Nghiên cứu quá trình tổng hợp vật liệu nano silic để chế tạo anode định hướng ứng dụng cho ắc quy li ion

MINISTRY OF EDUCATION AND TRAINING MINISTRY OF NATIONAL DEFENCE ACADEMY OF MILITARY SCIENCE AND TECHNOLOGY NGUYEN VAN THANG STUDY ON THE SYNTHESIS PROCESS OF SILICON NANOMATERIALS TO FABRICATE ANODE ORIENT APPLICATION FOR Li-ION BATTERIES DOCTORAL THESIS OF CHEMISTRY Hanoi – 2019 MINISTRY OF EDUCATION AND TRAINING MINISTRY OF NATIONAL DEFENCE ACADEMY OF MILITARY SCIENCE AND TECHNOLOGY NGUYEN VAN THANG STUDY ON THE SYNTHESIS PROCESS OF SILICON NANOMATERIALS TO FABRICATE ANODE ORIENT APPLICATION FOR Li-ION BATTERIES Specialization: Theoretical chemistry and Physical chemistry Code: 44 01 19 DOCTORAL THESIS OF CHEMISTRY Scientific supervisors: Dr Nguyen Tran Hung Assoc Prof Dr Nguyen Manh Tuong Hanoi – 2019 i STATEMENT OF AUTHORSHIP I assure that the thesis is my own research work The data and results presented in the dissertation are honest and have not been unpublished in other work The reference is fully cited Hanoi, date: Ph.D student Nguyen Van Thang ii ACKNOWLEDGMENTS First of all, I would like to express their deep gratitude to my supervisors Dr Nguyen Tran Hung and Assoc Prof Dr Nguyen Manh Tuong for their direct instruction guidance and support throughout my thesis implementation process I am grateful for the help of the Training Department, Academy of Military Science and Technology throughout the complete process of the thesis I sincerely express my deepest thanks to the head of the Institute of Materials Chemistry, the head of the Nanomaterials Department, the colleagues and my friends for their encouragement Ph.D student Nguyen Van Thang iii TABLE OF CONTENTS Page LIST OF FIGURES vi LIST OF TABLES x LIST OF SYMBOLS AND ABBREVIATIONS xi INTRODUCTION CHAPTER 1: OVERVIEW 1.1 Overview of LIB 1.1.1 The new generation of electrochemical sources 1.1.2 LIB 1.1.3 Domestic and foreign research situation on LIB 13 1.2 Anode materials of LIB 15 1.2.1 Ion storage material 15 1.2.2 Anode graphene 17 1.2.3 Anode from silicon material, silicon nanoparticles/graphene 19 1.3 Methods of synthesis silicon nanoparticles and current progress of thermodynamics, the kinetics of synthesis of silicon nanoparticles from rice husk 21 1.3.1 Overview of silicon 21 1.3.2 Introduction about rice husk and current status of rice husk use in our country .26 1.3.3 The synthesis nano Si from rice husk 27 1.4 Synthesis methods of graphene 29 1.4.1 Overview of graphene 29 1.4.2 Synthesis methods of graphene 31 1.5 Kinetics and thermodynamics 35 1.5.1 Kinetic conditions 35 1.5.2 Thermal analysis and reaction kinetics study by thermal analysis .36 1.5.3 Thermodynamic conditions 39 CHAPTER 2: SUBJECTS AND METHODS OF RESEARCH 41 2.1 Research subjects 41 2.2 Research Methods 41 iv 2.2.1 The synthesis method of nano Si from rice husk 41 2.2.2 Kinetic, thermodynamic characteristics of synthesis nano Si from rice husk 45 2.2.3 Synthesis of rGO from graphite 46 2.3 Synthesis of nano Si@rGO material for LIB's anode 47 2.4 Fabrication of LIB to test electrochemical properties of anode materials .48 2.4.1 The fabrication process of LIB’s anode 48 2.4.2 LIB fabrication process 49 2.5 Methods of studying the composition and material structure .50 2.5.1 Scanning electron microscope (SEM) method 50 2.5.2 Energy-dispersive X-ray spectroscopy (EDX) method 51 2.5.3 Transmission electron microscopy (TEM) method 51 2.5.4 Fourier-transform infrared spectroscopy method (FT-IR) 51 2.5.5 X-ray diffraction method (XRD) 52 2.5.6 Isothermal method adsorbed gas nitrogen 52 2.6 Methods of surveying electrochemical properties of electrodes 52 2.6.1 Cyclic voltammetry (CV) 52 2.6.2 Galvanostatic charge-discharge (GC) 55 CHAPTER 3: RESULTS AND DISCUSSION 57 3.1 Synthesis silica nanoparticles from rice husk 57 3.1.1 Investigate the effects of acid treatment 57 3.1.2 Investigate the effects of calcination mode 61 3.1.3 Thermodynamics, the kinetics of the process of synthesis silica nanoparticles from rice husk 67 3.2 Synthesis of silicon nanoparticles from silica nanoparticles 72 3.2.1 Investigation of factors affecting silicon nanoparticles synthesis process .72 3.2.2 Kinetics of the process of synthesis silicon nanoparticles from silica nanoparticles 77 3.3 Synthesis nano rGO and nano Si@rGO 79 3.3.1 Synthesis nano rGO 79 3.3.2 Investigate the structure and composition of nano Si@rGO materials 89 3.4 Application of rGO, nano Si and nano Si@rGO materials for fabrication LIB’s anode 92 v 3.4.1 Experimental fabrication anode material combination 92 3.4.2 The electrochemical characteristics of LIB 94 3.5 Conclusion of chapter 105 CONCLUSION 107 LIST OF PUBLICATIONS RELATING TO THESIS 109 LIST OF REFERENCES 110 vi LIST OF FIGURES Pages Figure 1.1 Comparison of energy densities and specific energy of different rechargeable batteries Figure 1.2 Some Li-ion batteries on the white background Figure 1.3 Schematic of the electrochemical process in LIB Figure 1.4 Structures of common cathode materials: 10 Figure 1.5 The model illustrates the formation of host-guest compound 16 Figure 1.6 Schematic picture of the failure mechanism of silicon nanoparticles during cycling 20 Figure 1.7 Schematic process for fabricating the silicon nanoparticles/graphene nanocomposite 21 Figure 1.8 Schematic of silicon synthesis silicon nanoparticles by chemical vapor deposition of silanes 24 Figure 1.9 Schematic of silicon synthesis by electrochemical etching method 25 Figure 1.10 Graphene is the basic structure of other carbon nanostructures 30 Figure 1.11 The bonds of carbon atoms in the graphene 30 Figure 1.12 Image illustrating graphene oxide film 33 Figure 1.13 The thermal reducing reaction of hydroxyl groups 34 Figure 1.14 The thermal reducing reaction of carbonyl groups 34 Figure 2.1 Process of synthesizing silica nanoparticles from rice husk 43 Figure 2.2 Process of synthesizing silicon nano from silica nano 44 Figure 2.3 Schematic diagram of the reduction facility for silicon nanoparticles synthesis process 44 Figure 2.4 rGO synthesis process from graphite 46 Figure 2.5 The thermal reduction process of GO in the furnace 47 Figure 2.6 The synthesis process of nano Si@rGO 48 Figure 2.7 The fabrication process of LIB’s anode 49 Figure 2.8 LIB with the two-electrode structure and glove box 50 Figure 2.9 Cyclic voltammetry waveform 53 vii Figure 2.10 LIB with the two-electrode structure to measure electrochemical characterizations 54 o Figure 3.1 TG/DTA curve of rice husk at the heating rate of C/min .57 Figure 3.2 SiO2 content in rice husk ash dependence on acid treatment time .58 Figure 3.3 SiO2 content in rice husk ash dependence on acid treatment temperature 59 Figure 3.4 SiO2 content in rice husk ash dependence on ratio rice husk/HCl acid 60 Figure 3.5 Influence of calcination temperature on SiO2 content in rice husk ash 62 Figure 3.6 Influence of calcination time on SiO2 content in rice husk ash 62 Figure 3.7 SEM images of rice husk ash samples after calcination at the temperature of o o 650 C at the heating rates of 3, 6, 9, 12, 15 C/min, respective 63 Figure 3.8 SEM and EDX images of nano SiO2 64 Figure 3.9 Particle size distribution of nano SiO2 65 Figure 3.10 XRD pattern of nano SiO2 65 Figure 3.11 SEM image of nano SiO2 sample in high-resolution .66 Figure 3.12: TEM image of nano SiO2 66 Figure 3.13 DSC curves of rice husk pyrolysis process with heating rates of 3, 6, o 9, 12, 15 C/min 67 Figure 3.14 Plots of lg and 1/Tp of RHs of the F-W-O model 68 Figure 3.15 Plots of ln(β/Tp ) and 1/Tp of RHs of the Kissinger model .68 Figure 3.16 DTA curves of rice husk pyrolysis process with heating rates of 3, 6, o 9, 12, 15 C/min 69 Figure 3.17 Plots of lg and 1/Tp of RHs of the F-W-O model 70 Figure 3.18 Plots of ln(β/Tp ) and 1/Tp of RHs of the Kissinger model .70 Figure 3.19 Si content dependence on mol ratio Mg/SiO2 72 Figure 3.20 Si content dependence on calcination temperature 73 Figure 3.21 SEM images of nano Si samples obtained by magnesiothermic reduction of nano SiO2 with heating rates of °C/min and 15 °C/min .74 Figure 3.22 N2 adsorption-desorption isotherms and the pore size distribution of nano Si RH-5 75 viii Figure 3.23 DSC curves of the reaction between nano SiO2 and Mg with different ramp rates 75 Figure 3.24 XRD pattern of nano Si RH-5 76 Figure 3.25 Particle size distribution of nano Si RH-5 76 Figure 3.26 TEM image of nano Si RH-5 77 Figure 3.27 DSC curves of nano SiO2 reduction process with Mg with heating rates of o 5, 9, 12, 15 C/min 77 Figure 3.28 Plots of lg and 1/Tp in the reduction of SiO2 by Mg of the F-W-O model 78 Figure 3.29 Plots of ln(β/Tp ) and 1/Tp in the reduction of SiO2 by Mg of Kissinger model 78 Figure 3.30 GO gel after acid washing 79 Figure 3.31 GO gel after freeze-drying 79 Figure 3.32 Graphite particle size distribution 80 Figure 3.33 GO particle size distribution 80 Figure 3.34 FT-IR spectra of graphite 81 Figure 3.35 FT-IR spectra of GO 81 o Figure 3.36 TG/DTA curve of GO at the heating rate of 10 C/min 83 Figure 3.37 XRD pattern of graphite 83 Figure 3.38 XRD pattern of GO 84 Figure 3.39 SEM image of graphite 84 Figure 3.40 SEM image of GO 85 Figure 3.41 TEM image of GO 85 Figure 3.43 Image of rGO sheets 86 Figure 3.44 rGO powder 86 Figure 3.45 FTIR spectra of rGO 87 o Figure 3.46 TG/DTA curve of GO at the heating rate of 10 C/min 87 Figure 3.47 SEM images of rGO at different resolutions 88 Figure 3.48 XRD pattern of rGO 88 Figure 3.49 EDX pattern of rGO (M1.1) 89 Figure 3.50 EDX pattern of rGO (M2.1) 89 106 - Synthesized rGO, nano Si@rGO and investigated the structure and morphology of rGO, nano Si@rGO materials The C content in the rGO sample is 75.2 %; Si and C content in nano Si@rGO samples were 69.96 % and 31.04 %, respectively - Successfully fabricated LIB with anode on rGO, nano Si and nano Si@rGO basis The specific electrochemical characteristics are as follows: + LIB with anode on rGO basis: Maximum theoretical capacity 372 mAh/g; maximum current density 50C (18600 mAh/g); maximum number of chargedischarge cycles: 100 cycles; Coulombic efficiency: 75 % + LIB with anode on nano Si basis: Maximum theoretical capacity 2250 mAh/g; maximum current density 1C (3800 mAh/g); maximum number of charge-discharge cycles: 35 cycles; Coulombic efficiency: 93 % + LIB with anode on nano Si@rGO basis: Maximum theoretical capacity 1800 mAh/g; maximum current density 5C (13850 mAh/g); maximum number of chargedischarge cycles: 500 cycles; Coulombic efficiency: 98 % 107 CONCLUSION Selected the suitable conditions for the synthesis of nano-silica from the rice husk which is the acid treatment concentration HCl: 10 %, the acid treatment temperature 90 °C, the treatment time hours, the ratio of the rice husk/acid g rice husk/40 ml o HCl 10 %, the calcination temperature 650 C during hours with the heating rate o of C/min The obtained silica nanoparticles have a size of 50-70 nm, the amorphous phase structure and the purity > 99% Determined the thermodynamic and kinetic parameters of synthesizing silica nano from the rice husk: the activation energy of synthesizing silica nano from the * * rice husk, E = 126.14 (kJ/mol) (FWO model); E = 122.6 (kJ/mol) and the 10 exponential factor in the Arrhenius equation is A = 1,033.10 (Kissinger model), thereby determining the reaction rate constant according to the Arrhenius equation: Determination of thermodynamic parameters of synthesis silica nanoparticles from * * * the rice husk: ∆G = 138,5  180,4 kJ/mol, ∆H = 114,9  120,1 kJ/mol ∆S = -70,9  -61,5 J/mol.K Selected the suitable conditions for the synthesis of silicon nanoparticles from silica nanoparticles with the reducing the agent magnesium: the molar ratio of o Mg/SiO2 is 2.1:1, the calcination temperature at 800 C during hours with the o heating rate of C/min Silicon nanoparticles obtained with the particle size from 30-50 nm, crystal phase structure and the purity > 99% * The activation energy of silica reduction process with magnesium: E = 308.34 * (kJ/mol) (F-W-O model); E = 314.13 (kJ/mol) and the exponential factor in the 26 Arrhenius equation is A = 8.19.10 (Kissinger model) Synthesized rGO, nano Si@rGO and investigated the structure and morphology of rGO, nano Si@rGO materials The C content in the rGO sample is 75.2 %; Si and C content in nano Si@rGO samples were 69.96 % and 31.04 %, respectively Successfully fabricated LIB with the anode on rGO, nano Si and nano Si@rGO basis The specific electrochemical characteristics are as follows: 108 + LIB with the anode on rGO basis: The maximum theoretical capacity 372 mAh/g; maximum current density 50C (18600 mAh/g); maximum number of chargedischarge cycles: 100 cycles; Coulombic efficiency: 75 % + LIB with the anode on nano Si basis: The maximum theoretical capacity 2250 mAh/g; maximum current density 1C (3800 mAh/g); maximum number of chargedischarge cycles: 35 cycles; Coulombic efficiency: 93 % + LIB with anode on nano Si@rGO basis: Maximum theoretical capacity 1800 mAh/g; maximum current density 5C (13850 mAh/g); maximum number of chargedischarge cycles: 500 cycles; Coulombic efficiency: 98 % The contribution: Determined the conditions to synthesis the silicon nanoparticles from the rice husk Fabricated an anode based on nano Si for the electrochemical characteristics such as the high specific capacity, the high current density and number of chargedischarge cycles, high Coulombic performance Further research directions: Further research on the thermodynamic and kinetic characteristics affecting the synthesis of silicon from nano-silica Further research on the anode fabrication processes based on the synthesis materials, which helps to optimize the anode fabrication process for LIB Further investigate the electrochemical characteristics of an anode made from rGO, nano Si and nano Si @ rGO to get more data about these batteries 109 LIST OF PUBLICATIONS Nguyen Van Thang, Nguyen Manh Tuong, Nguyen Tran Hung (2016), “Thermodynamic evaluation of synthesis of nanosilica from the rice husk”, Proceeding of The 5th Asian materials data symposium, Hanoi 11/2016, pp 331340 Nguyen Van Thang, Nguyen Manh Tuong, Nguyen Tran Hung (2017), “Silicon nanoparticles from the rice husk – thermodynamic evaluation and synthesis”, Vietnam journal of chemistry, 55(3e), pp 176-182 Nguyen Van Thang, Nguyen Manh Tuong, Nguyen Tran Hung (2018), “Characteristic of thermodynamics, kinetics of the process silicon nanoparticle synthesis from rice husk”, Journal of Military Science and Technology, Special Issue CBES2, pp 107-114 Nguyen Van Thang, Nguyen Manh Tuong, Nguyen Tran Hung (2018), “Synthesis and investigate the electrochemical performance of Si/Graphene nanocomposite anode for Lithium-ion batteries”, Vietnam journal of chemistry, 56(4e), pp 168-171 110 LIST OF REFERENCES Vietnamese Le Ha Chi (2012), Fabrication and survey of luminescent, photoelectric and electrochemical properties of nanostructured transition layers, PhD thesis in Physics, Vietnam National University, Hanoi Nguyen Tran Hung, Didier Pribat 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of synthesis of silicon nanoparticles... properties of anode electrodes based on silicon nanoparticles, rGO and nano Si@rGO materials Fabrication of LIB with the anode electrode on the basis of silicon nanoparticles, rGO, nano Si@rGO