臺灣博碩士論文加值系統

　　本論文研究以成本低廉的工業殺菌、防腐用化學品－苯基苯酚合成多孔活性碳，並藉由B和N的摻雜改變活性碳的孔洞結構來提升比電容值。未摻雜活性碳中，可藉由提升熱裂解溫度及增加含鉀造孔劑的量來提高活性碳的比表面積，並使孔洞變大且變多。對苯基苯酚作為前驅物且熱裂解溫度為900C時，苯基苯酚與鉀之莫耳數比從1:1.5增加到1:20，比表面積從948 m2 g-1增加到2528 m2 g-1；鄰苯基苯酚則從1323 m2 g-1增加到1740 m2 g-1。使用高比表面積之未摻雜活性碳在0.5 M H2SO4(aq)中掃描速率為0.5 mV s-1下測得的比電容值皆可大於200 F g-1，在1 M TEABF4 in ACN中掃描速率為1mV s-1下測得的比電容值也都可大於400 F g-1，且具有良好的循環穩定性。
　　當摻入5%硼酸後得到的摻硼活性碳，不管苯基苯酚與鉀之莫耳數比為1:12還是1:20，都可獲得比未摻雜活性碳大的比表面積，比表面積最大可達2609 m2 g-1，且孔洞也有變大的趨勢。最大比表面積之摻硼活性碳在0.5 M H2SO4(aq)中掃描速率為0.5 mV s-1下測得的比電容值為316.6 F g-1，在1 M TEABF4 in ACN中掃描速率為1mV s-1下測得的比電容值為509.7 F g-1。當硼酸摻雜量提升至10%後，比表面積及孔洞又比5%硼之活性碳提升更多，比表面積最大為2659 m2 g-1。而此摻硼活性碳在0.5 M H2SO4(aq)中掃描速率為0.5 mV s-1下測得的比電容值為344.7 F g-1，在1 M TEABF4 in ACN中掃描速率為1mV s-1下測得的比電容值為521.3 F g-1。不管硼的摻雜量為5%還是10%，都有良好的循環穩定性。
　　摻入N之後，熱裂解溫度為900C所得的摻氮活性碳，比表面積更是高達3000 m2 g-1以上，2 nm以上之中孔含量也明顯提高。而摻氮活性碳在0.5 M H2SO4(aq)中掃描速率為0.5 mV s-1下可得到高達500 F g-1以上的比電容值，在1 M TEABF4 in ACN中掃描速率為1mV s-1下也可獲得550 F g-1以上的比電容值，且循環穩定性也極佳，但產率卻不到20%。
　　最後利用2種不同電解質(TEABF4和TBABF4)及5種不同孔徑分佈之活性碳驗證不同孔洞大小對不同離子大小造成之影響，從不同電解液測得的循環伏安曲線之差異比對孔徑分佈圖，可發現TBA+幾乎不能進入1.5 nm以下之孔洞中。

In this study, a low-cost chemical phenylphenol has been implemented as the precursor of activated carbon for electrochemical capacitor applications. The energy storage capability of this activated carbon is further enhanced by doping of B and N.
In undoped activated carbon, the specific surface area of the activated carbon can be increased by raising the pyrolysis temperature and the amount of the pore-forming potassium agents, and the pore size also become larger and more. The molar ratio of phenylphenol to potassium increased from 1:1.5 to 1:20, specific surface area increased from 948 m2 g-1 to 2528 m2 g-1, when para-phenylphenol is used as a precursor at 900C; specific surface area increased from 1323 m2 g-1 to 1740 m2 g-1, when ortho-phenylphenol is used as a precursor. The specific capacitance can be greater than 200 F g-1, using a high specific surface area undoped activated carbon at scan rate of 0.5 mV s-1 in 0.5 M H2SO4(aq). The specific capacitance exceeds 400 F g-1 at scan rate of 1 mV s-1 in 1 M TEABF4 in ACN. Also it displays good cycle stability.
Boron-doped activated carbon obtained after incorporation of 5% boric acid, regardless of the molar ratio of phenylphenol to potassium is 1:12 or 1:20, both achieve a larger specific surface area than undoped activated carbon, the specific surface area can be up to 2609 m2 g-1, and the pore also tends to increase in size. The specific capacitance of the boron-doped activated carbon is 316.6 F g-1 at scan rate of 0.5 mV s-1 in 0.5 M H2SO4(aq). The specific capacitance is 509.7 F g-1 at a scan rate of 1 mV s-1 in 1 M TEABF4 in ACN. The specific surface area is up to 2659 m2 g-1, when the amount of boric acid is increased to 10%, the specific surface area and pores are more enhanced than 5% boron. The specific capacitance of the boron-doped activated carbon is 344.7 F g-1 at scan rate of 0.5 mV s-1 in 0.5 M H2SO4(aq). The specific capacitance is 521.3 F g-1 at a scan rate of 1 mV s-1 in 1 M TEABF4 in CAN, regardless of whether the doping amount of boron is 5% or 10%, and it shows good cycle stability.
After doping with nitrogen, the activated carbon obtained through pyrolysis at 900C, the specific surface area reaches 3000 m2 g-1 or more, and the amount of mesoporous pores is raised as well. Nitrogen-doped activated carbon is measured with specific capacitance more than 500 F g-1 at scan rate of 0.5 mV s-1 in 0.5 M H2SO4(aq). Specific capacitance more than 550 F g-1 can be obtained at a scan rate of 1 mV s-1 in 1 M TEABF4 in ACN, and the cycle stability is also excellent, but the yield is less than 20%.
Finally, two different electrolytes (TEABF4 and TBABF4) and five different pore size distributions of activated carbon were used to study the connections between different pore sizes on different ion sizes. We also find TBA+ hardly enter pores which the size is smaller than 1.5 nm, when comparing the difference in cyclic voltammetry curves measured from different electrolytes and the pore size distribution pattern.

摘要 I
ABSTRACT III
目錄 V
圖目錄 X
表目錄 XXIII
第一章 緒論 1
1.1 前言 1
1.2 研究動機 2
第二章 文獻回顧 5
2.1 苯基苯酚 5
2.1.1 苯基苯酚之性質 5
2.1.2 苯基苯酚之應用 5
2.2 能量儲存裝置 6
2.2.1 超級電容器之概述 7
2.2.2 超級電容器之應用 9
2.3 多孔碳材在超級電容器上之應用 10
2.4 雜原子摻雜石墨烯 11
2.4.1 化學氣相沉積法 15
2.4.2 球磨法 15
2.4.3 熱退火法 16
2.4.4 濕式化學法 17
2.5 電解液 18
2.5.1 水性電解液 20
2.5.2 有機電解液 21
2.5.3 離子液體 24
第三章 實驗方法與步驟 25
3.1 實驗藥品耗材與設備 25
3.1.1 碳材製備 25
3.1.2 電極製備 25
3.1.3 電解液配製 26
3.1.4 電化學測試儀器及設備 27
3.1.5 其它設備 27
3.2 實驗分析儀器 28
3.3 實驗流程圖 29
3.3.1 未摻雜活性碳製備 29
3.3.2 摻硼活性碳製備 30
3.3.3 摻氮活性碳製備 31
3.3.4 電極漿料製備 32
3.3.5 工作電極製備 33
3.4 實驗方法 34
3.4.1 碳材合成 34
3.4.2 電極製備 42
3.5 電極材料鑑定與分析 43
3.5.1 表面積及孔徑分析 43
3.5.2 表面結構分析 46
3.5.3 X光繞射分析 46
3.5.4 元素分析 47
3.5.5 拉曼光譜分析 48
3.6 電化學特性分析 49
3.6.1 循環伏安法 50
3.6.2 恆電流充放電量測及穩定性測試 51
第四章 結果與討論 53
4.1 未摻雜活性碳(Undoped Activated Carbon) 53
4.1.1 未摻雜活性碳之表面積及孔徑分析 54
4.1.2 未摻雜活性碳之表面結構分析 72
4.1.3 未摻雜活性碳之X光繞射分析 73
4.1.4 未摻雜活性碳之元素分析 75
4.1.5 未摻雜活性碳之拉曼光譜分析 76
4.1.6 未摻雜活性碳電極之循環伏安分析 80
4.1.7 未摻雜活性碳電極之循環穩定性測試 92
4.2 摻硼活性碳(B-doped Carbon) 97
4.2.1 摻硼活性碳之表面積及孔徑分析 98
4.2.2 摻硼活性碳之表面結構分析 116
4.2.3 摻硼活性碳之X光繞射分析 118
4.2.4 摻硼活性碳之元素分析 121
4.2.5 摻硼活性碳之拉曼光譜分析 122
4.2.6 摻硼活性碳電極之循環伏安分析 125
4.2.7 摻硼活性碳電極之循環穩定性測試 140
4.3 摻氮活性碳(N-doped Carbon) 145
4.3.1 摻氮活性碳之表面積及孔徑分析 146
4.3.2 摻氮活性碳之表面結構分析 152
4.3.3 摻氮活性碳之X光繞射分析 152
4.3.4 摻氮活性碳之元素分析 154
4.3.5 摻氮活性碳之拉曼光譜分析 154
4.3.6 摻氮活性碳電極之循環伏安分析 156
4.3.7 摻氮活性碳電極之循環穩定性測試 163
4.4 不同電解質離子大小對多孔碳造成之影響 166
4.4.1 孔徑分佈之差異 167
4.4.2 在1 M TBABF4 in ACN之循環伏安分析 168
第五章 結論 176
參考文獻 181

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