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UNIVERSITY of CALIFORNIA, IRVINE Ion Transport Phenomena UNIVERSITY OF CALIFORNIA, IRVINE Ion Transport Phenomena at the Nanoscale in Different Model Battery Systems DISSERTATION submitted in partial satisfaction of the requirements for the degree of DOCTOR OF PHILOSOPHY in Physics by Timothy Stephen Plett Dissertation Committee: Professor Zuzanna S. Siwy, Chair Professor Phil Collins Professor Reginald M. Penner 2017 Figures and text from T. S. Plett, T. Gamble, E. Gillette, S. B. Lee and Z. S. Siwy, Ionic conductivity of a single porous MnO2 mesorod at controlled oxidation states, J. Mater. Chem. A, © 2015, vol. 3, pg. 12858–12863 DOI: 10.1039/C5TA03196F were reproduced and adapted by permission of The Royal Society of Chemistry Figures and text from Plett, T. S.; Shi, W.; Zeng, Y.; Mann, W.; Vlassiouk, I.; Baker, L. A.; Siwy, Z. S. “Rectification of Nanopores in Aprotic Solvents – Transport Properties of Nanopores with Surface Dipoles”, Nanoscale © 2015, vol. 7, pg. 19080–19091, DOI: 10.1039/C5NR06340J were reproduced and adapted by permission of The Royal Society of Chemistry Figures and text from T.S. Plett, W. Cai, M. Le Thai, I. Vlassiouk, R.M. Penner, and Z.S. Siwy, Solid-State Ionic Diodes D2017, 121 (11), pp. 6170-6176, DOI: 10.1021/acsjpcc.7b00258 were reproduced by permission of the American Chemical Society. This is an unofficial adaptation of an article that appeared in an ACS publication. ACS has not endorsed the content of this adaptation or the context of its use. Reprinted Figure 1.1a with permission from M.R. Powell, I. Vlassiouk, C. Martens, Z.S. Siwy, “Non-equilibrium 1/f noise in rectifying nanopores,” Physical Review Letters, vol. 103, pp. 248104 (1-4) (2009) © 2009 by the American Physical Society. Figures reproduced from W. Mann, “USING ION CURRENT TO PROBE NANOSTRUCTURED BATTERY MATERIALS IN DIFFERENT OXIDATION STATES,” CSU LB, (August 2016) © 2016 with permission from W. Mann and Proquest LLC. © 2017 Timothy Stephen Plett DEDICATION For Mike Oberle (1960-2015) My first physics teacher to whom I am forever grateful ii TABLE OF CONTENTS Page LIST OF FIGURES v LIST OF TABLES vii ACKNOWLEDGMENTS viii CURRICULUM VITAE xi ABSTRACT OF THE DISSERTATION xiii INTRODUCTION 1 CHAPTER 1: The Effect of Surface Dipoles and Organic Electrolytes on 4 Nanopore Systems --Nanopore Fabrication and Characterization 7 --Aqueous LiClO4 Contrasted with LiClO4 in Propylene Carbonate 10 --Possible Mechanisms for Rectification in Propylene Carbonate 14 --Probing Possible Dipole Adsorption with I-V Curves and SICM 18 --Confirmation from Modeling and Conclusions 25 CHAPTER 2: Solid-State Ionic Diodes in Conical Nanopores with LiClO4-doped 28 PMMA Gel Electrolyte --Preparing and Testing PMMA Gels and Nanopore Samples 29 --LiClO4-PMMA Ion Transport Experiments in Cylindrical Nanopores 31 --Solid State Diodes in Conical Nanopores with LiClO4-PMMA Gel 33 --Modeling Space Charge to Understand PMMA Gel Rectification 37 CHAPTER 3: Nanopores in Compatible LiClO4-PMMA Gel and LiClO4-PC Liquid 41 Electrolyte System Gel-Liquid Hybrid Nanopore System --Gel-liquid systems in cylindrical nanopores 43 --Gel-liquid experiments in conical nanopores 51 --Modeling the gel-liquid system: competing mechanisms 56 --Discussion of findings 58 CHAPTER 4: Ion Transport for Manganese Oxide at Different Oxidation States 60 --Nanopore template preparation 61 --Template deposition and confirmation by SEM, CV, and I-V scans 65 --Probing oxidation change of MnO2 in aqueous electrolyte 70 --Probing MnO2 in non-aqueous electrolyte in multipore systems 76 --Probing MnO2 in non-aqueous electrolyte in single pore-rod systems and conclusions 81 iii CHAPTER 5: Summary and Conclusions 84 REFERENCES (OR BIBLIOGRAPHY) 87 APPENDIX A: Transmembrane Voltage Test on varying MnO2 Rod Length 99 iv LIST OF FIGURES Page Figure 1.1 Conical Pore Schematic and Rectification 5 Figure 1.2 Membrane Etching Schematic 9 Figure 1.3 Conical nanopore sizing I-V scan 10 Figure 1.4 Rectification of Aqueous Solutions in Polycarbonate 11 Figure 1.5 Rectification of LiClO4-PC in Polycarbonate and PET 13 Figure 1.6 Rectification of LiClO4-PC in Glass Nanopipettes 14 Figure 1.7 Comparison of Cations in PC 15 Figure 1.8 Surface Charge Probe with H2O in PC 19 Figure 1.9 Rectification of Organic Solvents with Different Dipole Moment 21 Figure 1.10 Scanning Ion Conductance Microscopy and Schematic 24 Figure 1.11 Comsol Modeling of Dipole Rectification 26 Figure 2.1 Experimental Set-Up for Gel-Electrolyte 30 Figure 2.2 LiClO4-PMMA in Cylindrical Nanopores 31 Figure 2.3 Blank PMMA in Cylindrical Nanopores 32 Figure 2.4 Demonstration of LiClO4-PMMA Conical Nanopore Diode 34 Figure 2.5 Fast-Switching in Solid-State Ionic Diode 35 Figure 2.6 LiClO4-PMMA in Conical Nanopores at Different Concentrations 36 Figure 2.7 Comsol Modeling of Space Charge Rectification 40 Figure 3.1 Immersed Gel Experimental Set-up 43 Figure 3.2 Photographs of LiClO4-PMMA Gel before and after LiClO4-PC 44 Figure 3.3 I-V Scans of gel deposited cylindrical samples 46 Figure 3.4 Conductivity summary of cylindrical samples 47 v Figure 3.5 Rectification in cylindrical samples with one-sided gel deposition 48 Figure 3.6 GLI experimental results in cylindrical samples 50 Figure 3.7 Rectification effects of gel orientation in conical pores 52 Figure 3.8 Conductivity comparisons in gel conical pore samples 54 Figure 3.9 GLI experimental results in conical samples 54 Figure 3.10 COMSOL modeling of gel-liquid system 56 Figure 4.1 Geometric system for solid-angle scattering 62 Figure 4.2 Geometry of particle scattering into a cylinder 63 Figure 4.3 Plots of gold thickness inside a nanopore 65 Figure 4.4 Schematic and photograph of deposition apparatus 66 Figure 4.5 Cyclic voltammetry of multipore samples 67 Figure 4.6 SEM images of electrodeposited MnO2 rods 67 Figure 4.7 I-V data of MnO2 rod before lithium insertion 69 Figure 4.8 Photographs of I-V and CV set-ups in conductivity cells 70 Figure 4.9 Multipore MnO2 summary resistance data 71 Figure 4.10 Lithiated and Delithiated MnO2 I-V data 73 Figure 4.11 Ion current saturation in MnO2 nanorods 74 Figure 4.12 Reversal potential measurement set-up 75 Figure 4.13 Multipore MnO2 samples in LiClO4-PC electrolyte 77 Figure 4.14 Multipore MnO2 experiments with transmembrane voltage 79 Figure 4.15 Summary resistance calculations in multipore MnO2 samples 80 Figure 4.16 Single pore MnO2 samples in LiClO4-PC electrolyte 81 Figure A.1 MnO2 Rod Length and Transmembrane Voltage Response 97 vi LIST OF TABLES Page Table 1.1 Dipole Effective Surface Charge Calculations 22 Table 4.1 Au film thickness calculations at various depths 64 Table 4.2 Reversal potential measurements 75 vii ACKNOWLEDGMENTS I am grateful for the opportunity to express my heartfelt thanks to those who were integral to my journey toward this moment. Firstly, to my committee chair and advisor, Professor Zuzanna Siwy, I offer my thanks. As an advisor, she has been the embodiment of encouragement, patience, and charity. At a moment when I was most undeserving, she gave me an opportunity to work alongside one of her students, Dr. Trevor Gamble. Neither of us knew that decision would lead us to today and I am blessed to have had her guidance, perseverance, and academic insight influence my journey in research. Indeed, without her support, it is unlikely I would have completed this program with the level of success we achieved together or even at all. I would also like to acknowledge Dr. Trevor Gamble, who went before me in this research and from whom I inherited technique and attitude in approaching research. His patience with me in the beginning and his willingness to endure my growing pains was crucial to my development as a researcher. He also gave me courage to step into leadership roles at NEES where he and I both served as student coordinators for a time, an experience which shall prove valuable after leaving grad school. To my committee members, Professor Phil Collins and Professor Reginald M. Penner, I express gratitude for challenging me to be precise in language and clear in procedure. Their regular input and perspectives on my work opened doors to new insights and opportunities and highlighted the value of academic collaboration. I also would like to thank fellow student researchers and post-docs, both current and former, both in the Siwy Group and those who participated in NEES. To those who have gone before, Dr. Laura Innes, Dr. Steve Buchsbaum, Dr. Mya Le Thai, Dr. Eleanor Gillette, Jill Pestana, Dr. Alexander Kozen, Dr. Tetyana Ignatova, Dr. Girija Chandran, William Mann, Wenjia (Josslyn) Cai: I offer my appreciation as you each have served as comrades-in-arms or mentors to me in pursuit of scientific knowledge, offering advice and perspective from a position I have now come to understand. To those who are with me now, Crystal Yang, Preston Hinkle, Dr. Yinghua Qiu, Gaurav Jha, Dr. Mina Abad, James Boyd, Juliette Experton, Jonathon Larson: my thanks in helping me endure and persevere to the end. As others involved in the daily challenges, struggles, and triumphs of research, your camaraderie has been a strength to lean on. Additionally, I acknowledge the researchers at the Energy Frontier Research Center – Nanostructures for Electrical Energy Storage (NEES). Specifically, I would like to offer thanks to Dr. Gary Rubloff of UMD, Dr. Sang-Bok Lee of UMD, and Dr. Kevin Leung of Sandia National Labs, each of whom I have collaborated with on projects. I also would like to thank Dr. Elizabeth Lathrop who has been an effective liaison and source of help and insight in terms of student development and organization. Additionally, I offer thanks to the Thrust 1 PIs for their comments and support, especially Dr.
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