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研究生： 吳依庭
Wu, Yi-Ting
論文名稱： 親兩媒含氟共聚高分子之合成及其於鋰離子電池水性黏著劑之應用
Synthesis of Amphiphilic Fluorinated Copolymer used as Water-Based Binder for 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： 77
中文關鍵詞： 鋰離子電池 、水性黏著劑 、無乳化劑乳化聚合法
外文關鍵詞： Lithium-ion battery, water-based binder, surfactant-free emulsion polymerization
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    • 本研究成功地使用無乳化劑乳化聚合法將親水單體和含氟單體聚合，製備出Poly(PEGMA-co-PFHEMA)高分子顆粒分散在水相中，形成親兩媒含氟共聚高分子乳膠溶液，並將其應用於鋰離子電池之電極水性黏著劑。由FT-IR和1H NMR鑑定共聚高分子的分子結構；TEM與DLS觀察親兩媒含氟共聚高分子顆粒球體粒徑約200 nm；從TGA結果得知共聚高分子的熱裂解溫度皆在200 ℃以上，具有熱穩定性；另外，藉由CV與半電池性能測試，水性黏著劑具有電化學穩定性和較小的極化現象，因此，在20C快速放電下與商用黏著劑PVdF相比具有更高的電容量，保有接近63.1 mAhg-1。在循環壽命測試中，1C/1C長效半電池於150次循環充放電的測試後，庫倫效率達98%與維持140 mAhg-1放電電容量。

    Using hydrophilic monomer and fluorinated monomer copolymerize into the latex particles via the surfactant-free emulsion polymerization, resulting in a water-based binder for lithium ion-battery, that is, poly(PEGMA-co-PFHEMA). It has been accomplished and characterized with FT-IR and 1H NMR. The spheric particle size of amphiphilic fluorinated copolymer aproximated 200 nm by TEM and DLS analysis. From the TGA and CV analyses, we found that the binder not only has great thermal stability but also shows good electrochemical stability. For battery application, the specific discharge capacity of half-cell using the new water-based binder possess is 63.1 mAhg-1 at a discharge rate of 20C. Compared with the commercial standard polyvinylidene fluoride, the as-synthesized binder presents a superior electrochemical performance. In cycle-life test, it can reach 98% coulombic efficiency and keep 140 mAhg-1 capacity in 1C/1C charge-discharge rate after 150 cycles test.

    摘要.................................................... I Abstract............................................... II 誌謝.................................................... IX 目錄.................................................... X 表目錄................................................... XV 圖目錄................................................... XVI 第壹章 緒論................................................1 1-1 簡介..................................................1 1-2 文獻回顧...............................................4 1-2-1 鋰離子電池介紹........................................4 1-2-2 鋰離子電池基本原理.....................................5 1-2-3 正極材料.............................................7 1-2-4 黏著劑(binder).......................................8 1-2-4-1 聚偏氟乙烯(polyvinylidene fluoride,PVdF)............8 1-2-4-2 聚醯亞胺(Polyimide,PI)..............................9 1-2-4-3 苯乙烯-丁二烯橡膠(styrene-butadiene rubber, SBR).....10 1-2-4-4 水性羧甲基纖維素(sodium carboxymethyl cellulose,CMC).11 1-2-4-5 玻璃轉移溫度(Tg)對黏著劑的影響........................12 1-2-5 聚乙二醇(polyethylene oxide,PEO).....................14 1-2-6 導電鋰鹽.............................................16 1-2-7 塑化劑...............................................17 1-2-8 隔離膜...............................................19 1-2-9 固體電解質介面膜(solid electrolyte interface,SEI)......20 1-2-10 無乳化劑乳化聚合法(surfactant-free emulsion polymerization,SFEP).....................................22 第貳章 研究方向.............................................24 2-1 研究動機...............................................24 2-2 研究架構...............................................25 第參章 實驗................................................26 3-1 實驗藥品與材料..........................................26 3-2 儀器設備...............................................27 3-3 樣品製備...............................................28 3-3-1 親兩媒含氟共聚高分子乳膠溶液製備..........................28 3-3-2 正極極片製作..........................................30 3-3-3 鈕扣型電池組裝........................................31 3-4 實驗鑑定與分析..........................................32 3-4-1 傅立葉轉換紅外線光譜(FT-IR)............................32 3-4-2 高解析核磁共振光譜儀(1H-NMR)...........................32 3-4-3 穿透式電子顯微鏡(Transmission Electron Microscope,TEM) ....................................................32 3-4-4 動態光散射粒徑分析儀(Dymanic Light Scattering,DLS).....33 3-4-5 熱重分析儀(Thermogravimetric Analysis,TGA)...........33 3-4-6 微差式掃描熱卡計(Differential Scanning Calorimeter,DSC) ....................................................34 3-4-7 線性掃描伏安法(Linear Sweep Voltammetry,LSV)..........34 3-4-8 超高解析場發射掃描式電子顯微鏡(HR-FESEM).................34 3-4-9 循環伏安法(Cyclic voltammogram,CV)...................35 3-4-10 電池效能與長效測試方法與步驟............................36 3-4-11 交流阻抗(AC impedance)..............................36 3-4-12 附著力測試(Adhesion test)...........................38 第肆章 結果與討論............................................39 4-1 親兩媒含氟共聚高分子Poly(PEGMA-co-PFHEMA)之合成與鑑定.......39 4-1-1 傅立葉轉換紅外線光譜(FT-IR)............................39 4-1-2 核磁共振光譜(1H-NMR)..................................41 4-2 親兩媒含氟共聚高分子Poly(PEGMA-co-PFHEMA)之外觀型態分析.....44 4-2-1 穿透式電子顯微鏡(TEM)..................................44 4-2-2 動態光散射粒徑分析儀(DLS)..............................46 4-3 熱重分析(TGA)..........................................47 4-4 DSC熱轉移性質(DSC Thermal transition property).........49 4-5 線性掃描伏安法(Linear Sweep Voltammetry,LSV)............51 4-6 掃描式電子顯微鏡(SEM)....................................52 4-7 循環伏安法(CV).........................................53 4-8 半電池性能測試..........................................57 4-8-1 半電池不同放電速率測試 ..................................57 4-9 半電池長效測試..........................................61 4-9-1 半電池長效...........................................61 4-9-2 電化學交流阻抗分析.....................................64 4-10 附著力測試............................................69 第伍章 結論................................................70 第陸章 參考文獻.............................................72

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