SYNTHESIS OF METAL OXIDE NANOSTRUCTURES AND THEIR APPLICATIONS AS LITHIUM ION BATTERY ANODES CHEN YU (B ENG., HONS.), NUS A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY (PH.D) DEPARTMENT OF MATERIALS SCIENCE AND ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2013 DECLARATION I hereby declare that this thesis is my original work and it has been written by me in its entirety I have duly acknowledged all the sources of information which has been used in this thesis This thesis has also not been submitted for any degree in any university previously Chen Yu 3rd Sep 2013 i LIST OF PUBLICATIONS The Majority of this thesis work has been published in various international journals and international conference: Journal paper: Y Chen, B Song, R M Chen, L Lu and J M Xue, A Study of Superior Electrochemical Performances of nm SnO2 Nanoparticles Supported by Graphene, Journal of Materials Chemistry A, DOI: DOI:10.1039/C3TA14745B (2014) Y Chen, B Song, X Tang, L Lu and J M Xue, Ultra-Small Fe3O4 Nanoparticle /MoS2 Nanosheet Composites with Superior Performances for Lithium Ion Batteries, Small, DOI: 10.1002/smll.201302879 (2014) Y Chen, B Song, L Lu and J M Xue, Fe3O4 Nanoparticles Embedded in Uniform Mesoporous Carbon Spheres for Superior High Rate Battery Application, Advanced Functional Materials, 24, 319-326 (2014) Y Chen, B Song, L Lu and J M Xue, Ultra-small Fe3O4 Nanoparticle Decorated Graphene Nanosheets with Superior Cyclic Performance and Rate Capability, Nanoscale, 5, 6797-6803 (2013) Y Chen, B Song, L Lu and J M Xue, Synthesis of Carbon Coated ii Fe3O4/SnO2 Composite Beads and Their Application as Anodes for Lithium Ion Batteries, Materials Technology: Advanced Performance Materials, 28, 254-259 (2013) Invited paper Y Chen, B Song, X Tang, L Lu and J M Xue, One-step Synthesis of Hollow Porous Fe3O4 Beads-Reduced Graphene Oxide Composites with Superior Battery Performance, Journal of Materials Chemistry, 22, 17656-17662 (2012) (Most Read Articles in Jul 2012: No 3) Y Chen, H Xia, L Lu and J M Xue, Synthesis of Porous Hollow Fe3O4 Beads and Their Applications in Lithium Ion Batteries, Journal of Materials Chemistry, 22, 5006-5012 (2012) (Most Read Articles in Feb 2012: No 1) Y Chen, Q Z Huang, J Wang, Q Wang and J M Xue, Synthesis of Monodispersed SnO2@C Composite Hollow Spheres for Lithium Ion Battery Anode Applications, Journal of Materials Chemistry, 21, 17448-17453 (2011) (Most Read Articles in Oct 2011: No 7) X Tang, Q Tay, Z Chen, Y Che n, G K L Goh and J M Xue, CuInZnS-Decorated Graphene Nanosheets for Highly Efficient Visible-Light-Driven Photocatalytic Hydrogen Production, Journal of Materials Chemistry A, 1, 6359-6365 (2013) iii 10 X Tang, Q Tay, Z Chen, Y Chen, G K L Goh and J M Xue, Cu–In–Zn–S Nanoporous Spheres for Highly Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution, New Journal of Chemistry, 37, 1878-1882 (2013) Conference presentation: Y Chen, B Song, L Lu and J M Xue, Fe3O4/Graphene Composite for Advanced Lithium Ion Battery Anode Application, 2013 MRS Spring Meeting, April 2013, -5, San Francisco, California, USA (Oral Presentation by Y Chen) iv ACKNOWLEDGEMENTS First of all, I would like to give my deepest gratitude to Dr Xue Junmin He supervised my FYP study, and encouraged me to pursue higher degrees He was more than a teacher to me since then I deeply appreciate his supervision, guidance, advice, and encouragement throughout my Ph.D study His knowledge, expertise, and scientific attitude are the foundation for this work It is a great honor of mine to carry out my Ph.D study under his supervision In addition, I would like to express my sincere gratitude to Prof John Wang I thank him for giving me the chance to carry out Ph.D study in this department His trust in me has been a great motivation for my graduate study Also, I wish to express my great appreciation to Prof Lu Li and Mr Song Bohang from department of Mechanical Engineering Their knowledge and efforts on electrochemical measurements make the completion of this work possible Besides, I extend my thanks to my labmates, Dr Eugene Choo, Dr Sheng Yang, Dr Yuan Jiaquan, Dr Tang Xiaosheng, Mr Li Meng, Mr Erwin, Mr Vincent Lee, Ms Wang Fenghe, and Dr Leng Mei for their cooperation and discussion My thanks also go to all lab technologists in my department for their coordination and assistance Finally, I would like to give my appreciation to my family for their encouragements, supports, and understandings that help to complete this thesis work v TABLE OF CONTENTS Declaration i List of Publications ii Acknowledgements v Table of Contents vi Summary x List of Figures .xii List of Abbreviations xix CHAPTER 1: Introduction 1.1 Overview of Lithium Ion Batteries 1.1.1 Principle of Operation 1.1.2 Current Status and Challenges 1.2 Anode Materials of Lithium Ion Batteries 1.2.1 Intercalation based anodes 1.2.2 Alloying based anodes 1.3.3 Conversion reaction based anodes 11 1.3 Literature Review of Metal Oxide Anode Materials 12 1.3.1 Overview 12 1.3.2 Tin Oxides as Anode Materials 13 1.3.3 Iron Oxides as Anode Materials 14 1.3.4 Strategies to Enhance Electrochemical Performances of Metal Oxides 15 1.4 Project Motivations and Designs 22 1.5 Research Objectives 25 1.6 Thesis Outline 25 CHAPTER 2: Experimental 27 2.1 Materials 27 2.2 Materials Synthesis 28 2.3 Characterizations 28 2.3.1 Morphological Study 28 2.3.2 Chemical Analysis 29 vi 2.3.3 Thermogravimetric Analysis 30 2.3.4 Electrochemical Measurements 30 CHAPTER 3: Carbon Coated Hollow SnO2 Beads with Enhanced Cyclic Stabilities 31 3.1 Motivations and Design of Experiment 31 3.2 Synthesis of Carbon Coated Tin oxide (SnO2@C) Hollow Spheres 34 3.2.1 Synthesis of PVP-Modified Polystyrene (PS) Beads 34 3.2.2 Synthesis of Tin Oxide coated Polystyrene (PS@SnO2) Beads 34 3.2.3 Synthesis of Tin Oxide hollow spheres 35 3.2.4 Synthesis of Carbon coated Tin oxide (SnO2@C) Hollow Spheres 35 3.2.5 Electrochemical Measurements for SnO2@C 35 3.3 Preparation Scheme of SnO2@C Beads 36 3.4 Characterizations of Carbon Coated Hollow SnO2 Beads 37 3.5 Effect of Carbon Coating on Structural Integrities 41 3.6 Electrochemical Analysis of SnO2@C 43 3.7 Remarks 46 CHAPTER 4: Carbon Coated Porous Hollow Fe3O4 Beads with Improved Cyclic Stabilities 47 4.1 Motivations and Design of Experiment 47 4.2 Synthesis of Carbon Coated Porous Hollow Fe3O4 beads (Fe3O4/C) 48 4.2.1 Preparation of Porous Hollow Magnetite (Fe3O4) Beads 48 4.2.2 Preparation of Carbon Coated Magnetite (Fe3O4/C) Beads 49 4.2.3 Electrochemical Measurements for Fe3O4/C 49 4.3 Morphological Characterization of Porous Hollow Fe3O4 Beads 50 4.4 Formation Mechanism of Porous Hollow Fe3O4 Beads 52 4.4.1 Morphological Characterization of Porous Hollow Fe3O4 Beads at Different Reaction Stages 52 4.4.2 Magnetic Reponses of Porous Hollow Fe3O4 Beads at Different Reaction Stages 55 4.4.3 Schematic Illustration of Porous Hollow Fe3O4 Beads Formation 56 4.5 Characterizations of Carbon Coating 57 4.5.1 Morphological Characterizations 57 4.5.2 Chemical Analysis 59 4.6 Synthesis of Porous Hollow α-Fe2O3 Beads 60 4.7 Electrochemical Performances of Carbon Coated Porous Hollow Fe3O4 Beads vii 61 4.8 Morphological Changes After Cycling 65 4.9 Remarks 66 CHAPTER 5: Hollow Porous Fe3O4 Beads/reduced Graphene Oxide Composites with Superior Capacity Retention Properties 68 5.1 Motivations and Design of Experiment 68 5.2 Synthesis of rGO Incorporated Porous Hollow Fe3O4 Beads (Fe3O4/rGO) 70 5.2.1 Preparation of GO 70 5.2.2 Synthesis of rGO Incorporated Porous Hollow Fe3O4 Beads (Fe3O4/rGO) 70 5.2.3 Synthesis of rGO 71 5.2.4 Electrochemical Measurements for Fe3O4/rGO 71 5.3 Morphological Characterization of Fe3O4/rGO 72 5.4 Synthesis Mechanism 74 5.5 Characterizations of GO and rGO 75 5.6 Chemical and Porosity Characterization of Fe3O4/rGO 77 5.7 Electrochemical Performances of Fe3O4/rGO 80 5.8 Remarks 87 CHAPTER 6: Fe3O4 nanoparticles embedded in uniform mesoporous carbon spheres for superior high rate battery applications 88 6.1 Motivation and Design of Experiment 88 6.2 Synthesis of Uniform Mesoporous Carbon Spheres embedded by Fe3O4 Nanoparticles (IONP@mC) 90 6.2.1 Synthesis of Water-soluble Fe3O4 Nanoparitlces (IONP) 90 6.2.2 Synthesis of Iron Oxide Nanoparticles Embedded in Polymeric Composite (IONP@PC) 90 6.2.3 Synthesis of Iron Oxide Nanoparticles Embededd in Mesoporous Carbon Beads (IONP@mC) 91 6.2.4 Electrochemical Measurements for IONP@mC 91 6.3 Synthesis Scheme 92 6.4 Morphological Characterizations 95 6.5 Porosity Characterizations 100 6.6 Chemical Analysis 103 viii 6.7 Electrochemical Characterizations 104 6.7.1 Electrochemical Performances of IONP/mC 104 6.7.2 Comparison with other reported Fe3O4/G Anodes 110 6.7.3 Morphological Effect on the battery performances of IONP@mC 111 6.7.4 Effect of IONP Percentage on Electrochemical Performances of IONP@mC 112 6.7.5 Effect of Carbonization Temperature on the Electrochemical Performances of IONP@mC 113 6.7.6 Morphological Characterizations of IONP@mC after Electrochemical Tests 116 6.8 Remarks 118 CHAPTER 7: Ultra-small Fe3O4 nanoparticles-decorated graphenes with superior cyclic performance and rate capability 120 7.1 Motivation and Design of Experiment 120 7.2 Synthesis of Ultra-small Fe3O4 nanoparticles decorated graphenes (USIO/G) 123 7.2.1 Preparation of GO 123 7.2.2 Synthesis of Ultra-small Fe3O4 nanoparticles decorated graphenes (USIO/G) 123 7.2.3 Electrochemical Measurements for USIO/G 124 7.3 Synthesis Scheme 124 7.4 Characterization of USIO/G 125 7.5 Chemical Analysis 130 7.6 Porosity Characterization of USIO/G 132 7.7 Electrochemical Performances of USIO/G 133 7.8 Remarks 140 CHAPTER 8: Conclusions and Recommendations for Future Works 141 8.1 Project Conclusions 141 8.2 Recommendations for Future Works 148 8.2.1 Ultra-Small Tin Oxide and Graphene Composite 148 8.2.2 Synergistic Effect between Iron Oxide and Tin Oxide 150 Bibliography 154 ix electrochemical tests are 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IONP@PC and IONP@mC-600 Insets of C and F: SAED patterns of IONP@PC and IONP@mC-600 95 Figure 6-4: Particle size distributions of (A) IONP@PC and (B) IONP@mC-600 96 Figure 6-5 TEM images of IONP@mC-600... iron oxides and lithium was in the 1980s.[51] However, the nature of the reaction was not clear until J M Tarascon and his coworkers reported the conversion reaction between transition metal oxides... as TiO2[30] and Li4Ti5O12[17]; (2) alloying based materials, such as Si,[31] Ge,[32] Sn,[33] and their oxides/composites; (3) conversion reaction based materials, including transition metal oxides,[34]