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研究生： 吳建驊
Jian-Hua Wu
論文名稱： 含氟官能基苯並咪唑鋰鹽添加劑用於高溫高電壓鋰離子電池之研究
The Investigation of Fluoro-Functionlized Benzimidazole Li Salt Electrolyte Additive in Lithium Ion Battery
指導教授： 王復民
Fu-Ming Wang
口試委員: 蘇威年
none
林正裕
none
楊長榮
none
學位類別： 碩士
Master
系所名稱： 應用科技學院 - 應用科技研究所
Graduate Institute of Applied Science and Technology
論文出版年： 2016
畢業學年度： 104
語文別： 中文
論文頁數： 132
中文關鍵詞： 苯並咪唑 、電解液 、添加劑 、鋰離子電池 、鈍性膜
外文關鍵詞： benzimidazole, electrolyte, additive, lithium ion battery, SEI
相關次數： 點閱：476  下載：3 
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  •  上一筆

    • 在鋰離子電池構成材料中，電解液扮演著讓正負極之間的鋰離子互相傳遞的重要角色。目前在電解液中常用的鋰鹽為LiPF6，不過LiPF6在高溫與高電壓環境下，容易產生PF5，使電解液降解形成LiF 和 HF，甚至破壞電極表面，使其安全性不佳，使其在應用上增添不少風險。本研究將苯並咪唑鋰鹽當作電解液添加劑行路易士酸反應，以減少PF5，以期維持電池性能。
    本研究探討以苯並咪唑結構為主體在結構上導入氟官能基，開發興新型態含氟鋰鹽做為電解液之添加劑。該並咪唑結構藉由氟官能基的高電負度來幫助鋰鹽解離，開發出高離子傳導與高電壓電解液。並搭配過量鋰正極材料(Li1.2Ni0.2Mn0.6O2)，進行循環伏安量測分析、交流阻抗測試、電池充放電與壽命趨勢，發現新型態含氟鋰鹽能提升電池性能。
    此外，藉由臨場質譜產氣分析上發現，含氟鋰鹽添加劑用於過量鋰正極時，由於含氟官能基的高電負度能維護電解液進行的電化學反應，使高電壓正極材料在充放電過程中釋出的氧氣量減少，使得電池性能得以維持。

    LiPF6 is widely used lithium salt, which plays a critical role in initiating electrochemical reaction in lithium ion batteries. However, LiPF6 is usually at several unreasonable surrounding such high T, high V, and high humidity. At high T, the LiPF6 suffers side reaction and forms PF5, which degrades the solid electrolyte interface (SEI) and leads the formations of LiF and HF. Due to the Lewis acid basic reaction, benzimidazole-based lithium salt (BZ) is used neutralized the PF5, which side reaction in lithium in battery.
    In this study, modified BZ salt additives are successfully synthesized, which is designed with the electron-withdrawing groups. In terms of the results, fluoro-modified BZ salt increases the ability of electrolyte within lithium cathode layer material. Related cyclic voltammetry, electrochemical impedance spectroscopy, charge-discharge, and cycle life are investigated.
    Our in-situ GC/MS analysis reveals that the fluoro-modified BZ inhibits the gas evolution from Li-rich cathode indication the electron-withdrawing groups is useful for maintain the anodic reaction of electrolyte. These materials are new, first publication for the application of high voltage lithium in battery.

    目錄 摘要 I Abstract III 致謝 V 目錄 VII 圖目錄 IX 表目錄 XIII 第一章 緒論 1 1.1前言 1 1.2鋰離子電池原理與介紹 4 1.2.1正極 6 1.2.2負極 14 1.2.3隔離膜 16 1.2.4電解液 17 第二章 電解液文獻回顧 21 2.1添加劑 21 2.1.1 SEI形成改良添加劑 22 2.1.2正極保護添加劑 30 2.1.3減少鋰金屬沉積之添加劑 32 2.1.4安全性添加劑 33 2.1.5鋰鹽穩定劑 37 2.2鋰鹽 41 2.2.1 LiBOB 41 2.2.2 Li2B12F12 43 2.3 Benzimidazole vs Imidazole 45 2.4研究動機 49 第三章 實驗方法與儀器設備 51 3.1實驗藥品 51 3.2儀器設備 52 3.3材料合成鑑定分析 54 3.3.1質譜儀(Mass Spectrometry) 54 3.3.2核磁共振儀分析(NMR) 55 3.4電解液性能測試 55 3.4.1離子導電度(Ionic Conductivity) 55 3.4.2微分掃描熱卡分析儀(Differential Scanning Calorimeter) 57 3.5電化學性能測試 59 3.5.1半電池循環伏安法(Cyclic Voltammetry(for half cell)) 60 3.5.2電池測試(Battery Test) 61 3.5.3交流阻抗分析(Electrochemical Impedance Spectroscopy) 62 3.6電極表面分析 65 3.6.1掃描電子顯微鏡(Scanning Electron Microscope) 65 3.6.2能量散佈分析儀(Energy-Dispersive X-ray Spectroscopy) 66 3.7臨場質譜產氣分析(In-situ Mass Spectroscopy Gas Analysis) 67 第四章結果與討論 69 4.1 鋰鹽合成 69 4.1.1 Synthesis of 2-amino-4-fluoroaniline and 2-amino-4,5-difluoroaniline 69 4.1.2 Synthesis of fluorobenzimidazole and difluorobenzimidazole 70 4.1.3 Synthesis of Lithium Benzimidazole 71 4.2 電解液性能測試 75 4.2.1 離子導電度(Ionic Conductivity) 76 4.2.2差示掃描量熱法(Differential Scanning Calorimeter) 79 4.3電化學與電池性能測試 81 4.3.1耐高電壓循環伏安量測分析(Cycle Voltammetry) 81 4.3.2正極半電池耐高壓特性 84 4.3.3正極半電池交流阻抗分析 88 4.4 添加劑對正極材料表面分析 96 4.4.1掃描電子顯微鏡(Scanning Electron Microscope) 96 4.4.2能量散佈分析儀(Energy-Dispersive X-ray Spectroscopy) 98 4.5臨場質譜產氣分析(In-situ Mass Spectroscopy Gas Analysis) 99 4.6正極半電池高溫(60℃)充放電性能測試 102 第五章：結論 105 5.1鋰鹽合成與電解液性能 105 5.2添加劑對電化學與電池影響 105 5.3添加劑對正極材料表面影響 107 5.4產氣分析 107 第六章：未來工作展望 109 參考資料 111

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