臺灣博碩士論文加值系統

本研究以碳酸亞乙烯酯(vinylene carbonate, VC)及在側鏈具有低聚乙二醇鏈段的poly(ethylene glycol)methyl ether methacrylate (PEGMA)做為單體，利用自由基聚合法合成出PVCA-co-P(PEGMA)嵌段共聚物，之後加入雙(三氟甲基磺醯)亞胺鋰(LiTFSI)製備出固態高分子電解質。接著在不同鋰鹽濃度情況下，透過傅立葉轉換紅外線光譜儀(Fourier transform infrared spectroscopy, FT-IR)、固態核磁共振(7Li Magic angle spinning NMR, 7Li MAS NMR)、微差式掃描熱卡計(Differential scanning calorimetry, DSC)、熱重分析(Thermogravimetric analyzer, TGA)及掃描式電子顯微鏡(Scanning electron microscope, SEM)，對此系列高分子電解質進行探討。可得知鋰離子會與PVCA的C＝O基團及P(PEGMA)的醚基基團產生配位作用，而形成暫時性的交聯結構，使得共聚高分子的玻璃轉移溫度上升，且其具有良好的熱穩定性及兩鏈段高分子間有不錯的相容性。最後藉由交流阻抗法(AC-impedance)測量導電度，從導電度(log σ)對溫度倒數(1/T)做圖呈一線性關係，即鋰離子傳導行為是遵循Arrhenius方程式，並且以activated hopping方式進行傳導。

PVCA-co-P(PEGMA) block copolymers were synthesize by free- radical polymerization using vinylene carbonate (VC) and poly(ethylene glycol)methyl ether methacrylate (PEGMA) as monomers. The block copolymers were doped with lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) to form solid polymer electrolytes. Fourier transform infrared spectroscopy (FT-IR), 7Li magic angle spinning NMR (7Li MAS NMR), differential scanning calorimetry (DSC), thermogravimetric analyzer (TGA) and scanning electron microscope (SEM) showed the interaction of Li+ with both the carbonyl group of PVCA and the ether group of P(PEGMA) segments. The glass transition temperatures increased for the block copolymers doped with LiTFSI, and these results indicated the interaction of Li+ with both the carbonyl group of PVCA and the ether group of P(PEGMA) segments form transient cross-linking. Moreover, the thermal stability and compatibility between the polymer segments were good for the polymer electrolytes. The conductivity (log σ) versus reciprocal temperature (1/T) plot was linear which indicated the conduction mechanism following Arrhenius equation and Li+ transport via a activated hopping mechanism.

摘要 i
Abstract ii
目錄 iii
圖目錄 vi
表目錄 ix
第一章 文獻回顧 1
1.1 前言 1
1.2 高分子電解質的介紹 3
1.3 高分子電解質的種類 5
1.3.1 固態高分子電解質 6
1.3.2 膠態高分子電解質 8
1.3.3 高分子電解質的改質 12
1.4 高分子電解質的離子傳導機制 16
1.5 研究動機 18
第二章 實驗儀器原理 20
2.1 阻抗分析法 20
2.1.1 交流阻抗分析 21
2.2 固態核磁共振光譜 24
2.2.1 魔術角旋轉 25
2.2.2 交叉極化 26
第三章 實驗部分 28
3.1 實驗藥品與器材 28
3.2 實驗步驟 29
3.2.1 Poly(vinylene carbonate) (PVCA)的合成 29
3.2.2 Poly(poly(ethylene glycol) methyl ether methacrylate) (Poly(PEGMA))的合成 30
3.2.3 PVCA-co-P(PEGMA)共聚高分子的合成 31
3.2.4 固態高分子電解質薄膜的製備 31
3.3 實驗儀器 32
3.3.1 傅立葉轉換紅外線光譜儀 (Fourier Transform Infrared Spectroscopy, FT-IR) 32
3.3.2 液態核磁共振光譜分析 (Nuclear Magnetic Resonance, NMR) 33
3.3.3 固態核磁共振光譜分析 (Solid-State Nuclear Magnetic Resonance, SS-NMR) 33
3.3.4 場發射型掃描式電子顯微鏡 (Field-Emission Scanning Electron Microscope, FE-SEM) 33
3.3.5 熱重分析儀 (Thermogravimetric Analyzer, TGA) 34
3.3.6 微差式掃描熱卡計 (Differential Scanning Calorimetry, DSC) 35
3.3.7 交流阻抗分析 (AC-impedance) 36
第四章 結果與討論 38
4.1 PVCA-co-P(PEGMA)共聚高分子之結構鑑定：核磁共振 (NMR)、傅立葉轉換紅外線光譜儀 (FT-IR) 38
4.2 添加LiTFSI對PVCA-co-P(PEGMA)共聚高分子之影響 43
4.2.1 傅立葉轉換紅外線光譜儀 (FT-IR) 43
4.2.2 固態核磁共振光譜分析 (7Li-NMR) 47
4.2.3 場發射型掃描式電子顯微鏡 (FE-SEM) 51
4.2.4 熱重分析儀 (TGA) 52
4.2.5 微差式掃描熱卡計 (DSC) 54
4.2.6 固態高分子電解質的導電度分析 59
第五章 結論 66
第六章 參考文獻 68
附錄 73

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