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研究生： 李堅境
Felix
論文名稱： 改善固態電解膜之新穎硫基添加劑應用於高電壓系鋰離子電池之研究
Investigation on Novel Sulfured-Based Additives for Solid Electrolyte Interface (SEI) Improver in High Voltage Lithium Ion Battery Application
指導教授： 黃炳照
Bing-Joe Hwang
口試委員: 杜景順
Jing-Shan Do
周澤川
Tse-Chuan Chou
王復民
Fu-Ming Wang
學位類別： 碩士
Master
系所名稱： 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年： 2012
畢業學年度： 100
語文別： 英文
論文頁數： 122
中文關鍵詞： 鋰離子電池 、高電壓電解液 、硫基添加劑 、固態電解質膜
外文關鍵詞： Lithium ion battery, high voltage electrolyte, surfur-based additive, SEI
相關次數： 點閱：227  下載：13 
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    • 硫基化合物於文獻中已被提出能有效應用於高電壓系電解液中，本研究亦選擇了多種不同之硫基化合物做為添加劑以期能形成較佳之固態電解質膜(SEI)。此SEI膜能防止現行商用電解液之分解以及正電材料之錳離子溶解。添加劑分別以不同重量百分比加入商用電解液中並進行評估其電化學效能及相容性。結果顯示，1,3 Propanediol Cyclic Sulfate (PCS)於全電池測試中具有最佳之電化學表現，於30圈循環充放電後，仍有第一圈放電電容量之85%。而molecular energy理論計算以及循環伏安法亦證實了PCS能比ethylene carbonate (EC)較早還原並可能形成較佳之SEI結構。XPS、SEM以及EDS之分析也發現PCS的加入能大幅抑制錳離子沉積於負極表面之情形。結果顯示，加入1,3 propanediol cyclic sulfate 添加劑之電解液能做為一具有潛力應用於高功率鋰離子電池之選擇

    The sulfured-based materials, which have been demonstrated to have an effective application in high voltage electrolyte system, are adapted as an additive to form better solid electrolyte interface (SEI) in this work. This SEI could help prevent the current electrolyte from decomposition and the manganese ion dissolution of positive electrode. Various weight ratios of these additives were added into commercial carbonate-based electrolyte to evaluate their performance and compatibility. The results imply that 1 wt.% PCS (1,3 Propanediol Cyclic Sulfate) in electrolyte exhibits the best electrochemical performance in the full-cell test. After 30 cycles, the discharge capacity is maintained at 85% of 1st discharge. The molecular energy calculation and cyclic voltammetry (CV) both prove the PCS was reduced earlier than the ethylene carbonate (EC), which may implied a better SEI was formed. The XPS, SEM and EDS analysis reveal the addition of PCS is capable of suppressing the manganese ion deposition onto the anode side. Therefore, it is verified that 1,3 propanediol cyclic sulfate additive in electrolyte is a competitive option in high power lithium ion battery

    Table of Contents ABSTRACT i 摘要 ii Acknowledgements iii Table of Contents iv List of Figures vii List of Tables xiii Chapter I Introduction 1 I.1. Background 1 I.2. Challenge in Real Application 4 I.3. Problems Formulation 7 I.4. Research Purposes 7 Chapter II Literature Review 8 II.1. Principle of Lithium Ion Battery 8 II.2. Cell Design Consideration 9 II.3. Electrode Materials 10 II.3.1. Cathode Materials 10 II.3.1.1. Three Dimensional Spinel Framework as Second Generation Lithium Battery 12 II.3.2. Anode Materials 16 II.3.2.1. Surface Film on Carbon Anodes 18 II.4. Principle of SEI Formation 21 II.4.1. SEI Layer on Carbon Anode 21 II.4.2. Carbon SEI on Elevated Temperature 23 II.4.3. SEI Layer on Cathode Materials 24 II.5. Electrolyte 27 II.5.1. Oxidation and Reduction of Electrolyte 30 II.6. Electrolyte Additives 33 II.6.1. Additives for Surface Chemistry Improvement 34 II.6.1.1. Additives for Anode SEI 35 II.6.1.2. Role of Carbonate and Sulfite as Additives 37 II.6.1.2.1. Reduction Mechanism of Vinylene Carbonate Additive 38 II.6.1.2.2. Reduction Mechanism of Ethylene Sulfite Additive 43 II.6.1.3. Additives for Cathode SEI 45 Chapter III Research Methodology 47 III.1. Research Design 47 III.2. Materials 49 III.3. Equipments 49 III.4. Experimental Procedure 50 III.4.1. Preliminary Experiment 50 III.4.1.1. Cathode Synthesis 50 III.4.1.2. Anode Preparation 51 III.4.1.3. Additives Evaluation 52 III.4.2. Electrochemical Measurement 52 III.4.2.1. Electrode Coating 52 III.4.2.2. Battery Coin Cell Assembling 53 III.4.3. Sample Characterization 54 III.4.3.1. X-Ray Diffraction 54 III.4.3.2. Scanning Electron Microscopy 54 III.4.3.3. Fourier Transform Infrared Spectroscopy 55 III.4.3.4. X-Ray Photoelectron Spectroscopy 55 Chapter IV Results and Discussion 56 IV.1. Preliminary Test 56 IV.1.1. Synthesized Li1.02Ni0.5Mn1.5O4 56 IV.1.2. Additives Evaluation 59 IV.2. Electrochemical Performance 64 IV.2.1. Additives Amount Determination 64 IV.2.2. Additives Effects on Half Cell 73 IV.3. Analysis 79 IV.3.1. EIS and SEM Results 79 IV.3.2. FTIR and XPS Results 89 IV.4. Possible Additive Mechanism 101 Chapter V Conclusions 102 Bibliography 103 Appendix 109

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