本篇論文主要是研究電解液的鋰鹽濃度對有機自由基電池性能的影響，利用循環伏安法、交流阻抗分析及定電流充放電，分析 PTMA 類∥Li 電池含 0.1、0.5、0.8、1.0、1.5 和 2.0 M LiClO 4 -EC/DEC = 1/1 (v/v) 電解液的電化學表現。充放電結果發現，當鋰鹽濃度提高時，電池的能量密度和功率密度變佳。循環伏安法顯示PTMA 電極的工作電位隨著鋰鹽濃度提高而下降。進一步地，以為交流阻抗分析發現鋰鹽濃度提高時，其電池阻抗下降。此外，利用原子轉移自由基聚合法合成多面體寡聚倍半矽氧烷 (POSS) 製備星形結構的 POSS-PTMA 高分子，藉由降低高分子的結晶性，使高分子鏈的運動性增加，並與一般線性的 PTMA 高分子做比較。發現在低鋰鹽濃度下，POSS-PTMA 電極會有較佳的高功率放電性能。POSS-PTMA∥Li 電池含 0.1 M 和 2.0 M 鋰鹽，在 10 C 的充放電速率經過 300 次循環後，其放電電容量分別為 86.5%和 95.1%。

　　In this thesis, the effects of concentration of lithium salt on the electrochemical performances of organic radical battery are investigated. The electrochemical performances of PTMA-based electrode∥Li cell with 0.1, 0.5, 0.8, 1.0, 1.5, and 2.0 M LiClO 4 -EC/DEC = 1/1 (v/v) are characterized by cyclic voltammetry (CV), AC impedance, and charge/discharge characteristics. The charge/discharge results show that the energy density and power density of the cells increase as the concentration of lithium salt increases. The CV results show that the potential of the PTMA electrode becomes lower as the concentration of lithium salt increases. The results of AC impedance indicate that the cell resistance decreases as the concentration of lithium salt increases. Furthermore, the polyhedral oligomeric silsesquioxane grafted with PTMA (POSS-PTMA) is synthesized by atom transfer radical polymerization. The star polymer of POSS-PTMA may reduce the crystallinity of the polymer and enhance the mobility of the polymer to improve the electrochemical performance of the electrodes. Compared to linear PTMA, the POSS-PTMA electrode in lower concentrations of lithium salt has better high C-rate performance. The cyclability results show that the energy density of POSS-PTMA∥Li cell with 0.1 and 2.0 M lithium salt remains 86.5 and 95.1% at a C-rate of 10 C, respectively.

論文審定書 i
誌謝 ii
摘要 iii
Abstract iv
目 錄 v
圖目錄 viii
表目錄 xi
第一章 文獻回顧 1
　1-1 簡介 1
　1-2 鋰離子電池 2
　1-3 有機鋰電池 3
　1-4 有機自由基電池 5
　1-5 原子轉移自由基聚合法 (ATRP) 6
　1-6 POSS 8
　1-7 研究動機 10
第二章 實驗藥品與儀器 11
　2-1 實驗藥品及材料 11
　2-2 實驗儀器 13
　　2-2-1 傅立葉轉換紅外光譜儀 (Fourier Transform Infrared spectroscometer，FTIR) 13
　　2-2-2 高磁場液態核磁共振儀 (Nuclear Magnetic Resonance，NMR) 13
　　2-2-3 膠體滲透層析儀 (Gel Permeation Chromatography，GPC) 13
　　2-2-4 電化學分析儀 (Electrochemical Analyzer Instrument) 15
　　2-2-5 高解析電子能譜儀 (High Resolution X-ray Photoelectron Spectrometer，HRXPS) 15
　　2-2-6 場發射型掃描式電子顯微鏡 (Field-Emission Scanning Electron Microscope，FE-SEM) 16
　2-3 電化學原理 16
　　2-3-1 循環伏安法 (Cyclic Voltammetry，CV) 16
　　2-3-2 交流阻抗法 (AC Impedance) 18
第三章 實驗流程 21
　3-1 起始劑POSS-INI之合成 21
　3-2 以ATRP合成POSS-PTMPM及Chain-PTMPM 22
　　3-2-1 POSS-PTMPM的合成 22
　　3-2-2 Chain-PTMPM的合成 23
　3-3 氧化POSS-PTMPM及Chain-PTMPM 24
　　3-3-1 POSS-PTMA的製備 24
　　3-3-2 Chain-PTMA的製備 25
　3-4 製備半電池之工作電極 25
　　3-4-1 POSS-PTMA 25
　　3-4-2 Chain-PTMA 25
　3-5 半電池的組裝 26
第四章 結果與討論 27
　4-1 核磁共振光譜圖 (NMR) 27
　4-2 紅外光譜圖 (IR) 28
　4-3 電子能譜圖 (ESCA) 30
　4-4 POSS-PTMA的探討 32
　　4-4-1 氧化當量的差異 32
　　4-4-2 與Chain-PTMA的比較 34
　4-5 掃描式電子顯微鏡圖 (SEM) 34
　4-6 電解液的離子導電度 37
　4-7 循環伏安法的探討 38
　4-8 不同鋰鹽濃度下半電池的交流阻抗 43
　4-9 定電流充放電 45
第五章 結論 49
參考文獻 50
附錄 52

(1) Poizot, P.; Dolhem, F. Energy Environ. Sci. 2011, 4, 2003–2019.
(2) Whittingham, M. S. Science 1976, 192, 1126–1127.
(3) Nishide, H.; Koshika, K.; Oyaizu, K. Pure Appl. Chem. 2009, 81, 1961–1970.
(4) Williams, D. L.; Byrne, J. J.; Driscoll, J. S. J. Electrochem. Soc. 1969, 116, 2–4.
(5) Ohzuku, T.; Wakamatsu, H.; Takehara, Z.; Yoshizawa, S. Electrochimica Acta 1979, 24, 723–726.
(6) Tobishima, S. J. Electrochem. Soc. 1984, 131, 57–63.
(7) Visco, S. J.; Mailhe, C. C.; Jonghe, L. C. D.; Armand, M. B. J. Electrochem. Soc. 1989, 136, 661–664.
(8) Oyama, N.; Tatsuma, T.; Sato, T.; Sotomura, T. Nature 1995, 373, 598–600.
(9) Nakahara, K.; Iwasa, S.; Satoh, M.; Morioka, Y.; Iriyama, J.; Suguro, M.; Hasegawa, E. Chem. Phys. Lett. 2002, 359, 351–354.
(10) Nishide, H.; Suga, T. Electrochem. Soc. Interface 2005, 32–36.
(11) Suga, T.; Pu, Y.-J.; Oyaizu, K.; Nishide, H. Bull. Chem. Soc. Jpn. 2004, 77, 2203–2204.
(12) Braunecker, W. A.; Matyjaszewski, K. Prog. Polym. Sci. 2007, 32, 93–146.
(13) Matyjaszewski, K.; Xia, J. Chem. Rev. 2001, 101, 2921–2990.
(14) Wang, J.-S.; Matyjaszewski, K. J. Am. Chem. Soc. 1995, 117, 5614–5615.
(15) Li, G.; Wang, L.; Ni, H.; Pittman Jr, C. U. J. Inorg. Organomet. Polym. 2001, 11, 123–154.
(16) Scott, D. W. J. Am. Chem. Soc. 1946, 68, 356–358.
(17) Kuo, S.-W.; Chang, F.-C. Prog. Polym. Sci. 2011, 36, 1649–1696.
(18) Baney, R. H.; Itoh, M.; Sakakibara, A.; Suzuki, T. Chem. Rev. 1995, 95, 1409–1430.
(19) Stevens, M. P. Polymer Chemistry: An Introduction; Oxford University Press, Inc: New York, 1999.
(20) Zoski, C. G. Handbook of electrochemistry; Elsevier: Amsterdam; Boston, 2007.
(21) Zanello, P. Inorganic electrochemistry theory, practice and applications; Royal Society of Chemistry: Cambridge, 2003.
(22) Hunter, T. B.; Tyler, P. S.; Smyrl, W. H.; White, H. S. J. Electrochem. Soc. 1987, 134, 2198–2204.
 
(23) Ohno, K.; Sugiyama, S.; Koh, K.; Tsujii, Y.; Fukuda, T.; Yamahiro, M.; Oikawa, H.; Yamamoto, Y.; Ootake, N.; Watanabe, K. Macromolecules 2004, 37, 8517–8522.
(24) Koh, K.; Sugiyama, S.; Morinaga, T.; Ohno, K.; Tsujii, Y.; Fukuda, T.; Yamahiro, M.; Iijima, T.; Oikawa, H.; Watanabe, K.; Miyashita, T. Macromolecules 2005, 38, 1264–1270.
(25) Launer, P. J. Infrared Analysis of Organosilicon Compounds: Spectra-Structure Correlations http://www.gelest.com/gelest/forms/GeneralPages/technology_library.aspx (accessed Jun 11, 2014).
(26) Shokri, B.; Firouzjah, M. A.; Hosseini, S. I. In Proceedings of 19th international symposium on plasma chemistry society, Bochum, Germany; 2009; pp. 26–31.
(27) Busolo, F.; Franco, L.; Armelao, L.; Maggini, M. Langmuir 2010, 26, 1889–1893.
(28) Hauffman, G.; Rolland, J.; Bourgeois, J.-P.; Vlad, A.; Gohy, J.-F. J. Polym. Sci. Part Polym. Chem. 2013, 51, 101–108.
(29) Ma, Y.; Loyns, C.; Price, P.; Chechik, V. Org. Biomol. Chem. 2011, 9, 5573–5578.
(30) Anderko, A.; Lencka, M. M. Ind. Eng. Chem. Res. 1997, 36, 1932–1943.
(31) Chae, I. S.; Koyano, M.; Sukegawa, T.; Oyaizu, K.; Nishide, H. J. Mater. Chem. A 2013, 1, 9608–9611.