Title Page
Contents
Abstract 13
Chapter 1. General Introduction of Renewable Energy 16
1.1. Proton Exchange Membrane Fuel Cell (PEMFC) 16
1.2. Electrolyte membranes for PEMFC 19
1.2.1. Perfluorinated sulfonic acid membranes 19
1.2.2. Aromatic hydrocarbon backbone membranes 23
1.3. Li-Ion batteries 24
1.4. Electrolyte for Li-ion batteries 25
1.5. Lithium salt for Li-ion batteries 27
1.6. Strategy and object 30
Chapter 2. Flexible blend polymer electrolyte membranes with excellent conductivity for fuel cells 32
2.1. Introduction 32
2.2. Materials and Methods 34
2.2.1. Materials 34
2.2.2. Synthesis of PDDPCSFS 35
2.2.3. Synthesis of SPmax-1200 36
2.2.4. Preparation of blend polymer membranes 37
2.2.5. Instrumentations and measurements 38
2.3. Result and discussion 39
2.3.1. Characterization of monomer and polymers 39
2.3.2. WU, IEC, hydration number, dimensional and thermal properties of the membranes 42
2.3.3. Proton conductivity (σ), chemical and mechanical stability of the membranes 44
2.3.4. Cell performance and surface morphology of the membranes 46
2.4. Conclusion 48
Chapter 3. Synthesis and Characterization of cross-linked polymer with Sulfonylimide group via UV-radical polymerization for PEMFC 50
3.1. Introduction 50
3.2. Materials and Methods 52
3.2.1. Materials 52
3.2.2. Measurements 52
3.2.3. Synthesis of Methacryloyl fluorosulfonyl imide (MAFSI) 54
3.2.4. Preparation of Poly(MAFSI-PEG) polymers(PMFP) 55
3.3. Result and discussion 56
3.3.1. Characterization of monomer (MAFSI) 56
3.3.2. Characterization of Polymers (PMFP) 57
3.3.3. IEC, Water uptake and dimensional stability of PMFP membranes 58
3.3.4. Proton Conductivity of the PMFP membranes 60
3.3.5. Thermal stability of PMFP membranes 62
3.3.6. Morphology of the membranes 63
3.3.7. Chemical stability of the membranes 64
3.3.8. Mechanical stability of the membranes 65
3.3.9. Cell performance of the PMFP membranes 66
3.4. Conclusion 67
Chapter 4. Study of UV-cured Cross-Linked Gel Polymer Electrolyte Containing Fluorosulfonyl urethane group for Safe and High Performance Li-ion Batteries 68
4.1. Introduction 68
4.2. Materials and Methods 70
4.2.1. Materials 70
4.2.2. Instrumentations and measurements 70
4.2.3. Synthesis of Fluorosulfonyl methacryloyl urethane(FSMU) monomer 71
4.2.4. Synthesis of Cross-linked polymer membranes 72
4.2.5. Fabrication of Symmetrical, Half Cells 73
4.3. Result and discussion 74
4.3.1. Characterization of monomer 74
4.3.2. Characterization of PFSPE membranes 74
4.3.3. Thermal properties of the membranes 75
4.3.4. Ionic Conductivity and Electrochemical Stability of Prepared Electrolyte Membranes 76
4.4. Conclusion 78
Chapter 5. Studies of In-situ Polymerization with Low Interfacial Resistance on Gel Polymer Electrolyte for Li-Ion Batteries 79
5.1. Introduction 79
5.2. Materials and Experiment 80
5.2.1. Materials 80
5.2.2. Instrumentations and measurements 81
5.2.3. Synthesis of Fluorosulfonyl methacryloyl urethane(FSMU) monomer 81
5.2.4. Synthesis of In-situ gel polymer electrolyte(PFSED) 82
5.3. Result and discussion 83
5.3.1. Characterization of monomer 83
5.3.2. Characterization of PFSEDs 84
5.3.3. Thermal stability of the polymer electrolyte 85
5.3.4. Ionic Conductivity and Electrochemical Stability of Gel Polymer Electrolyte 86
5.4. Conclusions 87
References 89
Abstract (in Korean) 107
Table 3.1. Properties of PMFP membranes. 58
Table 3.1. Properties of membranes. 61
Table 4.1. Synthesis ratio of PPE and PFSPEs electrolyte membranes 73
Table 5.1. Synthesis ratio of PFSEDs electrolyte membranes 83
Figure 1.1. Schematic of proton exchange membrane fuel cell. 16
Figure 1.2. Schematic illustration of different modes of proton conduction in a solid polymer electrolyte where (A) Grotthus, (B) Vehicular, and (C) surface mechanisms 18
Figure 1.3. Various PFSA polymer structures 20
Figure 1.4. Structural diagrams of fiber-reinforced membranes 21
Figure 1.5. (a) chemical structure of the perfluorinated polymer electrolyte membrane; (b) Nafion® cluster channel model[이미지참조] 22
Figure 1.6. Comparison of the different battery technologies in terms of volumetric and gravimetric energy density. 25
Figure 1.7. Improved corrosion resistance of next-generation lithium salts 28
Figure 1.8. Improved discharge capacity of electrolyte including next-generation lithium salt 29
Figure 1.9. test to improve battery life 30
Figure 2.1. ¹H NMR spectra of (a) DDPCSF monomer, (b) PDDPCSFS polymer, (c) Pmax-1200 polymer, and (d) SPmax-1200 polymer 40
Figure 2.2. (a) IEC and WU of the prepared membranes at 80℃, (b) Thermal degradation curves of the membranes. 42
Figure 2.3. (a) Proton conductivity of membranes at different temperatures under constant RH (80%). (b) Proton conductivity of membranes at 80℃ under different RHs. 44
Figure 2.4. (a) Fenton's reagent test of membranes at 80℃ (b) Tensile stress and elongation break of the membranes at 25℃ under the RH of 50%. 45
Figure 2.5. Cell performance of the polymer membranes under fully humidified inlet condition (RHa/RHc ¼ 100%/100%) at 70℃ 46
Figure 2.6. Tapping mode atomic force microscopic (AFM) images of (a) Blend (9:1), (b) Blend (8:2) polymer electrolyte. FE-SEM images of (c) Blend (9:1), (d)... 47
Figure 3.1. ¹H NMR spectra of (a) MMA and (b) MAFSI monomer 56
Figure 3.2. FTIR spectra of (a) MAFSI, PEGDMA and PMFP membranes and (b) corresponding to spectra of 1500 –1800 cm¯¹ 57
Figure 3.3. Ion exchange capacity (IEC) and water uptake (WU) for the PMFP polymers. 58
Figure 3.4. Proton conductivity for the PMFP polymer membranes in (a) different temperatures at 80% RH and (b) different relative humidity at 80℃ 60
Figure 3.5. Thermogravimetric analysis (TGA) of PMFP and Nafion211® membranes.[이미지참조] 62
Figure 3.6. Atomic force microscopy images for (a) PMFP-2, (b) PMFP-3 and (c) PMFP-4 membranes. 63
Figure 3.7. Fenton's reagent (5 ppm Fe²⁺) test for the PMFP and Nafion211® membranes.[이미지참조] 64
Figure 3.8. Tensile Strength-strain curves of the PMFP membranes and Nafion211 at 25℃ and Low Humidity and High Humidity. 65
Figure 3.9. Cell performance of PMFP membranes. 66
Figure 4.1. ¹H NMR spectra of (a) HEMA, (b) FSMU monomer 74
Figure 4.2. FTIR spectra of (a, b) FSMU, PEGDMA and PFSPE membranes 74
Figure 4.3. Thermal degradation curves of the membranes. 75
Figure 4.4. Li⁺ Ion conductivity vs temperature. 76
Figure 4.5. Linear sweep voltammetry (LSV) of as prepared electrolyte membranes at 30℃ (Scan rate 0.2 mV/s). 77
Figure 5.1. ¹H NMR spectra of (a) HEMA, (b) FSMU monomer 83
Figure 5.2. FTIR spectra of (a, b) FSMU and PFSEDs polymer electrolyte 84
Figure 5.3. TGA curves of the membranes. 85
Figure 5.4. Ion conductivity versus temperature plots of PFSEDs. 86
Figure 5.5. Linear sweep voltammetry (LSV) of as polymer electrolyte at 30℃ (Scan rate 0.2 mV/s). 87
Scheme 2.1. Synthesis Route of PDDPCSFS polymer. 35
Scheme 2.2. Synthesis Route of SPmax-1200 polymer 36
Scheme 2.3. Schematic Method Route and Photographic Images of PMFP Membranes 37
Scheme 3.1. Synthesis Route of Mathacryloyl Fluorosulfonyl Imide (MAFSI) 54
Scheme 3.2. Schematic Method Route and Photographic Images of PMFP Membranes 55
Scheme 4.1. Synthesis Route of Fluorosulfonyl methacryloyl urethane (FSMU) monomer. 71
Scheme 4.2. Schematic Method and Photofraphic Images of Cross-linked Polymer Membranes 72
Scheme 5.1. Synthesis Route of Fluorosulfonyl methacryloyl urethane (FSMU) 81
Scheme 5.2. Schematic Method of PFSED gel polymer electrolyte 82