Design, Fabrication and Electrochemical Performance of Nanostructured Carbon Based Materials for High-Energy Lithium-Sulfur Batteries (eBook)

Guangmin Zhou received his PhD from the Institute of Metal Research (IMR), Chinese Academy of Sciences in 2014 under the supervision of professors Hui-Ming Cheng and Feng Li, prior to serving for a year as a postdoc with Prof. Manthiram at UT Austin. He is currently a postdoc fellow at Stanford University with Prof. Yi Cui.His research mainly focuses on advanced carbon-based (porous carbon, graphene, carbon nanotubes) composites for energy storage: their synthesis, electrochemical properties and mechanisms. Zhou has published more than 50 articles in peer-reviewed scientific journals, and first-authored 21 papers published in Nature Communications, Advanced Materials, Advanced Energy Materials, ACS Nano, Energy & Environmental Science, Advanced Functional Materials, Chemistry of Materials, Nano Energy, etc. The paper published in Advanced Materials was selected as one of the Top 100 most influential papers in China in 2014. Additionally, he has authored 1 book chapter (Graphene Science Handbook) and holds 10 patents.

Supervisors’ Foreword 6
Parts of this thesis have been published in the following journal articles:[A1] Guangmin Zhou, Songfeng Pei, Lu Li, Da-Wei Wang, Shaogang Wang, Kun Huang, Li-Chang Yin, Feng Li, Hui-Ming Cheng. A graphene-pure sulphur sandwich structure for ultrafast, long-life lithium-sulphur batteries. Advanced Materials, 2014, 26, 625–631.[A2] Guangmin Zhou, Li-Chang Yin, Da-Wei Wang, Lu Li, Songfeng Pei, Ian R. Gentle, Feng Li, and Hui-Ming Cheng, Fibrous hybrid of graphene and sulfur nanocrystals for high performance lithium-sulfur batteries. ACS Nano, 2013, 7, 5367–5375.[A3] Guangmin Zhou, Da-Wei Wang, Feng Li, Peng-Xiang Hou, Li-Chang Yin, Chang Liu, Gaoqing (Max)Lu, Gentle, Ian, Hui-Ming Cheng. A flexible nanostructured sulphur-carbon nanotube cathode with high rate performance for Li-S batteries. Energy & Environmental Science, 2012, 5, 8901–8906.[A4] Guangmin Zhou, Lu Li, Chaoqun Ma, Shaogang Wang, Ying Shi, Nikhil Koratkar, Wencai Ren, Feng Li, Hui-Ming Cheng. A graphene foam electrode with high sulfur loading for flexible and high energy Li-S batteries. Nano Energy, 2015, 11, 356–365.[A5] Guangmin Zhou, Feng Li, Hui-Ming Cheng. Progress in flexible lithium batteries and future prospects, Energy &
Acknowledgements 9
Contents 12
About the Author 15
Other Academic Awards and Honors Include 15
Abbreviations 17
1 Introduction 19
1.1 Introduction of Lithium–Sulfur Secondary Battery 19
1.1.1 Cathode Materials 21
1.1.1.1 Sulfur–Carbon Composites 21
1.1.1.2 Sulfur-Conducting Polymer Composites 26
1.1.1.3 Sulfur/Metal Oxide Composite 26
1.1.1.4 Lithium Sulfide Materials 28
1.1.2 Anode Materials 31
1.1.3 Separators and Interlayers 33
1.1.4 Electrolyte 34
1.2 Motivations of the Thesis 36
References 37
2 Revealing Localized Electrochemical Transition of Sulfur in Sub-nanometer Confinement 41
2.1 Research Background 41
2.2 Design, Fabrication, and Characterization of Carbon–Sulfur Composite Cathode 43
2.2.1 Synthesis of Hierarchical Porous Carbon (HPC) 43
2.2.2 Synthesis of Carbon–Sulfur Composite 44
2.2.3 Structure Characterization of the Carbon–Sulfur Composite 44
2.2.4 Electrochemical Performance of the Carbon–Sulfur Composite Cathode 47
2.3 Mechanism Analysis of the Pore Size Dependence of Confinement on Electrochemical Performance in Li–S Batteries 50
2.4 Conclusion 53
References 53
3 Flexible Nanostructured Sulfur–Carbon Nanotube Cathode with High-Rate Performance for Li–S Batteries 56
3.1 Research Background 56
3.2 Design and Fabrication of Flexible Nanostructured S-CNT Cathode 58
3.2.1 Synthesis of S-Containing Anodic Aluminum Oxide (AAO) Template 58
3.2.2 Synthesis of S-CNTs Composites 58
3.2.3 Synthesis of CNTs 59
3.2.4 Fabrication of Flexible S-CNT Membranes 59
3.3 Sulfur Formation Mechanism 59
3.4 Characterization of S-CNTs 60
3.5 Control of the Sulfur Content in the S-CNTs 62
3.6 First-Principles Calculations of the Sulfur Molecules Diffusion Within the Micropores 63
3.7 Synthesis, Structure, and Performance of Flexible S-CNT Electrode 63
3.8 Electrochemical Performance of Flexible Nanostructured S-CNT Cathode 65
3.9 Fabrication of Flexible Silicon/Graphene Anode and Assembly of Flexible Li–S Full Battery Prototype 67
3.9.1 Fabrication of Flexible Silicon/Graphene Composite Film 67
3.9.2 Fabrication of Flexible Prelithiated Silicon/Graphene Composite Film 68
3.9.3 Assembly of Flexible Li–S Full Battery Prototype 69
3.10 Conclusion 70
References 70
4 Fibrous Hybrid of Graphene and Sulfur Nanocrystals for High-Performance Lithium–Sulfur Batteries 73
4.1 Research Background 73
4.2 Material Fabrication and Structure 74
4.2.1 Synthesis of GO 74
4.2.2 Synthesis of Intercalation Exfoliated Graphene 75
4.2.3 Synthesis of the Thermal Exfoliated-Reduced Graphene 75
4.2.4 Preparation of G–S Hybrids 75
4.2.5 Preparation of G–S Hybrids (Powder) 75
4.2.6 Preparation of G–Smix 75
4.2.7 Structure Characterization of the Composites 76
4.2.7.1 Effect of Graphene Precursor on Tuning the Morphology and Sulfur Contents 76
4.2.7.2 Effect of Oxygen Functional Groups on Tuning the Material Morphology and Structure 76
4.2.7.3 Crystal Structure and Surface Functionality Analysis 78
4.3 Interaction Mechanism Between Oxygen-Containing Groups and Sulfur/Polysulfides 81
4.4 Properties of Sulfur Nanocrystal/Graphene Composites 83
4.4.1 Electrical Property and Mechanical Flexibility 83
4.4.2 Electrochemical Performance 84
4.5 Conclusion 88
References 88
5 Graphene–Pure Sulfur Sandwich Structure for Ultrafast, Long-Life Lithium-Sulfur Batteries 91
5.1 Research Background 91
5.2 Construction of Sandwich Cathode Structure 93
5.2.1 GCC Fabrication 93
5.2.2 Fabrication of Sulfur-Coated GCC Electrodes 93
5.2.3 G-Separator Fabrication 93
5.3 Structure Characterization of the Sandwich Cathode Structure 94
5.3.1 Structure Characterization of the Graphene Powder 94
5.3.2 Structure Feature of the GCC 94
5.3.3 Structure Characterization of the GCC/S Cathode 96
5.3.4 Structure Characterization of the G-Separator 98
5.4 Electrochemical Performance of the Sandwich Cathode Structure 99
5.5 Interaction Between Graphene and Sulfur Species in Sandwich Cathode Structure 104
5.5.1 Function as a Current Collector 104
5.5.2 Function as a Separator Coating Layer 105
5.6 Conclusion 108
References 109
6 A Graphene Foam Electrode with High Sulfur Loading for Flexible and High-Energy Li–S Batteries 111
6.1 Research Background 111
6.2 Fabrication and Characterization of the 3D GF-Based Electrode 112
6.2.1 Preparation of PDMS/GF 112
6.2.2 Preparation of S-PDMS/GF Electrode 112
6.2.3 Structure Characterization of the S-PDMS/GF Electrode 113
6.3 Mechanical Properties of the 3D GF-Based Electrode 116
6.4 Electrochemical Performance of the 3D GF-Based Sulfur Electrode 117
6.5 Areal Capacity of the 3D GF-Based Sulfur Electrode 121
6.6 Conclusion 125
References 126
7 Conclusions and Perspective 129
7.1 Main Conclusion and Innovations 129
7.2 Perspective for Future Works 131