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研究生： GIYANTO
GIYANTO
論文名稱： 利用電負性官能基團影響馬來酰亞胺電解液添加劑應用於鋰離子電池之研究
The investigation of electronegativity functional group effects on maleimide electrolyte additive in lithium ion battery
指導教授： 王 復 民
Fu-Ming Wang
口試委員: 許榮木
Jung-Mu Hsu
陳崇賢
Chorng-Shyang Chern
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： 英文
論文頁數： 124
中文關鍵詞： 固體電解質界面 、電負性官能基團 、馬來酰 、亞胺添加劑 、鋰離子電池
外文關鍵詞： solid electrolyte interface, electronegativity functional group, maleimide-based additive
相關次數： 點閱：272  下載：3 
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    • 本研究目的在於用帶電負性官能基團之馬來酰亞胺電解液添加劑其對於石墨負極的固體電解質界面（SEI）生成影響作探討。兩種馬來酰亞胺生成物有著電負性官能基團之取代物成功地被合成出來，分別為：4-flouro-o-phenylenedimaleimide(F-MI)以及4-cyano-o-phenylenedimaleimide(CN-MI)。一體積莫爾濃度之LiPF6在體積比為3:2:5的碳酸乙烯酯(EC)：碳酸丙烯酯(PC)：碳酸二乙烯(DEC)下添加0.1 wt%的F-MI跟CN-MI添加劑，可以提供更高的電化學穩定性以及更佳的可逆性能力。電負性官能基團（F以及CN）被發現其SEI層的生成可以被用來抑制在較高的還原電位2.35到2.33伏特(相對於Li/Li+)所造成的電解質分解問題。和商業的電池(O-MI)以及空白對照組的電池做比較，利用F-MI跟CN-MI添加劑所組成的電池提供了較低的電荷轉移之電阻和較高的離子擴散速率。除此之外，也透過掃描型電子顯微鏡(SEM)和能量色散X射線光譜儀(EDX)分析來研究兩種添加劑對於MCMB電極表面形態所造成的影響。我們的結果發現，本實驗之添加劑其良好的SEI生成以及與商業的電池(O-MI)跟空白對照組相比之電池性能的提高，此兩種添加劑為最適當的添加劑。

    This research studies the electronegativity functional group effects on maleimide-based electrolyte additives to the solid electrolyte interface (SEI) formation on the graphite anode. Two maleimide compounds with the electronegativity functional groups as substituent, 4-flouro-o-phenylenedimaleimide (F-MI) and 4-cyano-o-phenylenedimaleimide (CN-MI) have been successfully synthesized. 1M LiPF6 in ethylene carbonate (EC): propylene carbonate (PC): di-ethylene carbonate (DEC) (3:2:5 in volume) containing 0.1 wt % of F-MI and CN-MI additives can provide higher electrochemical stability and higher reversibility capability. The presence of the electronegativity functional group (F and CN) was found that the SEI layer formation is used to suppress the decomposition electrolyte within higher reduction potential at 2.35 to 2.33 V vs. Li/Li+. The cells with F-MI and CN-MI additives provide lower charge-transfer resistance and higher ionic diffusivity in comparison with commercial product (O-MI) and blank electrolyte. In addition, scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) analysis were also conducted in order to understand the effects of additive on the morphology of the MCMB electrode surface. Our results show that F-MI and CN-MI additives are the most suitable additives due to its excellent SEI formation and battery performance enhancement compares with blank electrolyte and commercial product (O-MI).

    Abstract i 摘 要 iii Acknowledgement v Table of Contents vii List of Figures ix List of Tables xi CHAPTER I Introduction 1 1.1 Background 1 1.2 Problems Formulation 5 1.3 Research Purposes 6 CHAPTER II Literature Review 9 2.1 Lithium Ion Battery Components 9 2.1.1 Cathode 9 2.1.2 Anode 12 2.1.3 Electrolyte 15 2.2 Solid Electrolyte Interface (SEI) 21 2.2.1 SEI Formation Mechanism 22 2.2.2 Solvent Reduction Mechanism 23 2.2.3 Salt Decomposition 26 2.2.4 SEI Features, Morphology, and Chemical Composition 29 2.2.5 The Growth of SEI Layer 31 2.2.6 Characterization of SEI Layer 34 2.3 SEI Modification 35 2.3.1 Surface Modification of the Anode Materials 35 2.3.2 Surface Modification of the Cathode Materials 39 2.3.3 Modification on the Electrolyte System 41 2.4 Electrolyte Additives 46 2.5 Maleimide-based Additive 53 2.6 The Electronegativity Functional Group Effect on Electrolyte Additive 56 CHAPTER III Research Methodology 59 3.1 Research Design 59 3.2 Materials 61 3.3 Equipments 62 3.4 Experimental Procedure 63 3.4.1 Synthesis of F-MI and CN-MI additive 63 3.4.2 Electrochemical Measurement 63 3.4.3 SEI Evaluation Measurement 65 CHAPTER IV Synthesis of New Additives 67 4.1 Synthesis 67 4.1.1 Synthesis Procedure of F-MI 68 4.1.2 Synthesis Procedure of CN-MI 71 4.2 Characterization 72 4.2.1 4-fluoro-phenylenediamaleimide (F-MI) 72 4.2.2 4-cyano-phenylenediamaleimide (CN-MI) 74 4.3 Electrolyte Preparation 76 CHAPTER V Result and Discussion 79 5.1 Electrochemical Analysis 79 5.1.1 Cyclic Voltammetry (CV) Test 79 5.1.2 Charge Discharge Test 82 5.1.3 Electrochemical Impedance Spectroscopy (EIS) test 90 5.2 SEI Evaluation 95 5.2.1 SEM Result 95 5.2.2 EDX Result 97 CHAPTER VI Conclusion 101 Reference 103

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