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研究生： 楊登凱
Yang, Teng-Kai
論文名稱： 含磺酸或聚醚之聚醯亞胺合成與鑑定及其於鋰離子電池黏著劑之應用
Synthesis and Characterization of Sulfonater-Contained or Polyether-Contained Polyimide Used as Binder of Lithium-Ion Batteries
指導教授： 郭炳林
Kuo, Ping-Lin
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2016
畢業學年度： 104
語文別： 中文
論文頁數： 82
中文關鍵詞： 磺酸根(SO3-) 、聚醚(PEO) 、聚醯亞胺高分子 、鋰離子電池 、黏著劑 、循環壽命
外文關鍵詞： sulfonate(SO3-), polyether(PEO), polyimide, lithium-ion battery binder, cycle life
相關次數： 點閱：88  下載：6 
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    • 本研究以一步驟高溫聚合法以及二階段溶液環化法，分別製備含有磺酸根(SO3-)之聚醯亞胺高分子(PI-SO3)與含聚醚(EO)之聚醯亞胺高分子(PI-EO)，並將上述兩種高分子作為鋰離子電池之黏著劑。PISO3與PI-EO都因具有聚醯亞胺之結構使得其熱裂解溫度(Td)皆高於275℃，其中以PI-SO3作為電池黏著劑較PI-EO有較優異之特性，在充放電的實驗中PI-SO3在0.1C即擁有153mAhg-1之電容，5C、10C、20C則分別還保有86.9％、67.3％、20.3％之電容值維持率，達到商用黏著劑之等級，甚至在20C之表現優於商用黏著劑。在長效測試方面，聚醯亞胺高分子具有穩定之結構，使其擁有良好的循環壽命，在200圈幾乎沒有衰退之跡象，且庫倫效率值皆穩定保有98％以上。

    Synthesis of sulfonate-contained and polyether-contained polyimide by one-pot high temperature solution imidization and two-step solution imidization have been accomplished and characterized. These two polymers, PI-SO3 and PI-EO, are used as binder of lithium-ion batteries. From TGA analysis, we found out that PI-SO3 and PI-EO had good thermal stability up to 275℃.For battery applications, the PI-SO3 binder showed higher capacities than that of the PI-EO binder under different discharge rates. The cell specific capacity of PI-SO3 was 153mAhg-1 at 0.1C discharge rate and the capacity rentention were 86.9％, 67.3％ and 20.3％ at 5C, 10C and 20C discharge rate, respectively. Moreover, the capacity retention of PI-SO3 binder is higher than that of PVDF binder at 20C discharge. Both the PI-SO3 and PI-EO binders both showed good cycle life at 0.5C rate up to 200 cycles and the columbic efficiency still up to 98％ due to the strong structure of imide functional group.

    目錄 中文摘要 I Abstract II 致謝 X 目錄 XI 表目錄 XV 圖目錄 XVI 第一章 緒論 1 1-1 前言 1 1-2 二次電池發展史 3 1-2-1 鉛酸電池 3 1-2-2 鎳鎘電池 3 1-2-3 鎳氫電池 3 1-3 鋰離子電池介紹 4 第二章 文獻回顧 6 2-1 鋰離子電池之工作原理 6 2-2 正極材料 7 2-2-1 磷酸鋰鐵正極材料(LiFePO4) 8 2-2-2 鋰鈷氧化物正極材料(LiCoO2) 9 2-3 負極材料 12 2-4 隔離膜 14 2-5 電解質 14 2-5-1 高分子電解質 16 2-6 黏著劑(Binder) 17 2-6-1 聚偏二氟乙烯(PVDF) 18 2-6-2 水性黏著劑 20 2-7 聚醯亞胺(Polyimide, PI)簡介 21 2-7-1 兩階段合成 23 2-7-1-1 第一階段－聚醯胺酸之合成 25 2-7-1-2 第二階段－高溫環化法 26 2-7-1-3 第二階段－化學環化法 27 2-7-1-4 第二階段－溶液環化法 28 2-7-2 一階段環化法[39] 28 2-8 研究動機 30 第三章 實驗 31 3-1 實驗藥品與材料 31 3-2 儀器設備 33 3-3 聚醯亞胺高分子黏著劑之製備 34 3-3-1 含磺酸基(SO3-)之聚醯亞胺高分子之製備 34 3-3-2 含聚醚(EO)之聚醯亞胺高分子之製備 36 3-4 電池製備與組裝 38 3-4-1 LiFePO4之正極極片製作 38 3-4-2 鈕扣型電池組裝 38 3-5 實驗分析儀器與測試裝置 39 3-5-1 傅立葉轉換紅外線光譜儀(FT-IR) 39 3-5-2 核磁共振光譜(1H-NMR) 40 3-5-3 掃描式電子顯微鏡(SEM) 40 3-5-4 熱重分析(Thermogravimetric Analysis,TGA) 40 3-5-5 微差式掃描熱卡計(DSC) 41 3-5-6 循環伏安法分析(Cyclic voltammogram，CV) 41 3-5-7 交流阻抗分析(AC Impedance) 42 3-5-8 離子傳導度測量(Ionic conductivity) 43 3-5-9 電池性能測試 44 第四章 結果與討論 45 4-1 聚醯亞胺共聚高分子之鑑定 45 4-1-1 含磺酸根之聚醯亞胺高分子之鑑定 45 4-1-2 含聚醚(EO)之聚醯亞胺高分子之鑑定 48 4-1-3 醯亞胺化程度分析 50 4-2 TGA熱重分析 52 4-3 循環伏安法分析(CV) 54 4-4 含磺酸根或聚醚之聚醯亞胺高分子之離子傳導度 55 4-5 電極表面之SEM 58 4-6 鋰離子電池半電池充放電測試 59 4-6-1 不同放電速率 60 4-6-2 半電池長效分析 65 4-6-3 交流阻抗分析 67 第五章 結論 71 第六章 參考文獻 73 表目錄 表 2 1 正極材料特點比較 11 表 2 2 負極材料特點比較 13 表 2 3 鋰離子電解質特點比較 15 表 2 4 各類水性黏著劑 21 表4 1 FTIR各吸收峰及其對應官能基 50 表4 2 PI-SO3與PI-EO之離子傳導度 57 表4 3 不同放電速率之電池效能 61 表4 4 不同放電速率之電容維持率 61 表4 5 不同高分子黏著劑各圈阻抗值 68 圖目錄 圖 1–1 電池能量密度比較 2 圖 1–2 鋰枝晶生成示意圖 5 圖 2–1 鋰離子電池工作原理示意圖 6 圖 2–2 正極材料與負極材料之電位與電容量圖 7 圖 2–3 磷酸鋰鐵充放電之電壓曲線圖 8 圖 2–4 磷酸鋰鐵結構示意圖 9 圖 2–5 鋰鈷氧結構示意圖 10 圖 2–6 正極材料市場產量歷年成長狀況 11 圖 2–7 Li4Ti5O12晶格結構示意圖 13 圖 2–8 鋰離子在高分子電解質中之傳導示意圖 17 圖 2–9 黏著劑於電池內之示意圖 18 圖 2–10 聚偏二氟乙烯(PVDF)結構 19 圖 2–11 兩階段反應(two-step route) 24 圖 2–12 聚醯胺酸合成(Polyamic acid, PAA)之反應機制 25 圖 2–13 高溫環化法(Thermal Imidization)反應機制 26 圖 2–14 Kapton-H™ Polyimide 結構 27 圖 2–15 化學環化法(Chemical Imidization)反應機制 27 圖 2–16 溶液環化法(Solution Imidization)反應機制 28 圖 2–17 含有磺酸根之二胺離子化溶於m-cresol之結構 29 圖3–1 含磺酸基之聚醯亞胺高分子製備 35 圖3–2 Dean Stark裝置示意圖 36 圖3–3 含聚醚(EO)之聚醯亞胺共聚高分子之製備 37 圖3–4 鈕扣型電池零組件 39 圖3–5 等效電路 43 圖4–1 FT-IR光譜 含磺酸根之聚醯亞胺高分子 46 圖4–2 含磺酸根之聚醯亞胺高分子結構 47 圖4–3 1H-NMR 含磺酸根之聚醯亞胺高分子 47 圖4–4 FT-IR光譜 含聚醚(EO)之聚醯亞胺高分子 48 圖4–5 含聚醚之聚醯亞胺高分子結構 49 圖4–6 1H-NMR 含聚醚之聚醯亞胺高分子 49 圖4–7 FT-IR光譜 含磺酸根之聚醯亞胺高分子(不同反應時間) 51 圖4–8 FT-IR光譜 含聚醚(EO)之聚醯亞胺高分子(不同反應時間) 51 圖4–9 含磺酸根之聚醯亞胺共聚高分子之熱重曲線圖 53 圖4–10 含聚醚(EO)之聚醯亞胺共聚高分子之熱重曲線圖 53 圖4–11 PI-EO與PI-SO3之DSC圖譜 54 圖4–12 PI-SO3、PI-EO與PVDF之CV圖 55 圖4–13 PI-SO3與PI-EO之離子傳導度 57 圖4–14 PI-SO3電極表面SEM (a)x5000(b)x10000 58 圖4–15 PI-EO電極表面SEM(a)x5000(b)x10000 59 圖4–16 PVDF電極表面SEM(a)x5000(b)x10000 59 圖4–17 PI-SO3電池效能測試 62 圖4–18 PI-EO電池效能測試 63 圖4–19 PVDF電池效能測試 64 圖4–20 PI-SO3長效電池效能測試 66 圖4–21 PI-EO長效電池效能測試 66 圖4–22 PVDF長效電池效能測試 67 圖4–23 等效電路模擬 68 圖4–24 PI-SO3長效電池效能測試 69 圖4–25 PI-EO長效電池效能測試 69 圖4–26 PVDF長效電池效能測試 70 圖4–27 100th圈長效電池效能測試比較 70

    1. Tarascon, J.M. and M. Armand, Issues and challenges facing rechargeable lithium batteries. Nature, 2001. 414(6861): p. 359-367.
    2. Hajek, J., French Patent, 8,10, 1949.
    3. Yamaki, J.-i., et al., A consideration of the morphology of electrochemically deposited lithium in an organic electrolyte. Journal of Power Sources, 1998. 74(2): p. 219-227.
    4. Armand, M.B., Intercalation Electrodes, in Materials for Advanced Batteries, D.W. Murphy, J. Broadhead, and B.C.H. Steele, Editors. 1980, Springer US: Boston, MA. p. 145-161.
    5. Ozawa, K., Lithium-ion rechargeable batteries with LiCoO2 and carbon electrodes: the LiCoO2/C system. Solid State Ionics, 1994. 69(3): p. 212-221.
    6. Meyer, W.H., Polymer Electrolytes for Lithium-Ion Batteries. Advanced Materials, 1998. 10(6): p. 439-448.
    7. Padhi, A.K., K.S. Nanjundaswamy, and J.B. Goodenough, Phospho-olivines as positive-electrode materials for rechargeable lithium batteries. Journal of the Electrochemical Society, 1997. 144(4): p. 1188-1194.
    8. Croce, F., et al., A novel concept for the synthesis of an improved LiFePO4 lithium battery cathode. Electrochemical and Solid State Letters, 2002. 5(3): p. A47-A50.
    9. Chung, S.-Y., J.T. Bloking, and Y.-M. Chiang, Electronically conductive phospho-olivines as lithium storage electrodes. Nat Mater, 2002. 1(2): p. 123-128.
    10. Yang, S., et al., Performance of LiFePO4 as lithium battery cathode and comparison with manganese and vanadium oxides. Journal of Power Sources, 2003. 119–121: p. 239-246.
    11. Mizushima, K., et al., LixCoO2 (0<x<-1): A new cathode material for batteries of high energy density. Materials Research Bulletin, 1980. 15(6): p. 783-789.
    12. Ohzuku, T. and A. Ueda, SOLID-STATE REDOX REACTIONS OF LICOO2 (R(3)OVER-BAR-M) FOR 4 VOLT SECONDARY LITHIUM CELLS. Journal of the Electrochemical Society, 1994. 141(11): p. 2972-2977.
    13. Thomas, M.G.S.R., P.G. Bruce, and J.B. Goodenough, Lithium mobility in the layered oxide Li1−xCoO2. Solid State Ionics, 1985. 17(1): p. 13-19.
    14. Bazito, F.F.C. and R.M. Torresi, Cathodes for lithium ion batteries: the benefits of using nanostructured materials. Journal of the Brazilian Chemical Society, 2006. 17: p. 627-642.
    15. 呂學隆, 鋰電池正極材料技術與產業趨勢(一)-總體市場供需與發展. 2011.
    16. Yi, T.F., et al., Structure and Electrochemical Performance of Niobium-Substituted Spinel Lithium Titanium Oxide Synthesized by Solid-State Method. Journal of the Electrochemical Society, 2011. 158(3): p. A266-A274.
    17. Wertheim, G.K., P.T.T.M. Van Attekum, and S. Basu, Electronic structure of lithium graphite. Solid State Communications, 1980. 33(11): p. 1127-1130.
    18. Nalimova, V., et al., X-ray investigation of highly saturated Li-graphite intercalation compound. Carbon, 1995. 33(2): p. 177-181.
    19. Jiang, J. and J.R. Dahn, Effects of solvents and salts on the thermal stability of LiC6. Electrochimica Acta, 2004. 49(26): p. 4599-4604.
    20. 工業技術研究院, 鋰電池材料分析發展. 2009.
    21. Ratner, M.A. and D.F. Shriver, Ion transport in solvent-free polymers. Chemical Reviews, 1988. 88(1): p. 109-124.
    22. Fenton, D., J. Parker, and P. Wright, Complexes of alkali metal ions with poly (ethylene oxide). polymer, 1973. 14(11): p. 589.
    23. Fergus, J.W., Ceramic and polymeric solid electrolytes for lithium-ion batteries. Journal of Power Sources, 2010. 195(15): p. 4554-4569.
    24. Chou, S.-L., et al., Small things make a big difference: binder effects on the performance of Li and Na batteries. Physical Chemistry Chemical Physics, 2014. 16(38): p. 20347-20359.
    25. Kim, J.S., et al., Effect of polyimide binder on electrochemical characteristics of surface-modified silicon anode for lithium ion batteries. Journal of Power Sources, 2013. 244: p. 521-526.
    26. Qian, G.N., et al., Polyimide Binder: A Facile Way to Improve Safety of Lithium Ion Batteries. Electrochimica Acta, 2016. 187: p. 113-118.
    27. Guerfi, A., et al., LiFePO4 water-soluble binder electrode for Li-ion batteries. Journal of Power Sources, 2007. 163(2): p. 1047-1052.
    28. Tsao, C.-H., C.-H. Hsu, and P.-L. Kuo, Ionic Conducting and Surface Active Binder of Poly (ethylene oxide)-block-poly(acrylonitrile) for High Power Lithium-ion Battery. Electrochimica Acta, 2016. 196: p. 41-47.
    29. Yue, L., L. Zhang, and H. Zhong, Carboxymethyl chitosan: A new water soluble binder for Si anode of Li-ion batteries. Journal of Power Sources, 2014. 247: p. 327-331.
    30. Lee, J.-H., et al., Effect of Carboxymethyl Cellulose on Aqueous Processing of LiFePO4 Cathodes and Their Electrochemical Performance. Electrochemical and Solid-State Letters, 2008. 11(10): p. A175-A178.
    31. Lux, S.F., et al., Low Cost, Environmentally Benign Binders for Lithium-Ion Batteries. Journal of The Electrochemical Society, 2010. 157(3): p. A320-A325.
    32. Ding, N., et al., Improvement of cyclability of Si as anode for Li-ion batteries. Journal of Power Sources, 2009. 192(2): p. 644-651.
    33. Doberdò, I., et al., Enabling aqueous binders for lithium battery cathodes – Carbon coating of aluminum current collector. Journal of Power Sources, 2014. 248: p. 1000-1006.
    34. Liaw, D.-J., et al., Advanced polyimide materials: Syntheses, physical properties and applications. Progress in Polymer Science, 2012. 37(7): p. 907-974.
    35. 遠東學報第二十卷第三期. 2003.
    36. Sroog, C.E., et al., Aromatic polypyromellitimides from aromatic polyamic acids. Journal of Polymer Science Part A: General Papers, 1965. 3(4): p. 1373-1390.
    37. Kim, Y.-H., H.-S. Kim, and S.-K. Kwon, Synthesis and Characterization of Highly Soluble and Oxygen Permeable New Polyimides Based on Twisted Biphenyl Dianhydride and Spirobifluorene Diamine. Macromolecules, 2005. 38(19): p. 7950-7956.
    38. Chung, I.S. and S.Y. Kim, Soluble Polyimides from Unsymmetrical Diamine with Trifluoromethyl Pendent Group. Macromolecules, 2000. 33(9): p. 3190-3193.
    39. Gunduz, N., Synthesis and characterization of sulfonated polyimides as proton exchange membranes for fuel cells. 2001, Virginia Polytechnic Institute and State University.
    40. Kreuz, J.A., et al., Studies of thermal cyclizations of polyamic acids and tertiary amine salts. Journal of Polymer Science Part A-1: Polymer Chemistry, 1966. 4(10): p. 2607-2616.
    41. Zhai, Y., et al., The study on imidization degree of polyamic acid in solution and ordering degree of its polyimide film. Journal of Materials Science, 2007. 43(1): p. 338-344.
    42. Kailani, M.H. and C.S.P. Sung, Chemical Imidization Study by Spectroscopic Techniques. 1. Model Amic Acids. Macromolecules, 1998. 31(17): p. 5771-5778.
    43. Xia, S., et al., Synthesis of soluble polyimide derived from novel naphthalene diamines for liquid crystal alignment layers and a preliminary study on the mechanism of imidization. RSC Advances, 2013. 3(34): p. 14661-14670.
    44. Kim, Y.J., et al., Kinetic and mechanistic investigations of the formation of polyimides under homogeneous conditions. Macromolecules, 1993. 26(6): p. 1344-1358.
    45. Furukawa, N., M. Yuasa, and Y. Kimura, Structure analysis of a soluble polysiloxane-block-polyimide and kinetic analysis of the solution imidization of the relevant polyamic acid. Journal of Polymer Science Part A: Polymer Chemistry, 1998. 36(13): p. 2237-2245.
    46. Kuznetsov, A.A., et al., New Alternating Copolyimides by High Temperature Synthesis in Benzoic Acid Medium. High Performance Polymers, 2004. 16(1): p. 89-100.
    47. Zhai, Y., et al., The study on imidization degree of polyamic acid in solution and ordering degree of its polyimide film. Journal of Materials Science, 2008. 43(1): p. 338-344.
    48. Rodrigues, S., N. Munichandraiah, and K.A. Shukla, AC impedance and state-of-charge analysis of a sealed lithium-ion rechargeable battery. Journal of Solid State Electrochemistry, 1999. 3(7): p. 397-405.
    49. Aurbach, D., Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries. Journal of Power Sources, 2000. 89(2): p. 206-218.
    50. Bruce, P.G., Solid state electrochemistry. Vol. 5. 1997: Cambridge University Press.
    51. Huang, J.-Q., et al., Ionic shield for polysulfides towards highly-stable lithium-sulfur batteries. Energy & Environmental Science, 2014. 7(1): p. 347-353.
    52. Morita, M., et al., Proceedings of the Seventh International Meeting on Lithium BatteriesCharge/discharge characteristics of polyaniline-based polymer composite positives for rechargeable lithium batteries. Journal of Power Sources, 1995. 54(2): p. 214-217.
    53. Edman, L., et al., Transport Properties of the Solid Polymer Electrolyte System P(EO)nLiTFSI. The Journal of Physical Chemistry B, 2000. 104(15): p. 3476-3480.
    54. Porcarelli, L., et al., Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries. Scientific Reports, 2016. 6: p. 19892.
    55. Cheon, S.-E., et al., Structural Factors of Sulfur Cathodes with Poly(ethylene oxide) Binder for Performance of Rechargeable Lithium Sulfur Batteries. Journal of The Electrochemical Society, 2002. 149(11): p. A1437-A1441.
    56. Wilkes, B.N., et al., The Electrochemical Behavior of Polyimide Binders in Li and Na Cells. Journal of The Electrochemical Society, 2016. 163(3): p. A364-A372.

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