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論文名稱 Title |
單離子導體共聚物應用於鋰矽電池負極之黏結劑 Single-ion conductor copolymer as a binder for lithium-silicon battery anodes |
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系所名稱 Department |
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畢業學年期 Year, semester |
語文別 Language |
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學位類別 Degree |
頁數 Number of pages |
67 |
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研究生 Author |
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指導教授 Advisor |
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召集委員 Convenor |
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口試委員 Advisory Committee |
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口試日期 Date of Exam |
2018-07-10 |
繳交日期 Date of Submission |
2018-07-25 |
關鍵字 Keywords |
馬來酸酐、鋰離子電池、矽、單離子導體、黏結劑 binder, maleic anhydride, lithium-ion batteries, silicon, single-ion conductor |
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統計 Statistics |
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中文摘要 |
矽作為鋰離子電池負極材料,提供相較商業負極材料-石墨高一個數量級的比容量。然而穩定矽負極的生成仍存在著挑戰,因矽於鋰化/去鋰化之電化學過程中會產生劇烈的體積膨脹/收縮。黏結劑的選擇及優化可以明顯改善矽基負極的穩定性。本實驗主要著重在合成新單離子導體共聚物之黏結劑lithium (4-(N-((4-(trifluoromethyl)phenyl)sulfonyl)sulfamoyl)phenyl)((4-vinylphenyl)sulfonyl) amide (SSIFPSBSLi)並利用自由基聚合反應,使用偶氮二異丁腈( AIBN )當起始劑,藉由將SSIFPSBSLi與甲基丙烯酸(methacrylic acid, MAA)和聚甲基丙烯酸乙二醇酯(polyethylene glycol dimethacrylate , PEGMA) 共聚合,得到高分子 poly(SSIFPSBSLi-co-MAA-co-PEGMA)(SMP) 並作為矽基電池之黏結劑。與常規黏結劑聚偏二氟乙烯( PVDF )相比,透過將單離子導體導入黏結劑之方法,將降低電池阻抗,提升Crate 之表現;另外,透過使用順丁烯二酸酐( maliec acid anhydride,MA )與SMP高分子進行交聯將有效提升電池之循環壽命。 |
Abstract |
Silicon (Si) has a high theoretical specific capacity of 4200 mAh/g, which is about 10 times higher than that of commercial graphite anodes. However, its drastic volume change of Si during the lithiation/delithiation process affects the cycle life significantly, which hinders the practical applications. An ideal binder could maintain the integrity of Si particles during the electrochemical process and make a significant progress on the cycling stability. However, commercially used polyvinylidene fluoride (PVDF) is far from ideal binder. In this study, we synthesized a new single-ion conductor copolymer (SMP) as a binder of silicon battery. The results of cell performance show that SMP with its single-ion conducting ability could reduce the resistance of the battery and improve the C-rate performance compared to the binder without single-ion conductor. We have also identified that SMP binder cross-linked with maleic anhydride has the better cycle-life properties than SMP alone. |
目次 Table of Contents |
目錄 論文審定書 i 謝誌 ii 摘要 iii Abstract iv 目錄 v 圖目錄 viii 表目錄 x 第一章、緒論 1 1-1前言 2 1-2研究動機 3 第二章、文獻回顧 4 2-1 鋰離子電池 5 2-1.1 鋰離子電池歷史 5 2-1.2 鋰離子電池工作原理 6 2-2 鋰矽電池 7 2-2.1 矽( Silicon ) 7 2-2.2鋰矽電池之工作原理 8 2-2.3 比較不同鋰離子電池負極材料之性質 9 2-3 鋰矽電池之優化 10 2-3.1黏結劑 10 2-3.2特性官能基強化高分子機械性 11 2-3.4單離子導體電解質 (Single-Ion Conducting Electrolytes) 12 第三章、實驗部分 14 3-1 實驗藥品材料及器材 15 3-2 實驗步驟 18 3-2.1 單離子導體高分子合成 18 3-2.2 矽負極材料極片製作 27 3-2.3 鋰離子電池組裝 28 3-3 高分子結構鑑定儀器介紹 29 3-3.1 高磁場液態核磁共振儀 ( 500 MHz NMR ) 29 3-3.2 電噴灑質譜儀 ( ESI/MS ) 29 3-3.3 凝膠滲透層析儀 ( Gel permeation chromatography ) 29 3-3.4 傅立葉轉換紅外光光譜 ( FT-IR ) 29 3-3.5 掃描式電子顯微鏡 ( SEM ) 30 3-4電化學測試儀器介紹 31 3-4.1 交流阻抗測試 ( AC-impedance ) 31 3-4.2 循環伏安法測試 ( cyclic voltammetry, CV ) 31 3-4.3 半電池充放電性能測試 (Cycle life & C-rate performance) 32 第四章、結果討論 33 4-1單離子導體高分子結構鑑定 34 4-1.1 高磁場液態核磁共振光譜 34 4-1.2 電噴灑質譜儀&凝膠滲透層析儀 36 4-1.3 以順丁烯二酸酐為交聯劑與SMP高分子交聯 37 4-1.4 傅立葉轉換紅外線光譜儀 ( FT-IR Spectrum ) 38 4-2半電池測試 39 4-2.1 循環伏安法 ( Cyclic voltammetry, CV ) 39 4-2.2 循環壽命比較 ( Cycle life ) 40 4-2.2-1探討鋰矽電池以PSSIFPSBSLi作為負極黏結劑於不同混漿比例之 循環壽命表現 40 4-2.2-2探討以不同莫爾比例之單離子導體單體SSIFPSBSLi與MAA進 行共聚合反應對鋰矽電池之循環壽命影響 41 4-2.2-3探討SMP高分子與順丁烯二酸酐交聯與否對於鋰矽電池循環壽 命之影響 43 4-2.3 充放電曲線比較 44 4-2.4 交流阻抗比較 ( AC Impedance ) 46 4-3 掃描式電子顯微鏡比較 48 第五章、結論 49 第六章、參考資料 52 第七章、附錄 56 |
參考文獻 References |
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