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研究生： 傅冠穎
Fu, Guan-Ying
論文名稱： 環碳酸酯類對氟化乙烯基高分子/離子液體/鋰鹽之鋰離子電池類固態電解質性質與性能之影響
The Effect of Cyclic Carbonates on the Properties and Performance of Fluorinated Vinyl Polymer/Ionic Liquid/Lithium Salt Quasi-Solid Electrolyte of Li-ion Batteries
指導教授： 詹正雄
Jan, Jeng-Shiung
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： 英文
論文頁數： 107
中文關鍵詞： 鋰離子電解質 、固態電解質 、碳酸乙烯酯 、碳酸丙烯酯 、循環充放電效率
外文關鍵詞： Li-ion battery, solid electrolyte, ethylene carbonate, propylene carbonate, cycling efficiency
相關次數： 點閱：91  下載：5 
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    • 由於鋰離子電池的液態電解質本質上的高揮發性造成的安全問題，類固態電解質因其低揮發性和耐燃性而受到關注，P(VdF-HFP)和離子液體的是其中最簡單的系統之一，離子液體提供相對較高的導離子度，而P(VdF-HFP)高分子則保持足夠的機械強度。為了穩定的固體電解質介面(SEI)和良好的長效充放電效能，商用鋰離子電池使用某些特定的有機溶劑，例如碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二甲酯(DMC)……等。在這份研究中，我們以加入碳酸乙烯酯(EC)和碳酸丙烯酯(PC)改善了一個由P(VdF-co-HFP)和特定離子液體組成的類固態電解質，增進了導離子度，使不同速率的充放電效能有所進步，最重要的是，長效充放電效能有大幅度的改善，我們以交流阻抗分析了其半電池並以模型分析所得的圖譜，看到了更穩定的SEI。除此之外，我們比較了此類固態電解質和單純的離子液體/碳酸酯類混合的電解質的安全性，發現高分子P(VdF-HFP)能有效阻止碳酸酯類在高溫溢出。

    With the innately volatile nature of liquid electrolytes causing the safety concern of Li-ion batteries, solid-like electrolytes have attracted interest due to their intrinsic low volatility and flammability. The system of P(VDF- HFP) and ionic liquids is one of the simplest; while the ionic liquids inside provide relatively high ionic conductivity, the matrix, P(VDF-co-HFP), retains enough mechanical strength. In commercial liquid electrolytes, certain organic compounds are utilized in order for stable SEI (Solid Electrolyte Interface) and good cycling efficiency, including ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), and so on. Here, we improve a solid-like electrolyte, which is composed of P(VDF-co-HFP) and certain ionic liquids, by introducing EC and PC into the system. Improvement in ionic conductivity was obtained, enhancing the performance of charge-discharge at various C rates. Most importantly, the long-term cyclic performance is significantly improved. We examined the cells with EIS analysis (Electrochemical Impedance Spectroscopy) and performed modeling on the obtained diagrams. As expected, a more stable SEI was seen. In addition, the solid-like electrolytes were also compared with ionic liquid/carbonate electrolytes in terms of safety, and it was found that the polymer effectively prevent the carbonates from escape at elevated temperature.

    Abstract I 摘要 II 致謝 III Table of content IV List of tables VII List of figures VIII List of appendix XII Chapter 1 Introduction 1 Chapter 2 Review 3 2-1 The principle of lithium batteries 3 2-2 Cathode materials 4 2-2-1 LiFePO4 4 2-2-2 LiCoO2 5 2-3 Anode materials 5 2-3-1 Carbonaceous material 6 2-3-2 Lithium titanium oxide 7 2-4 Electrolyte 8 2-4-1 Lithium salts 9 2-4-2 Liquid electrolytes 9 2-4-3 Ionic liquids / room temperature molten salts 12 2-4-4 Polymer electrolytes 16 2-4-5 Mixture of ionic liquids and conventional liquid electrolytes 20 2-4-6 Ionic liquid-polymer composite electrolytes 22 2-5 Passivation 23 2-5-1 Passivation on a Lithium anode 23 2-5-2 Passivation on a carbonaceous anode 24 2-5-3 Passivation on a cathode 26 2-6 Electrochemical impedance spectroscopy modeling 26 Chapter 3 Experimental 29 3-1 Material 29 3-2 Equipment 30 3-3 Sample preparation 31 3-3-1 Anion substitution of Ionic liquids 31 3-3-2 Preparation of solid-like electrolyte 32 3-4 Cell fabrication and characterization 33 3-4-1 Preparation of LiFePO4 cathode 33 3-4-2 Half-cell assembly 33 3-4-3 Charge-discharge performance of different C rate 34 3-4-4 Cycle life 34 3-4-5 Ionic Conductivity 35 3-4-6 Lithium Transference Number 35 3-4-7 Linear sweep voltammetry 36 3-5 Equipment and analysis 36 3-5-1 Scanning electron microscopy (SEM) 36 3-5-2 X-ray diffraction (XRD) 37 3-5-3 Thermogravimetric analysis (TGA) 38 3-5-4 AC impedance spectroscopy 38 Chapter 4 Results & Discussion 46 4-1 Sample preparation 46 4-2 Morphology 48 4-3 TGA 52 4-4 Limited oxygen index (LOI) 56 4-5 Ionic conductivity 56 4-6 Lithium transference number (TLi+) 58 4-7 Linear sweep voltammetry 59 4-8 Half-cell charge/discharge performance 61 4-9 Cyclic performance 63 4-10 AC Impedance spectroscopy & modeling 68 4-10-1 AC Impedance diagrams 68 4-10-2 Modeling 72 4-10-3 Evolution of SEI 80 Chapter 5 Conclusion 87 Reference 88 Appendix 93

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