Lithium Ion Batteries and Supercapacitors
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A STUDY OF COMPONENTS FOR LITHIUM AND SODIUM BATTERIES AND OTHER STORAGE DEVICES A STUDY OF COMPONENTS FOR LITHIUM AND SODIUM BATTERIES AND OTHER STORAGE DEVICES By XAVIER DANIEL MICHAUD, M.A.Sc., B.Eng. A Thesis Submitted to the School of Graduate Studies in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy McMaster University © Copyright by Xavier Michaud, February 2019 DOCTOR OF PHILOSOPHY (2019) McMaster University Department of Materials Science & Engineering Hamilton, Ontario TITLE: A Study Of Components For Lithium And Sodium Batteries And Other Storage Devices AUTHOR: Xavier Daniel Michaud, M.A.Sc., (McMaster University), B.Eng., (Dalhousie University) SUPERVISOR: Prof. Anthony Petric, Professor Emeritus, Ph.D., P.Eng. CO-SUPERVISOR: Prof. Igor Zhitomirsky, Distinguished Engineering Professor, Ph.D., P.Eng. NUMBER OF PAGES: XXIII, 177. ii Lay Abstract The goal of this work is to examine materials used in different types of electrochemical storage devices. The modification of resistive properties of β-alumina electrolytes are examined for use in high temperature sodium batteries. Electrophoretic deposition methods are used to rapidly make thin electrodes for lithium ion batteries and supercapacitors. The stoichiometric compound NaSi, a potentially safer and greener method of producing hydrogen gas, is characterized for a better understanding of its properties, and therefore production. iii Abstract An investigation of electrochemical storage device materials has been undertaken in four parts. The bulk and interfacial resistance of Na + beta-alumina tubes were separated using a galvanostatic charge-discharge method. Sodium silicide was characterized to better understand its synthesis. BiMn 2O5 was produced using a sol-gel method and tested for pseudocapacity. Different lithium ion anode and cathode materials were deposited using a new electrophoretic deposition method. A novel galvanostatic charge-discharge method was developed for the determination of bulk and interface resistance in Na + beta-alumina solid electrolytes [BASE] . Dense and duplex BASE tubes were tested by varying the exposed surface area. The results of dense BASE tube pairs were used to determine the bulk and interfacial resistance components, while duplex BASE tubes were tested to determine the reduction in interfacial resistance. It was found that duplex tubes had reduced the interfacial resistance by 75%, when compared to a uniformly dense electrolyte. Sodium silicide was characterized using various methods to better understand the phase and the Na-Si phase diagram. EMF experiments using Na+ BASE tubes was used to determine the activity in the silicon rich region of the phase diagram, which showed a sodium activity of 0.5 at 550 °C. TGA/DSC was used to determine phase transformation temperatures, as well as the heat of formation for NaSi, which was recorded to be below 1 kJ mol -1. iv A sol-gel precipitation method was used to produce fine BiMn 2O5 powders used for supercapacitors. The powders resulting from a consistent method were tested for pseudocapacitance using bulk and thin film electrodes. Bulk electrodes had a gravimetric capacitance of 10 F g -1, while thin film electrodes only reached 2.6 F g -1. Lithium ion battery anode (Li 4Ti 5O12 ) and cathode (LiFePO 4, LiMn 2O4, LiMn 1.5 Ni 0.5 O4) materials were electrophoretically deposited with the assistance of PAZO-Na and CMC- Na. Cathodes were successfully deposited on aluminium substrates, and were tested in the -1 potential window 2 – 4.3 V. The LiFePO 4 cathodes showed capacity of 146.7 mAh g at C/10, while showing capacity retention of 103% after 50 cycles. v Acknowledgements As I begin the next steps in my career, I must look back to the past six years here at McMaster University. They were filled with many trials, from the personal to the professional. There were many victories, and many more disappointing failures. If it wasn’t for the people who have supported and encouraged me, pursuing my PhD would have remained an unreachable dream. I would like to thank you all from the bottom of my heart. Dr Anthony Petric, thank you for the dedication and support you provided me over the years. Throughout these six long years, you have given me the guidance to grow as an aspiring researcher, to one that is better prepared to tackle all aspects of a life dedicated to science. Thank you for placing your trust in my abilities, and for not giving up on me. I wish you the best of retirements. I would like to thank Dr Igor Zhitomirsky for accepting me into his lab when I branched out to find new projects. You and your group accepted me with the warmest hearts. For too long I had worked alone, and finding camaraderie with your students not only gave me the drive to finish my thesis, but general hope in the next generation of scientists. I would like to thank Dr Gillian Goward for putting the time and effort of being part of my supervisory committee. Your participation in my yearly meetings and examinations was crucial in refining my abilities and thought processes. vi I appreciate the various members of the university who I have encountered and worked with. I appreciate the help and advice given by Dr Alex Adronov, Dr James Britten, Doug Culley, Frank Gibbs, Victoria Jarvis, Xiaogang Li, Ed McCaffrey, and to all my fellow graduate students. Special thanks go to Dr Joey Kish, Dr Dmitri Malakhov, and Dr Hatem Zurob for the invaluable advice throughout my final years at McMaster. I would also like to thank Jim Garrett. You have provided me invaluable insight from the endless knowledge you have accumulated. There is no one with whom I would have rather worked alongside. I only wished that I could have learned more from you. To my family, thank you for cheering me on from afar. Your expectations and hopes for me helped me push through the clutter of life and find what was important for me. Most importantly, I must express my love and gratitude to my wife, Chiao-Ting Shen. You stood by me through all the years of hard work, frustration, and disappointments. When all seemed to crumble, you were the rock that I held onto as we weathered the roughest storms. I am excited to continue our journey through life together, into a brighter and thrilling future. I can only hope to now make your dreams come true. vii Table of Contents Lay Abstract ....................................................................................................................... iii Abstract .............................................................................................................................. iv Acknowledgements ............................................................................................................ vi Table of Contents ............................................................................................................. viii List of Figures ................................................................................................................... xii List of Tables .................................................................................................................. xviii List of Abbreviations and Symbols .................................................................................. xix Abbreviations ........................................................................................................... xix Symbols ..................................................................................................................... xx Declaration of Academic Achievement .......................................................................... xxii Chapter 1: Introduction ....................................................................................................... 1 Chapter 2: Literature Review .............................................................................................. 4 High Temperature Molten Sodium-Anode Batteries ...................................................... 4 Beta-Alumina Solid Electrolyte [BASE] .................................................................... 4 Ionic Conductivity in BASE ................................................................................... 6 Ion Exchange in BASE ........................................................................................... 9 BASE Synthesis & Production .............................................................................. 11 Sodium Sulfur Cell .................................................................................................... 13 Sodium Metal Halide Cell ......................................................................................... 17 Planar Cells ............................................................................................................... 20 Lithium Ion Batteries..................................................................................................... 22 Cathode Materials ..................................................................................................... 23 Intercalation Cathodes ........................................................................................... 24 Conversion Cathodes ............................................................................................. 25 Anode Materials ........................................................................................................ 27 Carbon-Based Anodes ........................................................................................... 27 Lithium Titanate