Engineering Ionomer Materials for Addressing Ohmic Resistances in Electrochemical Desalination and Waste Heat Recovery
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Louisiana State University LSU Digital Commons LSU Doctoral Dissertations Graduate School May 2020 Engineering Ionomer Materials for Addressing Ohmic Resistances in Electrochemical Desalination and Waste Heat Recovery Varada Menon Palakkal Louisiana State University and Agricultural and Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_dissertations Part of the Membrane Science Commons, and the Polymer Science Commons Recommended Citation Palakkal, Varada Menon, "Engineering Ionomer Materials for Addressing Ohmic Resistances in Electrochemical Desalination and Waste Heat Recovery" (2020). LSU Doctoral Dissertations. 5248. https://digitalcommons.lsu.edu/gradschool_dissertations/5248 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Doctoral Dissertations by an authorized graduate school editor of LSU Digital Commons. For more information, please [email protected]. ENGINEERING IONOMER MATERIALS FOR ADDRESSING OHMIC RESISTANCES IN ELECTROCHEMICAL DESALINATION AND WASTE HEAT RECOVERY A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Gordon A. and Mary Cain Department of Chemical Engineering by Varada Menon Palakkal B.S., National Institute of Technology, Calicut, India, 2015 August 2020 Dedicated to my Ammamma ii Acknowledgements I would like to express my sincere gratitude to my advisor Dr. Chris Arges, for his support, encouragement and motivation throughout my graduate studies. It was a great opportunity to work on several challenging and interesting research problems that has enabled my development as a scientist in his lab. He has always trusted me and given me freedom to explore my creativity as a researcher. I am extremely grateful for his guidance in writing papers and my dissertation. He has also given me several opportunities to present my work at conferences and meetings that has fostered collaborations withour research groups. I am also grateful to our collaborator at Argonne National Laboratory, Dr. Yupo Lin, for his kind guidance and funding for my research. I would also like to thank Dr. Lauren Valentino, Postdoctoral scholar and Louis Edano, the Lab technician at Argonne who have helped immensely in this project. I would also like to thank Dr. Xiuping Zhu, from Civil Engineering department of Louisiana State University and Dr. Marta Hatzell from Georgia Institute of Technology for their valuable inputs and providing guidance for the copper- ammonia flow battery project. I would like to thank everyone in my defense committee- Dr. John Flake, Dr. Bhuvnesh Bharti, Dr. John Pojman and Dr. Chao Wang for their invaluable time and support in shaping this dissertation and their suggestions in finishing it. Additionally, this dissertation would not have been possible without the help of my colleagues - Le Zhang, Gokul Venugopalan, Subarna Kole, Matthew Jordan, Deepra Bhattacharya and our undergraduate members - Thu Nguyen, Phuc Nguyen and Juan Rubio in our lab. They have extended their support and worked in several projects. I would also like to thank all employees at the Machine shop specifically Joe Bell and Nick Lombardo in Chemical Engineering department for their work, advice and suggestions regarding building the capacitive deionization cell, the conductivity cell and assistance in setting up other equipments. My experiments would not have been possible without their help. iii I would also like to thank my friends, Trina di, Mani, Sai, Pragathi, Gauri, Joselin, Sikha, Hao Wang and Athira who have always spoke in encouragement and motivated me towards the completion of this degree. Above all, I would like to thank my fiancé, Adhiraj Singh for his constant support and optimism at all lows and highs, he has motivated me to push forward throughout these 5 years. Last but not the least, I would like to thank my beautiful parents, Mohan and Maya and sister Kalpana for being supportive and motivating me to do well. iv Table of Contents Acknowledgements ........................................................................................................................ iii List of Acronyms .......................................................................................................................... vii Abstract .......................................................................................................................................... ix Chapter 1. Introduction ....................................................................................................................1 1.1 Significance and Background ...............................................................................................1 1.2 Ion-exchange materials .........................................................................................................8 1.3 Electrochemical platforms where ohmic resistances are addressed ...................................14 1.4 Conclusions .........................................................................................................................18 Chapter 2. Theory ..........................................................................................................................20 2.1 Research objective ..............................................................................................................20 2.2 Significance of ionic conductivity in electrochemical devices ...........................................20 2.3 Equivalent circuit modeling using electrochemical impedance spectroscopy ....................26 2.4 Bipolar junction ..................................................................................................................27 2.5 Butler-Volmer equation ......................................................................................................30 2.6 Pourbaix diagram ................................................................................................................31 2.7 Conclusions .........................................................................................................................32 Chapter 3. Experimental Methods .................................................................................................33 3.1 Introduction .........................................................................................................................33 3.2 Materials .............................................................................................................................33 3.3 For MCDI study .................................................................................................................34 3.4. For RW-EDI study .............................................................................................................41 3.5 For TRBs study ..................................................................................................................51 Chapter 4. Low-Resistant Ion-Exchange Membranes for Energy Efficient Membrane Capacitive Deionization (MCDI) .................................................................................................................59 4.1 Introduction ........................................................................................................................59 4.2 Results and discussion .......................................................................................................60 4.3 Conclusions ........................................................................................................................74 Chapter 5. Advancing Electrodeionization with Conductive Ionomer Binders that Immobilize Ion-Exchange Resin Particles into Porous Wafer Substrates .....................................................75 5.1 Introduction .........................................................................................................................75 5.2 Results and discussion ........................................................................................................78 5.3 Conclusions .........................................................................................................................92 Chapter 6. A High Power Thermally Regenerative Copper-Ammonia Redox Flow Battery Enabled by Zero Gap Cell Design and Low-Resistant Membranes and Protective Electrode Coatings .....................................................................................................................................94 6.1 Introduction .........................................................................................................................94 v 6.2 Results and discussion ........................................................................................................97 6.3 Conclusions .......................................................................................................................113 Chapter 7. Addressing Spacer Channel Resistances in Membrane Capacitive Deionization......115 7.1 Introduction .......................................................................................................................115 7.2 Results and discussion ......................................................................................................116 7.3 Conclusions .......................................................................................................................119