯微鏡-----27
3-5-2 穿透式電子顯微鏡-----27
3-5-3 熱重分析儀-----28
3-5-4 廣角X-ray分析儀-----28
3-5-5電化學裝置與原理-----29
3-5-5-1 三極式電極系統電化學裝置-----29
3-5-5-2 電化學原理-----31
第四章結果與討論-----32
4-1 負極材料之特性分析-----32
4-1-1 GF電極於不同熱處理溫度下之XRD分析-----32
4-1-2 氧化石墨烯之TEM分析-----34
4-1-3 GF電極之TGA分析-----35
4-1-4 GF電極之SEM分析-----36
4-1-5 GF電極於不同熱處理溫度下之電化學分析-----38
4-2 正極材料之特性分析-----43
4-2-1 NiO/Ni/GF電極於不同析鍍時間下之XRD分析-----43
4-2-2 NiO/Ni/GF電極於不同析鍍時間下之SEM分析-----44
4-2-3 NiO/Ni/GF電極於不同析鍍時間下之TGA分析-----47
4-2-4 不同析鍍時間下NiO/Ni/GF電極之電化學分析-----49
4-3 對稱型以及非對稱型超電容器之電化學性質-----57
4-3-1 以1M KOH做為電解質-----57
4-3-2 以高分子膠態電解薄膜做為電解質-----65
第五章結論-----74
參考文獻-----76

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