臺灣博碩士論文加值系統

碳氣凝膠為一種理想的電極材料，主要是因為碳氣凝膠擁有較高之比表面積及導電性與孔洞控制性。在我們研究中，利用氫氧化鉀為催化劑，以間苯二酚及甲醛經溶膠-凝膠程序後碳化製備而成，並藉由氫氧化鉀活化提高碳氣凝膠之比表面積及添加中孔型態二氧化鈦於碳氣凝膠前驅體中增加碳材料之中孔體積。並利用導電性填充物與高分子黏結劑進行製備電極，並探討其電化學性能之影響。
由結果顯示，間苯二酚及甲醛之莫爾比為1:2擁有較大之比表面積1208.8 m2 g-1。電極製備過程中，其黏結劑含量最佳為10wt%，經循環伏安分析得知，其電容值最高為195 F/g，經充放電結果顯示其充電電容為227 F/g，經Langmuir 吸附方程式分析單層飽和吸附量3.0748 mg/g。
碳氣凝膠的活化過程中可以發現，比表面積與孔體積隨著間苯二酚與氫氧化鉀的質量比增加(2-5)分別由1208.8提高至 1948 m2/g 及 0.6324提高至0.9406 cm3/g ，其間苯二酚及氫氧化鉀之最佳質量比為 4，氫氧化鉀含量過高導致過活化，當間苯二酚與氫氧化鉀的質量比為4時，其比表面積為1929.0 m2/g，經循環伏安測試分析其電容值為
255 F/g，由Langmuir 吸附方程式分析單層飽和吸附量5.075 mg/g。
以中孔二氧化鈦進行改質之結果可以得知，經循環伏安分析其電容值最高為272 F/g，由Langmuir 吸附方程式分析單層飽和吸附量最高為10.325 mg/g。由單層飽和吸附量可以得知，二氧化鈦添加後能增加離子之吸附量，能增加電容去鹽電極對離子的吸附強度，由此可知，二氧化鈦添加於碳氣凝膠中對鈉離子有效的電吸附，改善二氧化鈦/碳氣凝膠電容去鹽電極性能。

Carbon aerogel is an ideal electrode material because of its low electrical resistivity, high specific surface area, and controllable pore size distribution. Carbon Aerogel were prepared using resorcinol and formaldehyde catalyzed by KOH in a sol–gel process followed by carbonization, during which the KOH serves as an activating agent and increase specific surface area, and it was modified by adding mesopore titania to carbon precursor for increase mesopore volum. The electrode was fabricated by polymer binder and conductive filler, which to probe into the effect of electrochemical performance .
The results show that molar ratio of Resorcinol and Formaldehyde were 1:2 that has the highest surface area of 1208.8 m2 g-1, and found that 10wt% polytetrafluoroethene content by cyclic voltammetry and galvanostatic charge-discharge test have largest capacitance were 195 and 227 F/g. The saturation monolayer adsorption capacity of Langmuir isotherms was 4.2641 mg/g.
For activation by KOH , with an increase of mass ratio of KOH to resorcinol from 2 to 5, both the specific surface area and the pore volume of the carbons aerogel increased, from 1208.8 to 1948 m2/g and 0.6324 to 0.9406 cm3/g, respectively. The optimum mass ratio of KOH to resorcinol was 4, because the too high content of KOH lead to turn off . The specific surface area of 1929 m2/g and the highest specific capacitance of up to 255 F/g were obtained with the mass ratio of KOH to resorcinol of 4, for the same sample, the saturation monolayer adsorption capacity of Langmuir isotherms was 5.0751 mg/g.
For the modified by adding mesopore titania, the highest specific capacitance of TiO2/ carbon aerogel electrode was 277 F/g by cyclic voltammetry. The highest of saturation monolayer adsorption capacity of Langmuir isotherms was 10.325 mg/g , indicate increases in the number of ions per adsorption capacity and in capactive deionization electrode strength of ions by titania incorporation. For the results , electrosorption of Na ion on the carbon aerogel was significantly increased by titania incorporation,resulting in an improved performance of the TiO2-Carbon Aerogel as a CDI electrode.

目錄 I
圖目錄 VI
表目錄 XVI
致謝 XIX
摘要 XX
Abstract XXII
第一章 緒論 1
1.1 電容去鹽起源 3
1.2 電容去鹽簡介 7
1.3 電極材料 8
1.3.1 活性碳(Activated Carbon,AC) 9
1.3.2 奈米碳管(carbon nanotubes) 10
1.3.3 石墨烯(graphene) 16
1.3.4 活性碳纖維(activated carbon fibers) 19
1.3.5 活性碳布(activated carbon cloth , ACC) 20
1.3.6 碳氣凝膠(carbon aerogel) 22
1.4 黏結劑種類 31
1.5 影響電容去鹽效能之因素 35
1.6實驗目的 37
第二章 理論說明 38
2.1 電雙層理論 38
2.1.1 電雙層結構與原理 39
2.2 碳原料之碳化及活化 42
2.2.1 碳化 42
2.2.2 物理活化 43
2.2.3 化學活化 45
2.3 比表面積分析- BET等溫吸附理論 46
2.4 氮氣等溫吸附、脫附曲線 50
2.4.1 孔洞分析 57
2.4.2 微孔結構分析法 58
2.4.3 BJH理論 60
2.5 電化學檢測 61
2.5.1 循環伏安法 61
第三章 實驗方法與儀器 64
3.1 實驗藥品及器材與分析儀器 64
3.2 實驗儀器 65
3.3 分析儀器及參數 66
3.3.1 BET 比表面積測試與孔徑分析 66
3.3.2 熱游離掃描式電子顯微鏡 66
3.3.3 熱重分析儀 66
3.3.4 循環伏安測試（Cyclic Voltammetry） 67
3.3.5 充/放電測試 68
3.4 實驗方法 69
3.4.1 碳氣凝膠之合成 69
3.4.2 碳氣凝膠之活化 70
3.4.3 中孔二氧化鈦之合成 72
3.4.4 二氧化鈦/碳氣凝膠複合材料之製備 74
3.4.5 電容去鹽電極之製備 76
第四章 結果與討論 77
4.1 碳氣凝膠的合成及其電容去鹽電極之製備 77
4.1.1 比表面積分析 77
4.1.2 表面結構分析 81
4.1.3 電極制備分析-黏結劑對電極性能之影響 83
4.1.4 電極制備分析-導電性碳黑對電極性能之影響 92
4.1.5 不同單體濃度合成碳氣凝膠之電化學性質及電容去鹽性能 102
4.1.6 小結 124
4.2 碳氣凝膠之活化 125
4.2.1 比表面積分析 125
4.2.2 表面結構分析 129
4.2.3 循環伏安測試 131
4.2.4 充/放電測試 137
4.2.5 電容去鹽性能分析 139
4.2.6 吸附等溫線方程式分析 144
4.2.7 小結 147
4.3 二氧化鈦/碳氣凝膠複合材料之製備 148
4.3.1 多孔二氧化鈦之合成 148
4.3.2 界面活性劑對孔徑之影響 149
4.3.3 二氧化鈦前驅體對孔徑之影響 153
4.3.4 二氧化鈦/碳氣凝膠之製備 156
4.3.5 循環伏安測試 163
4.3.6 充放電測試 167
4.3.7 電容去鹽性能測試 169
4.3.8 吸附等溫線方程式分析 171
4.3.9 小結 174
第五章 結論與建議 175
5.1結論 175
5.2 建議 177
參考文獻 178

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