本研究主要是合成線性的poly(2,2,6,6-tetramethylpiperidinyl-1-oxy-4-yl methacrylate (PTMA)和多面體寡聚倍半矽氧烷(POSS)主體的POSS-PTMA高分子，及其應用於有機自由基電池正極的電化學特性。藉由電化學測試如定電流充放電、循環伏安法，選用0.1、0.5、0.8、1.0、1.5和2.0 M LiClO4-EC/DEC = 1/1 (v/v) 的電解液，對PTMA∥Li電池探討其電化學特性。PTMA經由循環伏安法測量其氧化、還原峰電位，並觀察到形式電位(E°')會隨著鋰鹽濃度增加而下降，而兩者之間的波峰電位差(ΔEp)卻會隨著不同鋰鹽濃度的導電度差異有所變化。此外，與一般線性的PTMA高分子做比較，在相同條件下利用原子轉移自由基聚合法(ATRP)製備以多面體寡聚倍半矽氧烷(POSS)主體的POSS-PTMA高分子，其星狀的結構不僅降低了結晶性並藉由長鏈增加其運動性，進而減少在有機電解液中的溶解度，因此在電池的循環壽命上會比較穩定且保有較高的電容量。

In this thesis, poly(2,2,6,6-temtramethylpiperidinyl-1-oxy-4-yl methacrylate (PTMA) and polyhedral oligomeric silsesquioxane-PTMA (POSS-PTMA) have been synthesized by atom transfer radical polymerization (ATRP). The electrochemical performance of the organic radical batteries with either PTMA or POSS-PTMA as cathode-active material was studied. The electrochemical properties of the PTMA∥Li cell with 0.1, 0.5, 0.8, 1.0, 1.5, and 2.0 M LiClO4-EC/DEC = 1/1 (v/v) are characterized by cyclic voltammetry (CV) and charge/discharge characteristics. The results of CV indicate that the formal potential (E°') decreases as the concentration of lithium salt increases. Besides, different concentrations of lithium salt result to the different peak difference potentials (ΔEp) of the redox peaks, which may be due from their ionic conductivity. Furthermore, compared with the linear PTMA in the same condition, the star-like polymer (POSS-PTMA) has relatively high molecular weight, which suppresses the dissolution of POSS-PTMA in organic electrolytes. Therefore, the POSS-PTMA∥Li cell has better cycle-life performance than the PTMA∥Li cell.

第一章 文獻回顧 1
1-1 前言 1
1-2 鋰離子電池 2
1-3 有機自由基電池 3
1-4 POSS介紹 5
1-5 研究動機 7
第二章 實驗藥品與儀器 8
2-1 實驗藥品及材料 8
2-2 實驗儀器 11
2-2-1 傅立葉轉換紅外光譜儀 (Fourier Transform Infrared spectroscometer，FTIR) ………………………………………………………………………………..11
2-2-2 膠體滲透層析儀 (Gel Permeation Chromatography，GPC) 11
2-2-3 化學分析電子光譜儀(Electron Spectroscopy for Chemical Analysis，ESCA) ………………………………………………………………………………..11
2-2-4 電化學儀器 (Electrochemical Analyzer Instrument) 12
2-2-5 電子順磁共振儀(Electron Paramagnetic Resonance，EPR) 12
第三章 實驗流程 13
3-1 起始劑POSS-INI之合成 13
3-2 以ATRP合成POSS-PTMPM及Chain-PTMPM 14
3-2-1 POSS-PTMPM的合成 14
3-2-2 Chain-PTMPM的合成 15
3-3 氧化POSS-PTMA 和 Chain-PTMA 的製備 16
3-3-1 POSS-PTMA的製備 16
3-3-2 Chain-PTMA的製備 17
3-4 製備半電池之工作電極 17
3-4-1 POSS-PTMA 17
3-4-2 Chain-PTMA 18
3-5 半電池的組裝 18
3-6 二極式系統 19
3-7 三極式系統 19
3-8 石英晶體微天秤裝置 : 工作電極製備 20
第四章 結果與討論 21
4-1 核磁共振光譜圖(NMR) 21
4-2 紅外光譜圖(IR) 22
4-3 電子能譜圖(ESCA) 23
4-4 不同聚合比下的POSS-PTMA 和Chain-PTMA 的差異 26
4-5 不同濃度電解液下的離子導電度 28
4-6 循環伏安法(Cyclic Voltammetry，CV)的探討 29
4-6-1 不同鋰鹽濃度下的循環伏安圖 30
4-6-2 形式電位 (Formal potential) 和能階 (Energy level) 的探討 36
4-7 石英晶體微天秤(Quartz crystal microbalance，QCM) 39
4-8 定電流充放電(Chronopotentiometry) 41
第五章 結論 44
參考資料 …………………………………………………………………………..45
附錄 …………………………………………………………………………..46

[1] A. Shafiee, M. M. Salleh, M. Yahaya, Sains Malaysiana 2011, 40, 173-176.
[2] S. Treado, Energies 2015, 8, 11120-11138.
[3] M. S. Whittingham, Science 1976, 192, 1126-1127.
[4] N. Nitta, F. Wu, J. T. Lee, G. Yushin, Materials Today 2015, 18, 252-264.
[5] H. Nishide, K. Koshika, K. Oyaizu, Pure and Applied Chemistry 2009, 81, 1961-1970.
[6] T. Suga, Y.-J. Pu, S. Kasatori, H. Nishide, Macromolecules 2007, 40, 3167-3173.
[7] P. Poizot, F. Dolhem, Energy & Environmental Science 2011, 4, 2003-2019.
[8] G. Hauffman, Q. Maguin, J.-P. Bourgeois, A. Vlad, J.-F. Gohy, Macromolecular Rapid Communications 2014, 35, 228-233.
[9] R. H. Baney, M. Itoh, A. Sakakibara, T. Suzuki, Chemical Reviews 1995, 95, 1409-1430.
[10] D. W. Scott, Journal of the American Chemical Society 1946, 68, 356-358.
[11] S.-W. Kuo, F.-C. Chang, Progress in Polymer Science 2011, 36, 1649-1696.
[12] G. Li, L. Wang, H. Ni, C. U. Pittman Jr, Journal of Inorganic and Organometallic Polymers 2001, 11, 123-154.
[13] R. Y. Kannan, H. J. Salacinski, P. E. Butler, A. M. Seifalian, Accounts of Chemical Research 2005, 38, 879-884.
[14] K. Pielichowski, J. Njuguna, B. Janowski, J. Pielichowski, in Supramolecular Polymers Polymeric Betains Oligomers, Vol. 201 (Eds. : B. Donnio, D. Guillon, A. Harada, A. Hashidzume, W. Jaeger, B. Janowski, S. Kudaibergenov, A. Laschewsky, J. Njuguna, J. Pielichowski, K. Pielichowski, Y. Takashima), 2006, pp. 225-296.
[15] P. J. Launer, Silicone compounds register and review 1987, 100.
[16] F. Busolo, L. Franco, L. Armelao, M. Maggini, Langmuir 2010, 26, 1889-1893.
[17] Y. Ma, C. Loyns, P. Price, V. Chechik, Organic & Biomolecular Chemistry 2011, 9, 5573-5578.
[18] A. Anderko, M. M. Lencka, Industrial & Engineering Chemistry Research 1997, 36, 1932-1943.
[19] P. Yeh, T. Kuwana, Chemistry Letters 1977, 1145-1148.
[20] J. Chen, N. Ding, Z. Li, Q. Zhang, S. Zhong, Progress in Chemistry 2015, 27, 1291-1301.
[21] L. Leonat, G. Sbarcea, I. V. Branzoi, Unversitatea Politehnica Bucuresti Scientific Bulletin, Series B, Vol. 75, Iss. 3 2013, 1454-2331.