臺灣博碩士論文加值系統

本研究製備聚苯胺/奈米碳材複合材料，並探討其電化學及電容性質。石墨烯為超級電容器常見的一種碳材，當尺寸縮小為量子點時會有良好的生物相容性、低毒性及良好的發光效應，在本研究中奈米碳點(CNDs)測得電容值在電流密度為0.1 A g-1時為11.02 F g-1。為提高奈米碳點的電容值，將聚苯胺原位聚合於CNDs表面。聚苯胺為一種共軛導電高分子，合成容易且具有高的比電容值 (電流密度為0.1 A g-1下電容值為187 F g-1)，將兩種材料製備成複合材料可有效將電容值提高。本研究分析不同比例酸摻雜及二次摻雜對於聚苯胺/奈米碳材複合材料 (CNDP)電容值的影響。不同比例酸摻雜會影響聚苯胺的合成型態，利用樟腦磺酸進行二次摻雜的複合材料型態變為片狀堆疊。最高的比電容值出現在二次摻雜且奈米碳點摻雜比例為10 wt.% (CNDP10-sd)的複合材料，在電流密度為0.1 A g-1時電容值可達約350 F g-1，在1 A g-1的電流密度下電容值仍有接近86 F g-1。結果顯示透過混成聚苯胺可有效提升奈米碳點的電容值，且聚苯胺的循環穩定性也得到提升。

Supercapacitors (SC) have attracted much attention due to their high power densities, wide temperature range, high energy densities and long cycle life compared to batteries. Carbon materials and conducting polymers are common electrode materials for electrical double layer capacitors (EDLC) and pseudo-capacitors, respectively. In order to enhance the performance of the SC, combined carbon materials and conducting polymers to form the hybrid capacitors have been reported. Polyaniline (PANI) is one of the conducting polymers, which has multiple redox states showing large pseudo-capacitance. Carbon nanodot (CND), one of the derivatives of nano carbons, has ultra-small size and unique electronic and optical properties. The CNDs have been recognized as superior electrode material for supercapacitors resulting from quantum confinement effect of wider band gap. Polyaniline/carbon nanodots composites were prepared by chemical oxidation polymerization of aniline in presence of CNDs. After secondary doping, the CNDP-sd composite shows better electrochemical properties and thermal stabilities than pristine PANIs and CNDs. The capacitance of CNDP-sd composite is about 350 F g-1 compared to 187 F g-1 of PANI-sd and 11 F g-1 of CNDs, respectively at a current density of 0.1 A g-1.

摘要 I
Abstract II
Catalog III
List of Figures VI
List of Tables X
Chapter 1 Introduction 1
1-1 Foreword 1
1-2 Research motives 3
Chapter 2 Literature review 4
2-1 Electrochemical capacitors 4
2-1-1 Types of supercapacitors 5
2-2 Polyaniline (PANI) 14
2-2-1 Introduction of polyaniline 14
2-2-2 Application of polyaniline composites for supercapacitors 16
2-3 Preparation of polyaniline 18
2-4 Carbon nanodots (CNDs) 22
2-4-1 Introduction of carbon nanodots 22
2-4-2 Preparation of carbon nanodots 24
2-4-3 Application of CNDs-based materials in supercapacitors 28
2-5 Synthesis methods of PANI/CNDs composites 30
Chapter 3 Research framework 31
Chapter 4 Experimental content 32
4-1 Materials 32
4-2 Instruments 34
4-3 Preparation of graphene oxide (GO) 35
4-4 Preparation of carbon nanodots (CNDs) 35
4-5 Preparation of polyaniline (PANI) 36
4-5-1 Synthesis of HCl doped PANI using HCl(aq) as solvent 36
4-5-2 Synthesis of HCl doped PANI using de-ionized water as solvent 36
4-5-3 Synthesis of secondary doping PANI (PANI-sd) 37
4-6 Preparation of CNDs/PANI composites (CNDP) 38
4-6-1 Preparation of CNDP composites 38
4-6-2 Preparation of CNDP-f composites 38
4-6-3 Preparation of secondary doping CNDP composites (CNDP-sd) 39
4-7 Preparation of electrodes 40
4-8 Electrochemical measurement 40
4-9 Material characterization 41
Chapter 5 Results and discussion 42
5-1 Characterization of graphene oxide (GO) and carbon nanodots(CNDs) 42
5-1-1 Identification of FT-IR 42
5-1-2 UV-vis absorption spectra 44
5-1-3 Thermogravimetric analysis 45
5-1-4 Surface morphology of FE-SEM images 47
5-1-5 Atomic force microscope analysis 48
5-1-6 Structure analysis by XRD 49
5-2 Characterization of polyaniline (PANI) synthesis by different process 51
5-2-1 Identification of FT-IR 51
5-2-2 UV-vis absorption spectra 53
5-2-3 Thermogravimetric analysis 54
5-2-4 Surface morphology of FE-SEM images 56
5-2-5 Structure analysis by XRD 58
5-3 Characterization of carbon nanodots/polyaniline (CNDP) composites synthesis by different process 59
5-3-1 Identification of FT-IR 59
5-3-2 UV-vis absorption spectra 63
5-3-3 Themogravimetric analysis 66
5-3-4 Surface morphology of FE-SEM images 70
5-3-5 Structure analysis by XRD 75
5-4 Electrochemical properties GO, CNDs, PANIs and CNDP composites 78
5-4-1 Cyclic voltammetry curves 78
5-4-1-1 Cyclic voltammetry curves of GO and CNDs 78
5-4-1-2 Cyclic voltammetry curves of PANIs 80
5-4-1-3 Cyclic voltammetry curves of different CNDP composites 82
5-4-2 Galvanostatic charge/discharge curves 87
5-4-2-1 Galvanostatic charge/discharge curves of GO and CNDs 87
5-4-2-2 Galvanostatic charge/discharge curves of PANI synthesis with different process 89
5-4-2-3 Galvanostatic charge/discharge curves of different CNDP composites 91
5-4-3 Cycle stability 96
Conclusion 97
Reference 98


List of Figures
Fig. 2-1 A simplified Ragone plot of specific power versus specific energy for the various electrochemical energy storage devices.[13] 4
Fig. 2-2 Schematic diagrams of EDLCs charge-discharge process. 7
Fig. 2-3 Schematic diagrams of pseudo-capacitors charge-discharge process. 9
Fig. 2-4 A simplified ragone plot of specific power versus specific energy for the various electrochemical energy storage devices. 15
Fig. 2-5 The types of aniline product with different oxidation.[61] 19
Fig. 2-6 Schematic diagram of the formation mechanism for PANI synthesis by self-assembly process.[60] 20
Fig. 2-7 The SEM images of PANI with different dopant. (a) HCl, (b) H2SO4, (c) HBF4, (d) H3PO4, (e) CH3COOH and (f) oxalic acid. [60, 62] 20
Fig. 2-8 Schematic diagrams of different carbon structures. 23
Fig. 2-9 Graphene is the basic building block of other carbon structures. 23
Fig. 2-10 Schematic diagrams of (a) bottom-up and (b) top-down methods.[76] 26
Fig. 2-11 Schematic diagram of preparation of GO from graphite by modified Hummers method.[77] 26
Fig. 5-1 FT-IR spectra of (a) pristine graphite, (b) GO and (c) CNDs. 43
Fig. 5-2 The UV-vis spectra of (a) GO and (b) CNDs. 44
Fig. 5-3 Thermogracimetry curve of (a) graphite, (b) GO and (c) CNDs. 46
Fig. 5-4 FE-SEM images of GO and CNDs at different magnification. (a), (b) are the structure of GO, (c) and (d) shows the structure of CNDs. 47
Fig. 5-5 Observation of CNDs particle size with AFM. 48
Fig. 5-6 XRD diffraction patterns of (a) graphite, (b) GO and (c) CNDs. 50
Fig. 5-7 FT-IR spectra of (a) PANI, (b) PANI-f and (c) PANI-sd. 52
Fig. 5-8 The UV-vis spectra of (a) PANI, (b) PANI-f and (c) PANI-sd. 53
Fig. 5-9 Thermogravimetry curves of PANIs synthesis by different process. 55
Fig. 5-10 FE-SEM images of different synthesis process of PANI, (a)-(b) PANI, (c)-(d) PANI-f and (e)-(f) PANI-sd. 57
Fig. 5-11 XRD diffraction patterns of (a) PANI, (b) PANI-f and (c) PANI-sd. 58
Fig. 5-12 FT-IR spectra of (a) CNDs, (b) PANI, (c) CNDP5, (d) CNDP10 and (e) CNDP20. 61
Fig. 5-13 FT-IR spectra of (a) CNDs, (b) PANI-f, (c) CNDP5-f, (d) CNDP10-f and (e) CNDP20-f. 61
Fig. 5-14 FT-IR spectra of (a) CNDs, (b) PANI-sd, (c) CNDP5-sd, (d) CNDP10-sd and (e) CNDP20-sd. 62
Fig. 5-15 The UV-vis spectra of (a) PANI, (b) CNDP5, (c) CNDP10 and (d) CNDP20. 64
Fig. 5-16 The UV-vis spectra of (a) PANI-f, (b) CNDP5-f, (c) CNDP10-f and (d) CNDP20-f. 64
Fig. 5-17 The UV-vis spectra of (a) PANI-sd, (b) CNDP5-sd, (c) CNDP10-sd and (d) CNDP20-sd. 65
Fig. 5-18 Thermogravimetry curve of PANI and CNDP composites. 68
Fig. 5-19 Thermogravimetry curve of PANI-f and CNDP-f composites. 68
Fig. 5-20 Thermogravimetry curve of PANI-sd and CNDP-sd composites. 68
Fig.5-21 FE-SEM images of (a) CNDs, (b) PANI, (c) CNDP5, (d) CNDP10 and (e) CNDP20. 72
Fig.5-22 FE-SEM images of (a) CNDs, (b) PANI-f, (c) CNDP5-f, (d) CNDP10-f and (e) CNDP20-f. 73
Fig.5-23 FE-SEM images of (a) CNDs, (b) PANI-sd, (c) CNDP5-sd, (d) CNDP10-sd and (e) CNDP20-sd. 74
Fig. 5- 24 XRD diffraction patterns of (a) PANI, (b) CNDP5, (c) CNDP10 and (d) CNDP20. 76
Fig. 5- 25 XRD diffraction patterns of (a) PANI-f, (b) CNDP5-f, (c) CNDP10-f and (d) CNDP20-f. 76
Fig. 5- 26 XRD diffraction patterns of (a) PANI-sd, (b) CNDP5-sd, (c) CNDP10-sd and (d) CNDP20-sd. 77
Fig.5-27 The CV curves of GO and CNDs at scan rates 10 mV s-1 in 1 M H2SO4. 79
Fig.5-28 The CV curves of PANI synthesis by different process at scan rate 10 mV s-1 in 1 M H2SO4. 81
Fig.5-29 The CV curves of PANI and CNDP composites compared with CNDs at scan rate 10 mV s-1 in 1 M H2SO4. 85
Fig.5-30 The CV curves of PANI-f and CNDP-f composites compared with CNDs at scan rate 10 mV s-1 in 1 M H2SO4. 85
Fig.5-31 The CV curves of PANI-sd and CNDP-sd composites compared with CNDs at scan rate 10 mV s-1 in 1 M H2SO4. 85
Fig.5-32 Galvanostatic charge/discharge curves of (a) GO and (b) CNDs at current density of 0.1 A g-1. 88
Fig. 5-33 Specific capacitance of (a) GO and (b) CNDs. 88
Fig. 5-34 Galvanostatic charge/discharge curves of three kinds of PANI at current density 0.1 A g-1. 90
Fig. 5-35 Specific capacitance of PANIs at different current density. 90
Fig. 5-36 Galvanostatic charge/discharge curves of CNDs, PANI and CNDP composites at current density 0.1 A g-1. 93
Fig. 5-37 Galvanostatic charge/discharge curves of CNDs, PANI-f and CNDP-f composites at current density 0.1 A g-1. 93
Fig. 5-38 Galvanostatic charge/discharge curves of CNDs, PANI-sd and CNDP-sd composites at current density 0.1 A g-1. 93
Fig. 5-39 Specific capacitance of CNDs, PANI and CNDP composites at different current density. 94
Fig. 5-40 Specific capacitance of CNDs, PANI-f and CNDP-f composites at different current density. 94
Fig. 5-41 Specific capacitance of CNDs, PANI-sd and CNDP-sd composites at different current density. 94
Fig. 5-42 5000 charge-discharge cycle stability of CNDP10-sd composite at current density of 1 A g-1. Inset GCD curves for 15 consecutive cycles. 96
 

List of Tables
Table 2-1 Summary of the different materials for EDLCs 7
Table 2-2 Summary of metal oxides materials for pseudo-capacitors 10
Table 2-3 Summary of conductive polymers for pseudo-capacitors 11
Table 2-4 Summary the materials for hybrid supercapacitors 13
Table 2-5 Pseudo-capacitive performance of pristine PANI 15
Table 2-6 Application of PANI composites in supercapacitors 17
Table 2-7 Assignments for IR absorption bands of PANI[58] 21
Table 2-8 Summary of typical synthesis methods of CNDs 27
Table 2-9 Application of CNDs-based materials in supercapacitors 29
Table 5-1 The weight loss of graphite, GO and CNDs 46
Table 5-2 The weight loss of PANIs with different synthesis process 55
Table 5-3 The weight loss of CNDs, PANI and CNDP composites synthesis by different process 69
Table 5-4 Specific capacitance of GO and CNDs at different scan rate 79
Table 5-5 Specific capacitance of three kinds of PANI at different scan rate 81
Table 5-6 Specific capacitance of CNDs, PANI and CNDP composites at different scan rate 86
Table 5-7 Specific capacitance (Csp) of GO and CNDs at different current density 88
Table 5-8 Specific capacitance (Csp) of PANI at different current density 90
Table 5-9 Specific capacitance (Csp) of CNDs, PANI and CNDP composites at different current density 95

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