INVESTIGATION OF SILICON ANODE FOR LITHIUM ION BATTERIES OMAMPULIYUR SWAMINATHAN RAJAMOULY (M Eng., MIT; B Eng (Hons.), NUS) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILIOSOPHY IN ADVANCED MATERIALS FOR MICRO‐ AND NANO- SYSTEMS (AMM&NS) SINGAPORE‐MIT ALLIANCE NATIONAL UNIVERSITY OF SINGAPORE 2013 i 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 have been used in the thesis This thesis has also not been submitted for any degree in any university previously Omampuliyur Swaminathan Rajamouly 17 January 2013 ii Acknowledgements This project would not have been feasible without the guidance, support and encouragement of many people I express my heartfelt gratitude to Prof Choi (SMA, NUS) for his invaluable guidance, unflinching encouragement and constant belief in me The weekly meetings with Prof Choi were crucial for me to be constantly cognizant of the project objectives and it helped me through many a lean patch Prof Fitzgerald (SMA, MIT) has been a great inspirational figure and was the main reason for me to embark upon the anode investigation project, for which I thank him earnestly Prof Thompson (SMA, MIT) has helped me greatly by guiding me through several critical twists and turns of the project and I thank him sincerely Prof Lu (NUS) allowed me to use his laboratory facilities for half-cell assembly and I am greatly indebted to him Prof Thong’s (NUS) lab was of indispensable value for my SEM and EDX analyses and I am very thankful to him Prof Shao-Horn (MIT) helped me gain important electrochemical insights with respect to the project and I genuinely thank her I would like to thank Koo Chee Keong for his help with numerous SEM and EDX analyses This project wouldn’t have become a reality without the help of Xia Hui and Zhu Jing in assembling several half-cells, almost every week Maruf has been of great help in this project and aided me with many an explorative discussion, and I am immensely thankful to him I am very much indebted to Mohammed Khalid and Zheng Han for all their help in the Glancing Angle Deposition of gold I am sincerely thankful to Zheng Fei, iii Tze Haw and Yun Jia; my senior laboratory mates for bringing me up to speed with respect to all the operating procedures of laboratory equipment I am also very thankful to Lim Walter (lab officer), Hong Yanling (SMA) and Juliana (SMA) for all the help during this project Over the course of this project my laboratory mates: Yudi, Ria, Zongbin, Cheng He, Changquan, Bihan, Zhu Mei, Thi and Jia Xin have helped one way or the other and I thank them all I would also like to thank Lin Thu and Wang Kai for all their help and wish them the very best in their projects I am greatly indebted to all my friends for their support and encouragement over the course of this project I thank my friend Krishandan for helping me with the thankless and frustrating task of proof-reading my thesis The ever growing fountain of scientific knowledge has only been made possible by the ardent works of earlier intellectual stalwarts and was succinctly expressed by Isaac Newton in : “If I have seen further, it is by standing on the shoulders of giants” I would like to take this opportunity to express my boundless gratitude to all the researchers whose works have been the basis and inspiration for my work “Parents, Teachers and only then god” has been a timeless Indian adage, which underscores the importance of parents in our lives I owe my existence and all my opportunities to my kind and loving parents My parents have given me infinite support and immense encouragement over the course of iv my life and this research project Though words cannot express the gratitude I feel for them, I try and sincerely thank them for all the help, support and love v Table of Contents Acknowledgements ii Summary x List of Tables .xii List of Figures xiii List of Acronyms xx Chapter Introduction 1.1 Background 1.2 Motivation 1.3 Organization of Thesis Chapter Literature Review 2.1 Introduction 2.2 Battery 2.2.1 Primary Batteries 2.2.2 Secondary Batteries 2.2.3 Lithium-ion Battery 10 2.3 Electrolytes for LIB 15 2.4 Cathodes for LIB 17 2.5 Anodes for LIB 18 2.5.1 Intercalation and de-intercalation 19 vi 2.5.2 Conversion Reaction 20 2.5.3 Alloying and de-alloying 20 2.6 Silicon Anode 25 2.6.1 Si powder anodes 27 2.6.2 Si dispersed in inactive or active matrix 28 2.6.3 Si thin films 30 2.6.4 Si nanostructures 33 2.7 Solid Electrolyte Interface (SEI) layer 38 2.8 Nanofabrication 40 2.8.1 Metal Assisted Chemical Etching 41 2.8.2 Glancing Angle Deposition 43 2.8.3 Laser Interference Lithography 44 2.9 Summary 47 Chapter Experimental Details 49 3.1 Introduction 49 3.2 Nanoporous and nanopillar Si 49 3.3 Stainless Steel substrate preparation 52 3.4 Silicon Sputtering 55 3.5 BHF Cleaning 59 3.6 Glancing Angle Deposition of Gold 60 vii 3.7 MACE for nanoporous Si 62 3.8 Laser Interference Lithography for Nanopillars 64 3.8.1 Photo Resist Coating 64 3.8.2 Llyod’s mirror setup, exposure and development 65 3.8.3 O2 Plasma 68 3.9 Thermal Deposition of Gold 69 3.10 MACE for nanopillar Si 70 3.11 Thin-film thickness measurement 71 3.12 Weight measurement 72 3.13 Scanning Electron Microscopy 73 3.14 Energy Dispersive X-ray Spectroscopy 75 3.15 Half-cell assembly and testing 75 Chapter Silicon - Thin film 81 4.1 Introduction 81 4.2 Effect of Si thin film thickness 81 4.3 Effect of RF sputtering power 84 4.3.1 EDX analysis 86 4.3.2 Voltage profile and differential capacity 87 4.3.3 Thermodynamic calculations 90 4.4 Effect of oxygen incorporation on cycling performance 92 viii 4.5 Summary 94 Chapter Nanoporous Si 96 5.1 Introduction 96 5.2 Residual film 96 5.3 Native Oxide Layer 99 5.4 Charging rate vs capacity 102 5.5 Effect of nanoporous Si thickness 104 5.6 750 nm nanoporous Si – 50 cycles 110 5.7 Summary 111 Chapter Nanopillar Si 113 6.1 Introduction 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Li-ion Microbatteries”, Submitted for publication Rajamouly S Omampuliyur, Maruf Bhuiyan, Zheng Hang, Zhi Jing, Xia Hui, Lu Li, Eugene A Fitzgerald and Wee Kiong Choi, “Investigation of thin film and nano-patterned amorphous Silicon as anode for Lithium Ion battery”, presented at MRS Spring Meeting 2012 Rajamouly S Omampuliyur, “Investigation of amorpous silicon as an anode material for Lithium-ion batteries”, SMA – AMM&NS symposium 2011 ... debilitating volume expansion during lithiation 2.6 Silicon Anode Silicon was electrochemically investigated to explore the possibility of using Si as an anode replacement for Li- metal (due to Li- metal’s... the formation of Li2 2Si5 alloy) during lithiation prevents good cycling performance of Si anodes To mitigate the problem associated with volume expansion of the Si anode on lithiation, many approaches... Conversion Reaction Binary metal oxides store Li via a conversion reaction with the formation and decomposition of Li2 O as shown in Eq (2.4) [74], lithiation  MO  2Li   2e  Li2 O