Title Page
Contents
Abstract 13
Chapter 1. Introduction of Fluorosulfonylimide Salt Electrolytes using in Secondary Lithium Battery 15
1.1. Introduction 15
1.2. The need for research 17
1.3. Strategy and Object 20
Chapter 2. Introduction of Ionic Liquid Electrolytes using in Secondary lithium Battery 22
2.1. Introduction 22
2.2. Necessity of technology development 25
2.3. Development target and technology 31
2.4. Strategies and Object 36
Chapter 3. Synthesis and Properties of Inflammable Ionic liquid 38
3.1. Development of a method for synthesizing flame retardant additives for lithium secondary batteries 38
3.1.1. Synthesis reaction using chlorosulfonyl isocyanate 38
3.1.2. Synthesis reaction using fluorosulfonyl isocyanate 41
3.1.3. Fluorination reaction to synthesize FSI 44
3.1.4. Reaction with Ammonium Fluoride 45
3.1.5. Synthesis of ionic liquid: Synthesis of TBAFSI (Tetrabutylammonium, FSI salt) 46
3.1.6. Synthesis of ionic liquid: Synthesis of TBMAFSI (Tributylmethylammonium, FSI salt) 47
3.2. Conclusion 48
Chapter 4. Pilot Synthesis and Flammable Test of Fluorosulfonylimide Ammonium Salt 49
4.1. Pilot synthesis of flame retardant additives for lithium secondary batteries 49
4.1.1. Synthesis using chlorosulfonyl isocyanate 49
4.1.2. Pilot synthesis using Ammonium fluoride 50
4.1.3. Pilot test of tributylmethyl ammonium difluorosulfonylimide 50
4.2. Self-evaluation of flame retardant products 51
4.2.1. Acidity Analysis of Flame Retardant Additives 51
4.2.2. Thermal stability self-analysis of flame retardant additives 52
4.2.3. Analysis of Water Content of Flame Retardant Additives 53
4.2.4. Analysis of Purity and Anion Content of Flame Retardant Additives 54
4.2.5. Analysis of Cationic Metal Content of Flame Retardant Additives 59
4.2.6. Coin-cell manufacturing and ionic conductivity measurement of flame retardant additives 60
4.2.7. Measurement of self-extinguishing time of flame retardant additives 62
4.3. Conclusions 64
Chapter 5. New Synthetic Method of fluorosulfonylimide salts 66
5.1. UV Curable Electrolyte Synthesis and Results 66
5.1.1. Preparation of fluorosulfonyl isocyanate 66
5.1.2. Preparation of acryloyl fluorosulfonyl urea 67
5.1.3. Preparation of fluorosulfonyl urea acrylic lithium salt 67
5.1.4. Manufacture of ALiFSI Polyelectrolyte Membrane 68
5.2. Experiment result 70
5.2.1. 19F-NMR study[이미지참조] 70
5.2.2. ¹H-NMR study 70
5.2.3. FTIR study 71
5.2.4. Photo-DSC study 72
5.2.5. ALiFSI membrane 72
5.2.6. Cyclic voltammetry 73
5.3. Experiment result of UV-curing reaction 75
5.3.1. Preparation of polymer membrane of acryloyl fluorosulfonyl urea 75
5.3.2. Manufacture of AHFSILi Polyelectrolyte Membrane 76
5.3.3. Photo-DSC study 77
5.3.4. AHFSILi membrane 77
5.3.5. Ion conductivity 78
5.3.6. Cyclic voltammetry 78
5.4. Synthesis of lithium polymer electrolyte for high temperature 79
5.4.1. Synthesis of nitrogen dioxide polyethersulfone 79
5.4.2. Synthesis of amine polyethersulfone 80
5.4.3. Synthesis of fluorosulfonyl isocyanate polyethersulfone 82
5.4.4. Preparation of sulfonic fluorosulfonyl isocyanate polyethersulfone 83
5.4.5. ¹H-NMR studies 84
5.5. Conclusions 85
Chapter 6. Cations and Anions in Fluorosulfonylimide Salt Using Chromatography Methodology 87
6.1. Analysis of cations and anions 87
6.1.1. Anion analysis 87
6.1.2. Cation analysis 90
6.2. Analysis of electrolyte samples 93
6.3. Conclusion 95
References 96
Abstract (in Korean) 104
Table 2.1. Characteristics of each type of secondary battery 22
Table 2.2. Representative characteristics of ionic liquids 26
Table 2.3. Comparison of characteristics of lithium electrolyte 27
Table 2.4. Viscosity comparison of ionic liquid electrolytes 28
Table 2.5. Viscosity comparison of ionic liquid electrolytes 29
Table 2.6. Comparative analysis of characteristics by type of electrolyte for lithium secondary batteries 32
Table 3.1. Experiments under synthetic conditions for each solvent using CSI 1. 38
Table 3.2. Reaction equivalence ratio experiment using chlorosulfonyl isocyanate 39
Table 3.3. Reaction temperature experiment using chlorosulfonyl isocyanate 40
Table 3.4. Reaction equivalence ratio experiment using fluorosulfonyl isocyanate 41
Table 3.5. Reaction temperature experiment using fluorosulfonyl isocyanate 43
Table 3.6. Experimental results of stirrability according to solvent during KF fluorination substitution reaction 44
Table 3.7. Test results of production of Tetrabutylammonium, FSI salt 46
Table 3.8. Tributylmethylammonium, FSI salt manufacturing test result 48
Table 4.1. Analysis result of flame retardant additive (TBMAFSI) using pH meter 51
Table 4.2. Analysis result of flame retardant additive (TBMAFSI) using pH meter 54
Table 4.3. Basic analysis conditions 56
Table 4.4. TMBAFSI anion ion chromatography analysis result 57
Table 4.5. Analysis result of TMBAFSI Pilot prototype 58
Table 4.6. ICP-OES metal content analysis result 60
Table 4.7. Ion Conductivity Analysis Results Using Cyclic Voltage Scanning Method 62
Table 5.1. Conductivity values of ALiFSIs 74
Table 5.2. Conductivity values of AHFSILis 79
Table 6.1. Ion chromatogram obtained using cation standard solution 91
Figure 1.1. Improved corrosion resistance of next-generation lithium salts 18
Figure 1.2. Improved discharge capacity of electrolyte including next-generation lithium salt 19
Figure 1.3. test to improve battery life 20
Figure 2.1. Comparison of operating voltage and energy capacity for each secondary battery 23
Figure 2.2. Lithium-ion battery operation principle 24
Figure 2.3. Thermal decomposition mechanism of BMI-BF₄ 27
Figure 2.4. Discharge characteristics of ionic liquids with TFSI and FSI 30
Figure 2.5. Types of representative cations and anions to compose an ionic liquid electrolyte 35
Figure 3.1. Synthesis of dichlorosulfonylimide I 38
Figure 3.2. Synthesis of dichlorosulfonylimide II 41
Figure 3.3. Synthesis of Potassium difluorosulfonylimide salt 44
Figure 3.4. Synthesis of Ammonium difluorosulfonylimide salt 45
Figure 3.5. HCSI reaction using Ammonium fluoride vs time and temperature 45
Figure 3.6. Synthesis of Tetrabutylammonium difluorosulfonylimide salt 46
Figure 3.7. Synthesis of tribyltyl-methyl-difluorosulfonylimide salt 47
Figure 4.1. manufacturing equipments: astelloy reactors, STS reactor pressure Nutsche filter. 49
Figure 4.2. Synthesis of dichlorosulfonylimide 49
Figure 4.3. Synthesis of ammoniumdifluorosulfonylimide 50
Figure 4.4. Synthesis of tributylmethyl ammonium difluorosulfonylimide 50
Figure 4.5. Tributylmethyl ammonium difluorosulfonylimide material 51
Figure 4.6. TGA analysis of flame retardant additive (TBMAFSI) 52
Figure 4.7. Long-term stability evaluation of TBMAFSI flame retardant additives 53
Figure 4.8. TBMAFSI Flame Retardant Additive Moisture Content Evaluation 54
Figure 4.9. Analysis principle of ion chromatography 55
Figure 4.10. Photo of IC measuring device 56
Figure 4.11. TMBAFSI anion ion chromatography measurement data 57
Figure 4.12. Photo of ICP-OES measuring device 59
Figure 4.13. Coin-cell structure and shape 61
Figure 4.14. CV measuring device for ion conductivity analysis 61
Figure 4.15. Results of flame retardancy analysis through self-extinguishing time measurement 63
Figure 5.1. Synthesis of Fluorosulfonylisocyanate. 66
Figure 5.2. Synthesis of AHFSI 67
Figure 5.3. Synthesis of ALiFSI 68
Figure 5.4. UV-curing reaction 69
Figure 5.5. F19 NMR study of fluorosulfonyl isocyante.[이미지참조] 70
Figure 5.6. H¹ NMR study of acrylamide-fluorosulfonyl imide. 71
Figure 5.7. FTIR study of acrylamide-fluorosulfonyl imide. 72
Figure 5.8. DSC studies of acrylamide-fluorosulfonyl imide lithium salt. 72
Figure 5.9. Film image of ALiFSI 73
Figure 5.10. Cyclic voltammetry studies of ALiFSIs 74
Figure 5.11. Resistance and conductivity of ALiFSIs 74
Figure 5.12. UV curing of acryloyl fluorosulfonyl urea 75
Figure 5.13. Photo-DSC studies of AHFSIs 77
Figure 5.14. Photo images after UV curing of AHFSIs 78
Figure 5.15. Resistance and conductivity of AHFSILis 78
Figure 5.16. Cyclic voltammetry studies of AHFSILis 79
Figure 5.17. Synthesis of nitro- polyethersulfone 80
Figure 5.18. Reduction of nitro- polyethersulfone 81
Figure 5.19. Fluorosulfonylimide reaction from amine-polyethersulfone 82
Figure 5.20. Sulfonation of Fluorosulfonylimide polyethersulfone 83
Figure 5.21. NO₂-PES ¹H-NMR 84
Figure 5.22. NH₂-PES ¹H-NMR data 85
Figure 6.1. Ion chromatogram obtained using anion standard solution 88
Figure 6.2. Calibration curve of F- and calibration curve of Cl-[이미지참조] 88
Figure 6.3. Calibration curve of Br- and calibration curve of NO3-[이미지참조] 89
Figure 6.4. Calibration curve of PO43- and calibration curve of SO42-[이미지참조] 90
Figure 6.5. Ion chromatogram of different concentrations. 91
Figure 6.6. Calibration curve for Li+ and calibration curve of Na+[이미지참조] 92
Figure 6.7. Calculation curve of NH4+ and K+ calibration curve[이미지참조] 92
Figure 6.8. Ca2+ calibration curve and calibration curve of Mg2+[이미지참조] 92
Figure 6.9. Anion chromatogram of sample 1 and cation chromatogram of sample 1 93
Figure 6.10. Anion chromatogram of sample 2 and cation chromatogram of sample 2 94
Figure 6.11. Anion chromatogram of sample 3 and cation chromatogram of sample 3 94