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Design and Controlled Synthesis of Complex Metal Oxide Nanostructures and Study of Their Advanced Energy Applications

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Design and Controlled Synthesis of Complex Metal Oxide Nanostructures and Study of Their Advanced Energy Applications Design and controlled synthesis of complex metal oxide nanostructures and study of their advanced energy applications Dissertation Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Mingzhe Yu Graduate Program in Chemistry The Ohio State University 2015 Dissertation Committee: Dr. Yiying Wu, Advisor Dr. Patrick Woodward Dr. Anne Co Copyright by Mingzhe Yu 2015 Abstract Nano-structured metal oxides are of significance for fundamental science and practical applications because of their widely tunable physiochemical properties and excellent stability under various conditions. The synthetic chemistry of metal oxide nanostructures with controlled properties and innovation of their device applications are two interesting and crucial topics towards large-scale industrial production and commercialization. The focus of this dissertation is on the design and controlled synthesis of wide-bandgap metal oxide semiconductor nanostructures and study of their device applications for electrocatalysis and photocatalysis. The controlled hydrothermal synthesis of p-type copper-based delafossite compounds (e.g. CuGaO2) and n-type titanium oxide (i.e., TiO2) on substrates are systematically studied. Their structural, chemical and optical properties are characterized via X-ray diffraction, electron microscopy, photoelectron spectroscopy and diffuse-reflectance spectroscopy. The obtained CuGaO2 and TiO2 nanostructures have been applied as semiconductor electrodes in p-type dye-sensitized solar cells, lithium-air and lithium-iodine solar batteries. A combination of absorption spectroscopy, electro-analytical techniques and photoelectrochemical methods are employed to evaluate the materials’ electrochemical and electronic performance within different device configurations. Obtaining delafossite CuGaO2 nanoparticles is challenging but desirable for high- surface area device applications such as dye-sensitization and trace gas detection. The ii phase formation and crystal growth mechanism of delafossite CuGaO2 under low- temperature hydrothermal conditions are studied. The stabilization of CuI cations in aqueous solution and the controlling of the hydrolysis of GaIII species are found to be the two crucial factors that determine the phase formation. The oriented attachment (OA) growth is proposed as the crystal growth mechanism to explain the formation of large CuGaO2 nanoplates. Delafossite CuGaO2 nanoparticles on a 20 nm-size have been successfully synthesized for the first time. The synthesized light-colored CuGaO2 is applied as photocathodes in p-type dye-sensitized solar cells for the first time and presents significantly higher photovoltage compared to conventional NiO-based solar cells. Under 1 Sun AM 1.5 illumination, a Voc of 357 mV has been achieved, which is among the highest values that have been reported for p-DSSCs. Well-aligned TiO2 nanorods on stainless steel and titanium substrates and nano- particles are synthesized through the hydrothermal process under controlled acidic conditions. The dye-sensitized TiO2 nano-structures have been applied as photoelectrodes in solar-powered electrochemical energy storage devices (i.e., solar batteries), for the simultaneous conversion and storage of solar energy. The solar battery integrates a photo-electrochemical cell and an electrochemical cell into a single device and is able to harvest solar energy and store it in-situ within the device via a photocharging process and distribute the energy as electric power when needed. A lithium-oxygen (Li-O2) solar battery is demonstrated with a dye-sensitized TiO2 photoelectrode. A triiodide/iodide redox shuttle is used to couple a built-in nano- structured photoelectrode with the oxygen air electrode for the photo-assisted charging of a Li-O2 battery. On charging under illumination, triiodide ions are generated on the iii photoelectrode, and subsequently oxidize Li2O2. Because of the contribution of the photovoltage, a “negative” charging overpotential appears. The introduction of the TiO2 photoelectrode here offers a novel strategy to address the overpotential issue of current non-aqueous Li-O2 batteries. Another lithium-iodine (Li-I) solar flow battery (SFB) has also been constructed with integrating the TiO2 semiconductor photoelectrode with a Li-I redox battery. During the photo-assisted charging process, I- ions are - photoelectrochemically oxidized to I3 , harvesting solar energy and storing it as chemical energy. The Li-I SFB can be charged at a voltage of 2.90 V under 1 sun AM 1.5 illumination, which is lower than its discharging voltage of 3.30 V. The charging voltage reduction translates to energy savings of close to 20% compared to conventional Li-I batteries. iv Acknowledgements The work presented here would have never been accomplished without those who have been helping me all the time. I would like to express my deepest appreciation to all of them. Dr. Yiying Wu, my adviser, has been a wonderful mentor, always motivating me to explore more and further towards the beauty of chemistry. Thank you for everything you have taught me in chemistry and beyond. Thank you for all the encouragement and inspiration, and all the support in my research and in real life! Many thanks to Dr. Anne Co and Dr. Patrick Woodward - my thesis committee members and professors - they have taught me a lot in electrochemistry and solid-state chemistry. They are always patient and supportive whenever I need help. I also appreciate Dr. Claudia Turro, the Department Vicechair, Dr. Shiekh Akbar from the Materials Science and Engineering Department and Dr. Khalil Amine from Argonne National Lab, for their support and endorsement for my fellowship and new position applications. I thank everyone in Wu Lab for being awesome labmates and helpful fellows. Dr. Zhiqiang Ji and Dr. Gayatri Natu taught me and helped a lot when I joined the group and started my research. Zhongjie Huang, Lu Ma, Xiaodi Ren, Tom Draskovic and Billy v McCulloch have been collaborating with me on various projects. It is not possible to finish my projects without their inputs and contributions. Many thanks to my friends here at Ohio State, and also those who scatter everywhere on the earth. They always cheer me up and cool me down at the moment I need it. Especially, I should thank my old friend, Chen Chen, for all the editing and revision she has done for many of my manuscripts. Thank you my dear family, my grandfather, my father and mother, and Jie, for your love and care. vi Vita Sep. 2006 to Jul. 2010 …B.Sc. with Honors, Physical Science; B.Sc., Materials Chemistry University of Science and Technology of China (USTC), China Publications of graduate study 1. M. Yu, G. Natu, Z. Ji & Y. Wu; “P-type Dye-sensitized Solar Cells based on Delafossite CuGaO2 Nanoplates with Saturation Photovoltages Exceeding 460 mV”, The Journal of Physical Chemistry Letters, 2012, 3, 1074 2. Z. Huang, G. Natu, Z. Ji, M. He, M. Yu & Y. Wu; “Probing the Low Fill Factor of NiO p-Type Dye-Sensitized Solar Cells”, The Journal of Physical Chemistry C, 2012, 116, 26239 3. J. Ahmed, C.K. Blakely, J. Prakash, S.R. Bruno, M. Yu, Y. Wu & V. V. Poltavets; “Scalable Synthesis of Delafossite CuAlO2 Nanoparticles for P-type Dye-sensitized Solar Cells Applications”, Journal of Alloys and Compounds, 2014, 591, 275 4. M. Yu, T. Draskovic & Y. Wu; “Cu (I)-based Delafossite Compounds as Photocathodes in p-type Dye-Sensitized Solar Cells”, Physical Chemistry Chemical Physics, 2014, 16, 5026 5. L. Ma, D. N. Nath, E. W. Lee II, C. H. Lee, M. Yu, A. Arehart, S. Rajan & Y. Wu; “Epitaxial Growth of Large Area Single-Crystalline Few-Layer MoS2 with Room Temperature Mobility of 192 cm2V-1s-1”, Applied Physics Letters, 2014, 105, 072105 vii 6. M. Yu, T. Draskovic & Y. Wu; “Understanding the Crystallization Mechanism of Delafossite CuGaO2 for Controlled Hydrothermal Synthesis of Nanoparticles and Nanoplates”, Inorganic Chemistry, 2014, 53, 5845 7. M. Yu, X. Ren, L. Ma & Y. Wu; “Integrating a Redox-Coupled Dye-Sensitized Photoelectrode into a Li-O2 Battery for Photoassisted Charging”, Nature Communications, 2014, 5:5111 8. X. Ren, K. C. Lau, M. Yu, X. Bi, E. Kreidler, L. A. Curtiss & Y. Wu; “Understanding Side Reactions in K-O2 Batteries for Improved Cycle Life” , ACS Applied Materials & Interfaces, 2014, 6, 19299 9. X. Bi, X. Ren, Z. Huang, M. Yu, E. Kreidler and Y. Wu; “Investigating dendrites and side reactions in sodium oxygen batteries for improved cycle lives”, Chemical Communications, 2015, 51,7665 10. Z. Huang, M. He, M. Yu, K. Click, D. Beauchamp & Y. Wu; “Dye-Controlled Interfacial Electron Transfer for High-Current Indium Tin Oxide Photocathodes”, Angewandte Chemie Int. Ed., 2015, 54, 6857 11. T. Draskovic, M. Yu & Y. Wu; “2H-CuScO2 Prepared by Low Temperature Hydrothermal Methods and Post-Annealing Effects on Optical and Photoelectrochemical Properties”, Inorganic Chemistry, 2015, 54 , 5519 12. M. Yu, W. McCulloch, D. Beauchamp, Z. Huang, X. Ren &Y. Wu; “Aqueous Lithium-Iodine Solar Flow Battery for the Simultaneous Conversion and Storage of Solar Energy”, Journal of the American Chemical Society, 2015, 137, 8332 13. M. Yu, W. McCulloch, Z. Huang, Brittany Trang & Y. Wu; “Solar-powered Electrochemical Energy Storage: An Alternative to Solar Fuels”, Journal of Materials Chemistry A, 2015, DOI: 10.1039/C5TA06950E Fields of Study Major Field: Chemistry viii Table of Contents Abstract ..............................................................................................................................
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