Poly(2,2,6,6-tetramethylpiperidin-1-oxy-4-yl methacrylate) (PTMA) 為有機自由基鋰電池 (Li-ORB) 中最常使用的正極高分子材料之一，其氧化還原電位為 3.6 V vs. Li/Li+, 在有機自由基鋰電池中若要改變正極材料的氧化還原電位，通常藉由進行高分子的結構調整，如：改變高分子鏈上官能基、或與其他共軛高分子形成共聚物。本研究利用改變電解液的結構性組成，添加不同濃度的鋰鹽以及螯合配體 12-冠醚-4 (12-crown-4)，發現藉由改變電解質的成份比例，即使不進行高分子結構的修飾也可調控有機自由基鋰電池的氧化還原電位。由循環伏安法顯示，在 PTMA||鋰電池含 0.25、0.5、1.0、2.0 M LiClO4-EC/DEC (1/1, v/v) 以及 1、2、4 當量數 12-冠醚-4 的條件下，當僅增加鋰鹽濃度時有機自由基鋰電池之氧化還原電位將往左偏移，若固定鋰鹽濃度並提昇 12-冠醚-4 當量數時，有機自由基鋰電池之氧化還原電位則往右偏移，其電化學電位窗口可在 3.557-3.865 V 區間調控。再由定電流充放電以及交流阻抗分析界定其電化學表現如：循環壽命、離子導電度，與不同電解液組成比例之關係，並結合理論計算探討其形成機制。

Poly(2,2,6,6-tetramethylpiperidin-1-oxy-4-yl methacrylate) (PTMA) is one of the most promising cathode-active polymer materials in organic radical batteries (ORB) with a redox potential of 3.6 V versus Li/Li+. To modulate the redox potential of lithium organic batteries (Li-ORB), modifications of polymer structure such as adding functional groups to the polymer chain or polymerizing with other conjugated polymers to form copolymers, are usually required. Herein, we report an electrolyte system using various concentrations of electrolyte salt and chelating ligand to regulate the redox potential of PTMA without changing the polymer structure. From the cyclic voltammetry of Li︱0.25, 0.5, 1.0, and 2.0 M LiClO4-EC/DEC (1/1, v/v)︱PTMA cells with 1, 2, and 4 equiv. of 12-crown-4 (12C4) corresponded to LiClO4, respectively, the redox potential shifts anodically when the LiClO4 concentration is increased in the electrolyte solution; in contrast, a cathodic shift of the redox potential is observed with the incorporation of a larger equivalent of 12C4 in the solution. By applying different concentrations of LiClO4 and 12C4, the redox potential can be modulated between 3.557 to 3.865 V. The redox potentials calculated using density functional theory (DFT)/base set of B3LYP/6-31G(d,p) in polarized continuum model (PCM) also show good agreement with experimental results.

論文審定書 i
Acknowledgements ii
摘要 iv
Abstract v
Table of Contents vi
List of Figures viii
List of Tables xi
Chapter 1: General Introduction 1
1.1 Introduction 2
1.2 Lithium-ion Batteries 2
1.3 Organic Radical Batteries 4
1.4 Research Motivation 7
Chapter 2: Chemicals and Instruments 8
2.1 Chemicals 9
2.2 Instruments 11
2.2.1 Nuclear Magnetic Resonance (NMR) 11
2.2.2 Electron Paramagnetic Resonance (EPR) 11
2.2.3 Gel Permeation Chromatography (GPC) 11
2.2.4 Electrochemical Analyzer Instrument 12
Chapter 3: Experimental Section 13
3.1 Synthesis of PTMPM via Atom Transfer Radical Polymerization (ATRP) 14
3.2 Oxidation of PTMPM to PTMA 16
3.3 Preparation of PTMA Composite Electrode 17
3.4 Fabrication of Coin Cells 18
3.5 Computational Details in DFT Calculation 19
Chapter 4: Results and Discussion 23
4.1 Properties of PTMA 24
4.2 Ionic Conductivity of Electrolytes 26
4.3 Cyclic Voltammetry Analysis 29
4.3.1 Lithium Salt Concentration 29
4.3.2 Equivalents of 12C4 31
4.4 AC Impedance, Charge-discharge and Cycle Life Characteristics 38
4.5 DFT Calculation 41
Chapter 5: Conclusion 43
References 45
List of Publications 48
List of Presentations 48
Appendix 49

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