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Exploring Advanced Electrode Materials for Sodium-Ion Batteries

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Exploring Advanced Electrode Materials for Sodium-Ion Batteries University of Wollongong Research Online University of Wollongong Thesis Collection 2017+ University of Wollongong Thesis Collections 2020 Exploring Advanced Electrode Materials for Sodium-Ion Batteries Nana Wang University of Wollongong Follow this and additional works at: https://ro.uow.edu.au/theses1 University of Wollongong Copyright Warning You may print or download ONE copy of this document for the purpose of your own research or study. The University does not authorise you to copy, communicate or otherwise make available electronically to any other person any copyright material contained on this site. You are reminded of the following: This work is copyright. Apart from any use permitted under the Copyright Act 1968, no part of this work may be reproduced by any process, nor may any other exclusive right be exercised, without the permission of the author. Copyright owners are entitled to take legal action against persons who infringe their copyright. A reproduction of material that is protected by copyright may be a copyright infringement. A court may impose penalties and award damages in relation to offences and infringements relating to copyright material. Higher penalties may apply, and higher damages may be awarded, for offences and infringements involving the conversion of material into digital or electronic form. Unless otherwise indicated, the views expressed in this thesis are those of the author and do not necessarily represent the views of the University of Wollongong. Recommended Citation Wang, Nana, Exploring Advanced Electrode Materials for Sodium-Ion Batteries, Doctor of Philosophy thesis, Institute for Superconducting and Electronic Materials, University of Wollongong, 2020. https://ro.uow.edu.au/theses1/813 Research Online is the open access institutional repository for the University of Wollongong. For further information contact the UOW Library: [email protected] Exploring Advanced Electrode Materials for Sodium-Ion Batteries This thesis is presented as part of the requirement for the conferral of the degree: DOCTOR of PHILOSOPHY From the University of Wollongong by Nana Wang Institute for Superconducting and Electronic Materials Australian Institute of Innovative Materials Faculty of Mechanical, Material and Mechatronics Engineering 3 Mar 2020 Abstract i Abstract Sodium-ion and sodium metal batteries are the most promising candidates for large- scale energy storage systems, on account of sodium’s superiority of low cost and large abundance. To develop suitable electrode materials is the main scientific challenge for their practical application. This thesis project aims to fabricate a series of electrode materials with advantages of economic benefits, environmental friendliness, nontoxicity and structural stability, such as carbon-based and titanium-based materials for sodium-ion batteries, as well as sulfur-based cathode materials for sodium metal batteries. Here, novel hierarchical 3D porous carbon materials are synthesized through an in-situ template carbonization process. Electrochemical examination demonstrates that the carbonization temperature is a key factor that affects Na+ ion storage performance, owing to the consequent differences in surface area, pore-volume, and degree of crystallinity. The sample obtained at 600 °C delivers the best sodium storage performance, including long-term cycling stability (15000 cycles) and high rate capacity (126 mAh g-1 at 20 A g-1). Pseudocapacitive behavior in the Na+ ion storage process has been confirmed and studied via cyclic voltammetry. Full cells based on the porous carbon anode and Na3V2(PO4)3-C cathode also deliver good cycling stability (400 cycles). The porous carbon, combining the merit of high energy density and extraordinary pseudocapacitive behavior after cycling stability, can be a promising replacement for battery/supercapacitors hybrid and suggest a design strategy for new energy storage materials. In the second work, sulfur-doped double-shell sodium titanate (Na2Ti3O7) microspheres constructed from two-dimensional (2D) ultrathin nanosheets are Abstract ii synthesized via a templating route combined with a low-temperature sulfurization process. The resulting double-shell microspheres delivered a high specific capacity (~222 mA h g−1 at 1 C), excellent cycling stability (162 mAh g-1 after 15000 cycles at 20 C), and superior rate capability (122 mAh g-1 at 50 C) as anode for SIBs. The improved electrochemical properties are originated from synergistic effects between the unique double-shell nanostructures built from 2D nanosheets architecture and sulfur doping. This synergistic effect not only stabilize Na2Ti3O7 based electrode during the cycling, but also improve the sluggish Na insertion/extraction kinetics by narrowing the bandgap of Na2Ti3O7. The synthesis strategy proposed in this work can be developed into a technical rationale for generating high-performance sodium storage device. Finally, room-temperature sodium-sulfur (RT-Na-S) batteries are highly desirable for grid-scale stationary energy storage due to its low cost; however, short cycling stability caused by the incomplete conversion of sodium polysulfides is a major issue for their applications. Herein, we introduce an effective sulfur host, gold nanodots decorated on hierarchical N-doped carbon microspheres (CN/Au/S), to achieve completely reversible conversion reactions in the S cathode through electrocatalyzing low-kinetics conversion Na2S4 into NaS2 (discharge process) or S (charge process). Besides, gold nanodots and N-doped carbon can increase the conductivity of the S cathode and provide strong polar-polar adsorption of sodium polysulfides to alleviate the shuttling effects. When serving as cathode, the CN/Au/S can realize enhanced sulfur utilization, excellent cycling stability, and outstanding rate capability. This work deepens our understanding of the catalytic effect of gold atoms on sulfur molecules, opening a new avenue for cathode design and the development of advanced RT-Na-S batteries. Acknowledgments iii Acknowledgments Upon the completion of this thesis, firstly, I would like to express my heartfelt thanks to my supervisor Professor Shi Xue Dou, who offered me a good opportunity to research this great platform. Prof. Dou not only gave me a lot of helpful guidance and valuable suggestions on my research, he also encouraged me constantly both in my study and life. Besides, Prof. Dou created a free and warm work atmosphere, moreover, he provided strong financial supports, as well as many chances to conduct academic exchanges and attend high-level seminars. The great attitude would be expressed to my supervisor Dr. Xun Xu, for his constructive and practical pieces of advice on my research, as well as the great support to my study and life. Also, thanks to my other co-supervisor Dr. Ting Liao, who gave me helpful suggestions on my papers. I also would like to express my sincere gratitude to Dr. Yi Du and Dr. Yunxiao Wang, for their valuable suggestions and guidance on my work and life. Special thanks to Dr. Shulei Chou and Prof. Jiazhao Wang for their help. My thanks to Dr. Germanas Peleckis, Dr. Dongqi Shi, Dr. Kosta Konstantinov, Dr. Tony Romeo, and Dr. Gilberto Casillas-Garcia for their training on test instruments. Sincere thanks to my colleagues, Dr. Long Ren, Dr. Jingcheng Zhuang, Dr. Haifeng Feng, Dr. Amar AlKeisy, Dr. Li Wang, Dr. Weihong Lai, Dr. Binwei Zhang, Dr. Zhongfei Xu, Dr. Zhongchao Bai, Miss Dandan Cui, Mr. Liang Wang, Miss Ningyan Cheng, Miss Yani Liu, Miss Guyue Bo, Miss Nana Liu, Miss Yaping Chen, Miss Huiling Yang, Miss Qian Zhou for the happy time spent with them. Deep gratefulness to my family for their unconditional love. Certificate of Originality i Certification I, Nana Wang, declare that this thesis submitted in fulfilment of the requirements for the conferral of the Doctor of Philosophy Degree, from the University of Wollongong, is wholly my own work unless otherwise referenced or acknowledged. This document has not been submitted for qualifications at any other academic institution. Nana Wang 3 Mar 2020 Lists of Nomenclature ii Lists of Nomenclature Abbreviations 2D Two-dimensional 3D Three-dimensional CB Conduction band CE Coulombic efficiency CMC Sodium carboxymethyl cellulose CV Cyclic voltammetry DFT Density functional theory DOS Density of states EC Ethylene carbonate EDS Energy-dispersive X-ray spectroscopy EIS Electrochemical impedance spectroscopy FEC Fluoroethylene carbonate FT-IR Fourier-transform infrared spectroscopy HAADF High-angle annular dark-field JCPDS Joint Committee Powder Diffraction Standards LIBs Lithium-ion batteries NMP N-methyl pyrrolidone PC Propylene carbonate Raman Raman Spectroscopy RT-Na-S Room temperature sodium sulfur batteries SAED Selected area electron diffraction SEI Solid electrolyte interphase SEM Scanning electron microscopy SIB Sodium-ion batteries STEM Scanning transmission electron microscopy TEM Transmission electron microscopy Lists of Nomenclature iii TGA Thermogravimetric analysis UV Ultraviolet VB Valence band XPS X-ray photoelectron spectroscopy XRD X-ray diffraction List of Symbols θ Angle of incidence with the lattice plane degree d Lattice spacing nm λ Wavelength Å T Temperature ℃ Rct Charge transfer resistance Ω W Warburg impedance Ω List of Organisations AIIM Australian Institute of Innovative Materials ARC Australian Research Council EMC Electron Microscopy Centre ISEM Institute for Superconducting and Electronic Materials NSW The New South Wales UOW University of Wollongong
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