將氮氧自由基高分子刷接枝在二氧化矽球上，作為無需額外添加黏著劑的有機自由基電池的陰極。利用掃描式電子顯微鏡、穿透式電子顯微鏡、紅外線光譜儀、電子自旋共振儀來鑑定氮氧自由基高分子刷是否經由表面起始原子轉移自由基聚合法(SI-ATRP)成功地接枝在二氧化矽球表面；而從熱重分析圖可以得知，氮氧自由基高分子刷的裂解溫度約為201 ℃，表示有良好的熱穩定性。而二氧化矽球上的氮氧自由基高分子刷的接枝密度為0.74-1.01 chains nm-2。
從電化學石英晶體微天秤結果顯示，利用非交聯的方法將氮氧自由基高分子刷接枝在二氧化矽球上，可以有效地防止高分子刷溶解於有機電解液中；此外，從電化學表現得知，接枝有氮氧自由基高分子刷的二氧化矽球，其放電電容量在10 C的充放電速率下為84.9-111.1 mAhg-1，且在室溫下，以10 C速率進行充放電循環，即使經過300個循環，其放電電容量仍保有原本電容量的96.3 %。

Nitroxide polymer brushes grafted on silica nanoparticles as binder-free cathode for organic radical battery have been investigated. Scanning electron microscopy, transmission electron microscopy, infrared spectroscopy and electron spin resonance confirm that the nitroxide polymer brushes are successfully grafted onto silica nanoparticles via surface-initiated atom transfer radical polymerization. The thermogravimetric analysis results indicate that the onset decomposition temperature of these nitroxide polymer brushes is found to be ca. 201 ◦C. The grafting density of the nitroxide polymer brushes grafted on silica nanoparticles is 0.74–1.01 chains nm−2.
The results of the electrochemical quartz crystal microbalance indicate that the non-crosslinking nitroxide polymer brushes prevent the polymer from dissolving into organic electrolytes. Furthermore, the electrochemical results show that the discharge capacity of the polymer brushes is 84.9–111.1 mAh g−1 at 10 C and the cells with the nitroxide polymer brush electrodes have a very good cycle-life performance of 96.3% retention after 300 cycles.

第一章 文獻回顧........................................................................................................1
1-1 前言………………………………………………………………………...2
1-2 有機自由基高分子………………………………………………………...4
1-3 研究動機…………………………………………………………………...9
1-4 參考文獻………………………………………………………………….10
第二章 實驗藥品與儀器..........................................................................................12
2-1 實驗藥品………………………………………………………………….13
2-2 實驗儀器………………………………………………………………….16
2-2-1 傅立葉轉換紅外線光譜儀………………………………………...16
2-2-2 場發射型掃描式電子顯微鏡……………………………………...16
2-2-3 穿透式電子顯微鏡………………………………………………...17
2-2-4 高解析電子能譜儀………………………………………………...17
2-2-5 熱重分析儀.......................................................................................18
2-2-6 電子順磁共振儀...............................................................................18
2-2-7 膠體滲透層析儀...............................................................................19
2-2-8 電化學分析儀……………………………………………………...20
2-2-9 石英晶體微天秤…………………………………………………...21
2-2-10高磁場液態核磁共振儀…………………………………………..21
2-2-11傅利葉轉換式質譜儀……………………………………………...22
第三章 實驗流程…………………………………………………………………..23
3-1 400 nm二氧化矽球的合成…………………………………………......24
3-2 化合物的合成(But-3-enyl 2-bromo-2-methylpropanoate) (1)………...25
3-3 起始劑的合成 (4-(Trichlorosilyl)butyl 2-bromo-2-methyl
propanoate) (BMPBTS)………………………………………......…….27
3-4 將起始劑 (BMPBTS)修飾在二氧化矽球表面………………………...29
3-5 以表面起始原子轉移自由基聚合法(SI-ATRP)將PTMPM
高分子刷接枝於二氧化矽球上……………………………........….……31
3-6 氧化接枝於二氧化矽球上的PTMPM高分子刷....……………………33
3-7 製備半電池之工作電極………………………………………………….35
3-8 石英晶體微天秤：工作電極製備……………………………………….36
3-9 半電池組裝……………………………………………………………….37
3-10 參考文獻...................................................................................................38
第四章 結果與討論………………………………………………………………..39
4-1 紅外線光譜圖…………………………………………………………….40
4-1-1二氧化矽球組成成份的鑑定……………………………………….40
4-1-2氧化條件的探討……………………………………………….……42
4-2 電子順磁共振圖……………………………………………………….…43
4-3 熱重分析圖……………………………………………………………….45
4-4 二氧化矽球上PTMA高分子刷接枝密度的探討………………………50
4-5 掃描式電子顯微鏡圖…………………………………………………….52
4-6 穿透式電子顯微鏡圖…………………………………………………….55
4-7 電子能譜圖……………………………………………………………….57
4-8 石英晶體微天秤………………………………………………………….63
4-9 電化學分析……………………………………………………………….67
4-9-1 室溫下之循環伏安法及定電流充放電圖………………………...67
4-9-2 氧化濃度的探討…………………………………………………...75
4-9-3 電解液的探討……………………………………………………...77
4-9-4 室溫下之循環壽命圖…………………………………………...…79
4-9-5 擴散速率的探討…………………………………………………...83
4-9-5-1電極在有機溶液中的擴散情形…………………………...83
4-9-5-2半電池的擴散情形………………………………………...88
4-9-6 溫度的探討………………………………………………………...92
4-9-6-1循環壽命圖………………………………………………...92
4-9-6-2定電流放電圖……………………………………………...96
4-9-6-3電阻的探討………………………………………………...98
4-10 參考文獻……………………………………………………………….104
第五章 結論………………………………………………………………………106
5 結論………………………………………………………………………..107
附錄…………………………………………………………………………………109

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