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研究生： Muhammad Hendra Pebrianto
Muhammad - Hendra Pebrianto
論文名稱： 高性能鋰電池用電解液添加劑合成開發及其電化學反應動力學研究
Synthesis and characteristic of electrolyte additive and its electrochemical kinetic study in lithium ion battery
指導教授： 王復民
Fu-Ming Wang, Ph.D.
口試委員: 吳乃立
Nae-Lih Wu
黃炳照
Bing Joe Hwang
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： 2015
畢業學年度： 103
語文別： 英文
論文頁數： 117
中文關鍵詞： 氟吸電子基團 、馬來酰 、亞胺 、鋰離子電池。
外文關鍵詞： fluorine electron withdrawing groups, maleimide
相關次數： 點閱：271  下載：45 
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    • 研究的主軸在於比較兩種馬來酰亞胺化合物與其氟吸電子基團，分別為4-氟鄰亞苯基(F-MI)以及4,5-二氟鄰亞苯基(2F-MI)，與無氟的鄰苯基(O-MI)，並且評估氟官能基團對石墨電極的固態電解質界面(SEI)形成之影響力。配置六氟磷鋰(1M)加於碳酸乙烯酯：碳酸丙烯酯：碳酸二乙酯(體積比3:2:5)電解液，並加入0.1wt%的F-MI以及2F-MI作為添加劑，促使固態電解質界面的形成，並抑制當鋰嵌入或脫去的不可逆性。無添加劑的電解液與包含0.1wt%的O-MI添加劑的電解液作比較，氟官能基提供較高的還原電位在鋰/鋰離子的CV曲線為2.4-2.3伏特。由於鋰離子電池MCMB/Li陽極半電池添加劑馬來酰亞胺基中的氟官能基影響，使得電解液添加劑為2F-MI的電池電容量提升11%，使用F-MI作為添加劑的電池電容量提升7%，將前述結果與以O-MI為添加劑的對照組(電池電容量提升3%)進行比較。電化學交流阻抗分析(EIS)結果顯示，石墨表面上形成一種新穎的固態電解質界面，並且與對照組相較下有較低的電阻表現。同時藉由電化學石英晶體微量天平(EQCM)測試結果，提供了電解液還原過程之動力學研究依據。在全電池LiCoO2/MCMB變頻掃描速率的充放電表現結果，顯示了電池使用氟官能基團為添加劑的循環充放電能力最為穩定。核磁共振(NMR)的分析結果顯示出MI添加劑會造成固態電解質界面產生分解。針對MCMB之二十次循環以後的型態和元素分析方面，則利用掃描電子顯微鏡和X射線光電子能譜來進行。

    This research focuses on a comparison of two maleimide compounds possessing fluorine electron withdrawing groups, namely 4-flouro-o-phenylenedimaleimide (F-MI) and 4,5-diflouro-o-phenylenedimaleimide (2F-MI) with non-fluoridated o-phenylenedimaleimide (O-MI). This study evaluates the effect of the fluorine functional group on solid electrolyte interphase (SEI) formation on graphite electrodes. LIPF6 (1M) in ethylene carbonate (EC): propylene carbonate (PC): di-ethylene carbonate (DEC) (3:2:5 in volume) containing 0.1 wt % of F-MI and 2F-MI additives promoted SEI formation and inhibited irreversibility during lithium intercalation and de-intercalation. Compared with electrolytes without additives and an electrolyte containing 0.1 wt % O-MI additive, the presence of the fluorine group was found to provide a higher reduction potential, i.e. 2.4 - 2.3 V vs. Li/Li+ as shown by CV curves. The presence of the fluorine group in the maleimide-base additives used in lithium ion battery MesoCarbon MicroBeads (MCMB)/Li anode half cells led to capacity improvements of 11% (using 2F-MI), and 7% (using FMI) – a control using O-MI led to a 3% improvement. Electrochemical Impedance Spectroscopy (EIS) shows that a novel SEI formation on graphite’s surface shows a lower resistance when compared to the electrolyte containing only O-MI additive or an additive-free electrolyte. Dynamic studies of electrolyte during the reduction process are provided by Electrochemical Quarts Crystal Microbalance (EQCM) test. Charge discharge performance of full cell LiCoO2/MCMB in variant scan rate shows that batteries using fluorine group base additives exhibit a stable cycle-ability performance. Nuclear Magnetic Resonance (NMR) results show SEI decomposition promoted by MI additives. Morphological and elemental analysis of the MCMB after the 20th cycle was examined by scanning electron microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS).

    Abstract i 摘要 ii List of Figures vi List of Table xi Chapter 1 Introduction 1 1.1 Background 1 1.2 Lithium Ion Battery components 5 1.2.1 Cathode 5 1.2.2 Anode 7 1.2.3 Electrolyte 9 1.3 Electrolyte application 14 1.3.1 Improving battery performance 14 1.3.2 Battery safety 16 Chapter 2 Solid Electrolyte Interphase (SEI) Formation and modification 20 2.1 SEI formation mechanism 21 2.2 SEI Improvement 25 2.2.1 Electrode surface modification 25 2.2.2 Electrolyte additive 28 2.3 The new Maleimide (MI) base additive electrolyte 37 2.4 Problem Formulation 38 2.5 Experiment Purpose and Innovation 39 Chapter 3 Research Methodology 40 3.1 Research design 40 3.2 Material 42 3.3 Equipment 43 3.4 Experimental Procedure 43 3.4.1 Preliminary Experiment 43 3.4.2 Electrochemical Measurement 44 3.4.3 SEI Evaluation 47 Chapter 4 Synthesis and Electrolyte Preparation 49 4.1 Synthesis Part 49 4.1.1 Hydrogenation Part 50 4.1.2 Dehydration Part 52 4.2 Characterization 56 4.2.1 4-flouro-phenylenediamine 56 4.2.2 FMI 57 4.2.3 4,5-diflouro-phenylenediamine 58 4.2.4 2-FMI 59 4.3 Electrolyte Preparation 60 Chapter 5 Electrochemical testing 62 5.1 Cyclic Voltammetry (CV) on MCMB anode half cell 62 5.2 Electrochemical Impedance Spectroscopy (EIS) test 65 5.2.1 EIS after 1st cycle CDC test 65 5.3 Charge Discharge test 67 5.4 Electrochemical Quart Crystal Microbalance (EQCM) test 69 5.5 Full cell battery performance 72 5.6 EIS test after several cycle with variant C-rate for full cell MCMB/LiCoO2 75 Chapter 6 SEI identification 77 6.1 Scanning Electron Microscopy (SEM) & Energy Dispersive X-ray (EDX) of MCMB anode half cell 78 6.1.1 SEM Result 78 6.1.2 EDX result 80 6.2 Nuclear Magnetic Resonance (NMR) and X-ray Photoelectron Spectroscopy (XPS) 82 6.2.1 NMR test after EQCM test 82 6.2.2 X-ray Photo Electron Spectroscopy (XPS) analysis of MCMB full cell 89 Chapter 7 Conclusion 96 Reference 97

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