[Thesis Title Goes Here]

DETERMINISTICALLY ENGINEERED, HIGH POWER DENSITY ENERGY STORAGE DEVICES ENABLED BY MEMS TECHNOLOGIES A Dissertation Presented to The Academic Faculty by Andac Armutlulu In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Chemical and Biomolecular Engineering Georgia Institute of Technology December 2014 COPYRIGHT 2014 BY ANDAC ARMUTLULU DETERMINISTICALLY ENGINEERED, HIGH POWER DENSITY ENERGY STORAGE DEVICES ENABLED BY MEMS TECHNOLOGIES Approved by: Dr. Sue Ann Bidstrup Allen, Advisor Dr. Tom Fuller School of Chemical and Biomolecular School of Chemical and Biomolecular Engineering Engineering Georgia Institute of Technology Georgia Institute of Technology Dr. Mark G. Allen, Advisor Dr. Hang Lu School of Electrical and Computer School of Chemical and Biomolecular Engineering Engineering Georgia Institute of Technology Georgia Institute of Technology Dr. Dennis Hess Dr. Meilin Liu School of Chemical and Biomolecular School of Materials Science and Engineering Engineering Georgia Institute of Technology Georgia Institute of Technology Date Approved: August 11, 2014 Anne ve babama… ACKNOWLEDGEMENTS First and foremost, I would like to thank my advisors, Dr. Sue Ann Bidstrup Allen and Dr. Mark G. Allen, for their continuous guidance, advice, and support over the course of my PhD studies, and for accepting me as their academic child. I was very fortunate to have Dr. Dennis Hess, Dr. Tom Fuller, Dr. Hang Lu, and Dr. Meilin Liu as my committee members, whom I confidently consider to be the best in their respective fields, and who have been an academic inspiration to me throughout these years. As well, I must acknowledge my unofficial academic advisor Dr. Lawrence Bottomley for treating me like his own student and providing me with both technical and non-technical support whenever needed. Many thanks go to both previous and current members of the MSMA group, with whom I have had the honor to work alongside. In particular: Richard Shafer, for making the lab run smoothly; Dr. Seong-Hyok Kim, for his excellent mentorship; Dr. Preston Galle, for his endless support; and Purnima Sharma, for all the administrative support. I would like to present my sincere gratitude and appreciation to Dr. Turkan Haliloglu and Dr. Oner Hortacsu for their guidance and for making this long but rewarding PhD journey possible for me. I am grateful to Dr. Seda Keskin Avci, Dr. Emmanuel Haldoupis, and Dr. Sung Gu Kang for helping me get started with my PhD adventure. I am also appreciative of my Italiano friends Alessio, Andrea, and Gabriele for making me feel home in this far-away continent; and my dearest study group members Carine, Christine, Deepraj, Jose, Nitesh, and Wilmarie. Last but not least, I owe a special debt of gratitude to my beloved parents, in particular my father, Dr. Ismail Hakki Armutlulu, for their endless love and unconditional support from as far back as I can remember. iv TABLE OF CONTENTS Page ACKNOWLEDGEMENTS iv LIST OF TABLES viii LIST OF FIGURES x SUMMARY xix CHAPTER 1 INTRODUCTION 1 1.1 Motivation 1 1.2 Selection of the Appropriate Energy Storage System 2 1.3 Fundamental Principles and Design Considerations 3 1.4 Structures Designed for High-Power Applications from the Literature 9 1.5 Contributions of This Work 16 1.6 Thesis Outline 17 1.7 References 20 2 DESIGN AND FABRICATION OF MEMS-ENABLED MULTILAYER STRUCTURES 23 2.1 Sequential Multilayer Deposition 23 2.2 Mold Preparation 50 2.3 Etching of the Sacrificial Layers 60 2.4 Surface Area Characterization 67 2.5 References 70 3 ZINC-AIR MICROBATTERIES 74 3.1 Background and Motivation 74 v 3.2 Fabrication Process 77 3.3 Performance Characterization of the Microbatteries 92 3.4 Conclusions 97 3.5 References 99 4 NICKEL HYDROXIDE-BASED ELECTRODES 101 4.1 Background and Motivation 101 4.2 Design and Modeling of the Electrodes 102 4.3 Fabrication of the Multilayer Current Collector 117 4.4 Synthesis of Ni(OH)2 130 4.5 Performance Characterization of the Electrodes 142 4.6 Modeling of the Fabricated Electrodes 157 4.7 Performance Projections Using the Models 160 4.8 Conclusions 164 4.9 References 168 5 ELECTRODES FOR LITHIUM-ION BATTERIES 173 5.1 Background and Motivation 173 5.2 Choice of Materials 176 5.3 Fabrication of the Electrodes 182 5.4 Design and Modeling of the Electrodes 187 5.5 Performance Characterization of the Electrodes 205 5.6 Modeling of the Fabricated Electrodes 211 5.7 Conclusions 212 5.8 References 216 6 MEMS-ENABLED ELECTROCHEMICAL CAPACITORS 219 6.1 Background and Motivation 219 vi 6.2 NiO- and Ni(OH)2-based Electrodes 227 6.3 Fabrication of the Electrodes 231 6.4 Performance Characterization of the Electrodes 251 6.5 Conclusions 259 6.6 References 262 7 CONCLUSIONS AND FUTURE WORK 267 7.1 Summary and Conclusions 267 7.2 Suggestions for Future Work 270 7.3 References 281 APPENDIX A: MATLAB CODES 282 VITA 285 vii LIST OF TABLES Page Table 1.1: Ionic conductivities of various commonly used electrolytes in batteries 5 Table 1.2: Common electrode materials used in batteries along with their ionic diffusivities and electronic conductivities 6 Table 2.1: Compositions of the Ni and Cu plating baths 28 Table 2.2: Comparison of various polymer pairs used in the fabrication of multilayer structures 37 Table 2.3: The specifications for the laser used in the ablation process 41 Table 2.4: Plasma specifications for the removal of the sacrificial polymer layers 44 Table 3.1: The composition of Cu immersion and Zn electroplating baths 79 + Table 4.1: Concentration profiles of H within the Ni(OH)2 active material as a function of time at various thicknesses 107 Table 4.2: Concentration profiles of the OH- ions in the electrolyte located inside the channels with a width of 300 µm 113 Table 4.3: Modeling results for various channel dimensions 114 Table 4.4: Comparison of the electrodeposition methods for Ni(OH)2/NiOOH 137 Table 5.1: The composition of the NiSn electroplating bath 186 Table 5.2: Concentration profiles of Li within the NiSn active material as a function of time at various thicknesses 192 Table 5.3: Concentration profiles of the Li ions in the electrolyte located inside the channels 197 Table 5.4: Impact of the width between the etching holes (i.e., L) on the other dimensions and capacity of the multilayer electrode with a total thickness of 300 viii μm 200 Table 6.1: Selected types of materials for electrochemical capacitors 224 Table 6.2: Performance of various Ni(OH)2-based electrochemical capacitors 229 Table 6.3: Performance comparison of various NiO-based electrochemical capacitors 230 ix LIST OF FIGURES Page Figure 1.1: Simplified Ragone plot showing the specific power vs. specific energy of various energy storage systems 3 Figure 1.2: Demonstration of the kinetics and transport phenomena within three main components of a conventional battery electrode 4 Figure 1.3: Cu pillars fabricated through Al2O3 templates 11 Figure 1.4: Schematic of the assembly of Si-coated carbon black particles into spherical granules 12 Figure 1.5: Schematic describing morphological changes in Si after electrochemical cycling 14 Figure 1.6: High-power electrodes enabled by inverted opal structures 16 Figure 2.1: Comparison of lateral and vertical high-aspect-ratio structures 24 Figure 2.2: Conceptual rendering of the robotically-assisted sequential electroplating setup for the fabrication of the metallic multilayer structures 26 Figure 2.3: Multilayer Ni structures following the removal of Cu layers 29 Figure 2.4: Fabrication sequence for the partially-etched multilayer structures 33 Figure 2.5: Fabrication sequence for the anchor-supported structures 34 Figure 2.6: Fabrication sequence for the anchor-supported multilayer polymer structures 36 Figure 2.7: Fabrication sequence for the partially etched multilayer polymer structures 37 Figure 2.8: SEM images of the multilayer polymer structures based on 3 pairs of Unity/POSS 38 x Figure 2.9: Optical and SEM images of the polymer-based multilayer structure with 3 pairs of Avatrel/POSS layers 42 Figure 2.10: POSS layers following the thermal removal of Avatrel at 405 oC 43 Figure 2.11: Optical images showing the top view of the high-density array of holes enabled by laser ablation 45 Figure 2.12: SEM images of the multilayer POSS/Avatrel structures following partial plasma etching of Avatrel layers 46 Figure 2.13: Fabrication scheme for the vertical high-aspect-ratio structures 49 Figure 2.14: SEM images of the partially etched SU-8 mold and multilayer Ni/Cu structure following partial etching of the Cu layers 53 Figure 2.15: Schematic illustration of removal of SU-8 molds with the help of a strong adhesive tape 54 Figure 2.16: Conceptual rendering of the SU-8 removal process via boiling water 54 Figure 2.17: Optical images showing the top view of the AZ molds in the form of varying number of cylindrical pillars all built on a footprint of 1 cm2 56 Figure 2.18: Optical images showing the top view of the AZ molds in the form of varying number of rectangular pillars all built on a footprint of 1 cm2 57 Figure 2.19: Thick AZ mold with rectangular pillar array 58 Figure 2.20: Thick AZ mold with cylindrical pillar array 59 Figure 2.21: Uneven etching distribution across the multilayer structures due to the accumulation of the higher-density etch products on the bottom 61 Figure 2.22: Illustration of the PMMA platforms used for the Cu etching 62 Figure 2.23: Optical images showing the backside of the Cu/Ni-coated glass substrate following various durations of Cu etching 64 Figure 2.24: Potentiodynamic

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