我們以非交聯的方式製作出高分子刷薄膜電極作為正極材料，藉由表面起始原子轉移自由基聚合 (SI-ATRP) 的方式成功製作不同接枝密度且表面均勻平整的有機自由基高分子刷。而有機高分子刷薄膜與導電基板之間使用共價鍵作為鍵結，這個方式不僅可有效防止有機高分子溶解於有機電解液中，也改善了電池的循環壽命。
經由表面接枝密度的計算，可以了解表面起始劑密度與高分子鏈接枝數目的關係。我們將針對不同接枝密度氮氧自由基高分子刷的電化學特性及其表面性質進行探討。在表面性質分析藉由接觸角量測儀、原子力顯微鏡 (AFM) 及電子能譜化學分析儀 (ESCA) 進行表面型態鑑定。在電化學性質分析使用循環伏安法 (CV) 及計時電勢法 (CP)，進行氧化還原訊號的觀察與其電容量的量測。結合了原子力顯微鏡與計時安培測定法 (CA) 進行同步 (in-situ) 量測高分子刷薄膜電極表面，以了解在特定電壓下進行反應時的作用機制。
實驗結果發現，起始劑密度1% 的高分子刷不論薄膜厚度的高低，電化學表現上皆相當突出，在電解液中的膨潤效應 (swelling effect) 也較明顯，表示高分子鏈段的活動性也較佳，接枝密度的降低同時也增加離子通道的空間，使離子擴散速度增加，同步實驗中，起始劑密度 1% 的高分子刷在氧化還原時厚度的變化量總是大於起始密度 100% 的高分子刷，這也直接證明起始劑密度 1% 的高分子刷確實擁有較大的離子通道，以利於陰離子的移動。將同步量測氧化條件下的厚度換算活物濃度，代入Cottrell equation，得到了確切的表觀擴散係數，且實驗結果與分子動力模擬是相符合的，起始劑密度1% 的高分子刷具有最快速的表觀擴散係數。

We report a novel approach to study the electrochemical performance of nitroxide radical polymer brushes for thin-film electrodes, in association with the in-situ surface morphology characteristics. In this thesis, we synthesized non-cross-linked nitroxide radical polymer brushes as the positive electrode material for thin-film electrodes via surface-initiated atom transfer radical polymerization (SI-ATRP), which is an effective method to produce smoothly surfaced organic radical polymer brushes with different grafting densities. After SI-ATRP, the covalent bonds between the nitroxide polymers and the conducting substrate are formed, which not only prevent the organic polymer from dissolving into organic electrolyte solution but also improve the cycle life performance of batteries. To understand the correlation between the density of surface-initiator and the amount of polymer chains via calculations of grafting density, we examined the electrochemical performance and the morphology of nitroxide radical polymers by varying their grafting densities. The polymer brushes with different grafting densities are characterized by water contact angle goniometer, atomic force microscope (AFM) and electron spectroscopy for chemical analysis (ESCA), along with electrochemistry techniques such as cyclic voltammetry (CV) and chronopotentiometry (CP). For further study of the mechanism in the polymer layer during electrochemical reactions within designated voltage ranges, in-situ measurements are performed by combining AFM and chronoamperometry (CA). The experimental results show that at 1% initiator composition polymer brushes exhibit better electrochemical performance, and the swelling effect in this electrolyte is also more obvious, implying an enhanced motion of polymer chains. Moreover, the space between ionic channels is enlarged by lowing the grafting density, which leads to a faster ionic diffusion rate. Through in-situ measurements, we found that polymer brushes at 1% initiator composition possess larger variation in thickness than at 100% initiator composition, and the value of apparent diffusion coefficients of polymer brushes reaches its maximum at 1% initiator composition as well, which are both in agreement with the molecular dynamic stimulation results. This study provides direct evidence showing that polymer brushes at 1% initiator composition have larger ionic-channel space, allowing more rapid passage of the anions.

第一章 緒論 1
1-1 簡介 3
1-2 研究動機 6
第二章 文獻回顧 7
2-1 有機自由基高分子 9
2-1.1 自由基 9
2-1.2 氮氧自由基高分子 10
2-1.3 高能量密度高分子設計 11
2-2 有機自由基高分子電池 15
2-2.1 氮氧自由基高分子電池反應機制 17
2-2.2 高分子層內部電子轉移 19
2-3 有機自由基高分子刷 21
2-3.1 原子轉移自由基聚合法 (ATRP) 23
2-3.2 表面起始原子轉移自由基聚合法 (SI-ATRP) 24
2-3.3 控制表面高分子刷密度方法 26
2-4 氮氧自由基高分子刷薄膜電極 27
2-4.1 氮氧自由基高分子刷製備 28
2-4.2 氮氧自由基高分子刷電化學表現 30
2-4.3 氮氧自由基高分子刷的氧化 32
2-5 不同接枝密度氮氧自由基高分子刷薄膜電極 35
2-5.1 不同接枝密度氮氧自由基高分子刷製備 36
2-5.2 不同接枝密度氮氧自由基高分子刷電化學表現 38
2-6 羰基高分子刷薄膜電極 44
第三章 實驗流程 47
3-1 實驗藥品及材料 49
3-2起始劑 (BMPBTS) 的合成 53
3-2.1 化合物but-3-enyl 2-bromo-2-methylpropanoate 合成 53
3-2.2 起始劑 (4-(2-bromo-2-methyl)propionyloxy)butyltrichlorosilane (BMPBTS) 合成 53
3-3 mCPBA的純化 55
3-4 氮氧自由基高分子刷薄膜電極製備 56
3-4.1 ITO 導電玻璃表面修飾 56
3-4.2 氮氧自由基高分子刷薄膜電極製備 57
3-4.3 不同表面起始劑密度PTMA brushes製備 58
3-5 羰基醌類化合物合成 60
3-5.1 化合物1,4-dioxo-1,4-dihydronaphthalen-2-yl acrylate 合成 60
3-5.2 化合物2-Iodoanthraquinone 合成 61
3-5.3 化合物 2-vinylanthraquinone 合成 61
3-5.4 Poly(1,4-dioxo-1,4-dihydronaphthalen-2-yl acrylate) 合成 63
3-5.5 Poly(2 -vinylanthraquinone) 合成 64
3-6 羰基高分子刷薄膜電極製備 64
3-6.1 ITO 導電玻璃表面修飾 64
3-6.2 ITO 表面羰基高分子刷製備 64
3-6.3 鍍金矽晶片表面修飾 65
3-6.4 鍍金矽晶片表面羰基高分子刷製備 66
3-7實驗儀器鑑定分析與原理 67
3-7.1 核磁共振光譜法 (Nuclear Magnetic Resonance, NMR) 67
3-7.2 循環伏安法 (Cyclic Voltammetry, CV) 69
3-7.3 計時安培法 (Chronoamperometry, CA) 71
3-7.4 計時電勢法 (Chronopotentiometry, CP) 71
3-7.5 原子力顯微鏡 (Atomic Force Microscope, AFM) 71
3-7.6 接觸角量測儀 (Contact angle goniometer) 75
3-7.7 膠體滲透層析儀 (Gel Permeation Chromatography, GPC) 76
3-7.8 電子能譜化學分析儀(Electron Spectroscopy for Chemical Analyzer, ESCA) 77
第四章 結果與討論 79
4-1 表面型態測定 81
4-1.1 水接觸角測試 81
4-1.2 原子力顯微鏡測試 82
4-1.3 電子能譜化學分析儀鑑定 84
4-2 接枝密度的計算 87
4-3 電化學性質分析 89
4-4 同步 (in-situ) 量測 90
4-5 擴散係數探討 108
4-5.1 表觀擴散係數的計算 108
4-5.2 分子動力模擬高分子刷的擴散行為 111
4-6 羰基高分子刷 113
第五章 結論與未來展望 115
5-1 結論 117
5-2 未來展望 118
5-2.1 PTMA brushes在不同溶劑下的表面型態 118
5-2.2 改變陰離子大小 118
第六章 參考文獻 119
附錄 127

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