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研究生： 黃崇一
Huang, Chong-Yi
論文名稱： 含醚基之聚醯亞胺高分子合成鑑定與其做為鋰離子電池矽負極黏合劑之行為
Synthesis and Characterization of Ether-containing Polyimide and its Behavior as Silicon Anode Binder for Lithium-Ion Battery
指導教授： 郭炳林
Kuo, Ping-Lin
邱繼正
Chiu, Chi-Cheng
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： 2021
畢業學年度： 109
語文別： 中文
論文頁數： 78
中文關鍵詞： 聚醯亞胺 、醚基 、黏合劑 、鋰離子電池 、矽負極
外文關鍵詞： binder, ether group, lithium-ion battery, polyimide, silicon anode
相關次數： 點閱：161  下載：0 
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    • 近年來矽因為本身的高電容量與高蘊藏量，使其成為最有希望取代石墨的負極材料。然而，矽劇烈的體積變化是其商業化過程中最大的阻礙，而解決問題的其中一種方法為利用適合的黏合劑，抑制矽的體積膨脹，提高循環壽命。
    本研究以二步聚合法製備三種含不同醚基數量之聚醯亞胺高分子PI-M、PI-O與PI-T，並將高分子做為鋰離子電池矽負極黏合劑。由FTIR光譜得知，經由熱閉環法處理過後PI-M、PI-O與PI-T的醯亞胺化程度可高達98~99 %。從TGA曲線可發現三種聚醯亞胺高分子的熱裂解溫度皆大於500 oC，熱穩定性良好。拉伸試驗結果顯示，PI-T的斷裂伸長率最高(208 %)，PI-O則擁有最大的抗拉強度(165 MPa)。從剝離力測試與光學顯微鏡的結果發現，醚基的導入除了對集電器能產生額外的作用力，進而提高黏合力之外，還能改善導電碳與矽粉的分散。而PI-T由於導電碳與矽粉的分散程度最佳，因此在不同充放電速率測試中，PI-T在各個充放電速率下都擁有最高的電容值。由循環伏安法可以得知，三種聚醯亞胺黏合劑皆有良好的電化學穩定性。循環壽命測試結果顯示，PI-T因為導電碳分散程度最好，電容值表現最佳；而PI-O的抗拉強度最高，抑制矽體積膨脹的效果最明顯，因此電容衰退速率最低。

    In recent years, silicon has become the most promising anode material to replace graphite due to its high capacity and abundance. However, the dramatic volume change of silicon is the biggest obstacle in its commercialization process, and one of the ways to solve the problem is to use a suitable binder to suppress the volume expansion of silicon and increase the cycle life.
    In this study, three kinds of polyimide (PI) containing different numbers of ether groups, PI-M, PI-O, and PI-T, were prepared by two-step polymerization, and used as silicon anode binders for lithium-ion batteries. According to FTIR spectrum, the degree of imidization of PI-M, PI-O, and PI-T could reach up to 98~99 % after thermal imidization. From TGA curves, it could be found that all three PIs possessed excellent thermal stability with thermal degradation temperature greater than 500 oC. Tensile test results showed that PI-T has the highest elongation at break (208 %) due to the largest number of ether groups on the polymer chain; PI-O had more rigid backbone than PI-T and higher bond strength than PI-M, and thus it exhibited the greatest tensile strength (165 MPa) among three binders. From the results of peeling test and optical microscope images, it could be found that the introduction of ether groups into polymer chains not only formed additional interaction with current collector, which further increased the adhesive strength, but was also beneficial to the dispersion of conductive carbon and silicon particles, leading to better conductivity. Due to the largest number of ether groups on the backbone, PI-T had the superior dispersion of conductive carbon and silicon particles, resulting in the highest capacity at each charging and discharging rate in C-rate performance. From CV curves, it was evident that all three PI binders demonstrated good electrochemical stability. Cycle life test showed that PI-T had the best specific capacity performance due to its better dispersion of conductive carbon; PI-O showed the lowest fading rate, which could be attributed to its high tensile strength that could alleviate the volume expansion of silicon.

    中文摘要 I Abstract II 誌謝 XI 目錄 XIII 表目錄 XVII 圖目錄 XVIII 第一章 緒論 1 1.1 前言 1 1.2 鋰離子電池簡介 2 1.3 鋰離子電池工作原理 4 1.4 研究動機 6 第二章 文獻回顧 7 2.1 負極材料 7 2.1.1 碳負極材料 9 2.1.2 矽負極材料 10 2.2 黏合劑 12 2.2.1 聚偏二氟乙烯(Polyvinylidene fluoride, PVDF) 13 2.2.2 羧甲基纖維素(Carboxymethyl cellulose, CMC) 14 2.2.3 聚丙烯酸(Polyacrylic acid, PAA) 15 2.3 聚醯亞胺(Polyimide, PI)簡介 16 2.3.1 聚醯亞胺之合成 18 2.3.1.1 一步聚合法 18 2.3.1.2 二步聚合法 18 2.3.2 醯亞胺化(Imidization) 20 2.3.2.1 熱閉環法(Thermal imidization) 20 2.3.2.2 化學環化法(Chemical imidization) 21 2.3.2.3 溶液環化法(Solution imidization) 22 第三章 實驗 23 3.1 實驗藥品與材料 23 3.2 儀器設備 25 3.3 聚醯胺酸製備 27 3.4 電池組裝 28 3.4.1 負極極片製作與聚醯胺酸閉環 28 3.4.2 鈕扣型電池組裝 29 3.5 材料鑑定與分析 30 3.5.1 傅立葉轉換紅外線光譜儀(FTIR) 30 3.5.2 熱重分析儀(TGA) 30 3.5.3 微差式掃描熱卡計(DSC) 31 3.5.4 拉伸試驗(Tensile test) 32 3.5.5 剝離力測試(Peeling test) 32 3.5.6 掃描式電子顯微鏡(SEM) 32 3.5.7 光學顯微鏡(OM) 33 3.6 電化學性質分析 34 3.6.1 循環伏安法(CV) 34 3.6.2 電化學阻抗頻譜(EIS) 34 3.6.3 循環壽命測試(Cycle life test) 36 3.6.4 不同充放電速率測試(C-rate performance) 36 第四章 結果與討論 37 4.1 材料鑑定 37 4.1.1 傅立葉轉換紅外線光譜儀(FTIR) 37 4.1.2 醯亞胺化程度(Degree of imidization) 40 4.1.3 熱重損失分析(TGA) 43 4.1.4 微差式掃描熱卡計(DSC) 45 4.1.5 拉伸試驗(Tensile test) 47 4.1.6 剝離力測試(Peeling) 49 4.2 顯微鏡分析 50 4.2.1 掃描式電子顯微鏡(SEM) 50 4.2.2 光學顯微鏡(OM) 52 4.3 電化學性質分析 54 4.3.1 不同充放電速率測試(C-rate performance) 54 4.3.2 循環伏安法(CV) 57 4.3.3 循環壽命測試(Cycle life test) 60 4.3.4 充放電後SEM圖 63 4.3.5 電化學阻抗頻譜(EIS) 64 第五章 結論 68 第六章 參考文獻 69

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