{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/105849"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/105849","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Soluble redox active macromolecular architectures and their electrochemical analysis for energy storage applications","abstract":"Organic redox-active materials offer advantages of material tunability while maintaining high performance for next-generation energy storage and conversion solutions. Macromolecular architectures such as oligomers, polymers, and colloids have recently gained interest for their size-exclusion capabilities for preventing capacity fades in flow batteries. These architectures are highly tunable and made redox-active by the incorporation of organic redox motifs as pendants. Traditionally, redox active polymers (RAPs) have been electrochemically studied as films or composites, with few examples of solution-based studies until recently. In this dissertation, I explore the design and electrochemical characterization of the redox activity of these RAPs in solution and their behavior at electrode interfaces. The main polymers of interest evaluated contain viologen, ferrocene, and cyclopropenium-based pendant groups. The introduction of crosslinked versions of these polymers, called redox active colloids (RACs), that can be fully excluded from crossing porous membranes are introduced as morphologically controlled redox active material. Importantly, prototype flow battery testing of these RAPs as catholyte/anolyte pairs are investigated for demonstrating their potential use in enabling next-generation nonaqueous redox flow batteries. Alternative applications for these RAPs are also explored by taking advantage of their redox potentials to catalyze chemical reactions in solution. This RAP electrocatalysis is investigated for catalyzing reactions such as peroxide formation in varied lithium environments. For these studies, a combination of experimental techniques including cyclic voltammetry, potential-controlled electrolysis, spectro-electrochemistry, and Galvanostatic cycling were used to characterize RAP and RAC reactivity. In sum, this dissertation elucidates the electrochemical properties of varied macromolecular architectures for use in the field of energy storage.","abstract_html":"Organic redox-active materials offer advantages of material tunability while maintaining high performance for next-generation energy storage and conversion solutions. Macromolecular architectures such as oligomers, polymers, and colloids have recently gained interest for their size-exclusion capabilities for preventing capacity fades in flow batteries. These architectures are highly tunable and made redox-active by the incorporation of organic redox motifs as pendants. Traditionally, redox active polymers (RAPs) have been electrochemically studied as films or composites, with few examples of solution-based studies until recently. In this dissertation, I explore the design and electrochemical characterization of the redox activity of these RAPs in solution and their behavior at electrode interfaces. The main polymers of interest evaluated contain viologen, ferrocene, and cyclopropenium-based pendant groups. The introduction of crosslinked versions of these polymers, called redox active colloids (RACs), that can be fully excluded from crossing porous membranes are introduced as morphologically controlled redox active material. Importantly, prototype flow battery testing of these RAPs as catholyte/anolyte pairs are investigated for demonstrating their potential use in enabling next-generation nonaqueous redox flow batteries. Alternative applications for these RAPs are also explored by taking advantage of their redox potentials to catalyze chemical reactions in solution. This RAP electrocatalysis is investigated for catalyzing reactions such as peroxide formation in varied lithium environments. For these studies, a combination of experimental techniques including cyclic voltammetry, potential-controlled electrolysis, spectro-electrochemistry, and Galvanostatic cycling were used to characterize RAP and RAC reactivity. In sum, this dissertation elucidates the electrochemical properties of varied macromolecular architectures for use in the field of energy storage.","abstract_has_math":false,"creators":["Montoto Blanco, Elena C"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Rodriguez-Lopez, Joaquin","van der Veen, Renske","Moore, Jeffrey S.","Kenis, Paul J. A."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2019,"date_issued":"2019-11-26T20:56:43Z","date_published":"2019-11-26T20:56:43Z","updated_at":"2026-07-22T22:24:45Z","subjects":["redox active polymers","energy storage","flow batteries","electrochemical characterization"],"languages":["en"],"rights":["Copyright 2019 Elena C. 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In this dissertation, I explore the design and electrochemical characterization of the redox activity of these RAPs in solution and their behavior at electrode interfaces. The main polymers of interest evaluated contain viologen, ferrocene, and cyclopropenium-based pendant groups. The introduction of crosslinked versions of these polymers, called redox active colloids (RACs), that can be fully excluded from crossing porous membranes are introduced as morphologically controlled redox active material. Importantly, prototype flow battery testing of these RAPs as catholyte/anolyte pairs are investigated for demonstrating their potential use in enabling next-generation nonaqueous redox flow batteries. Alternative applications for these RAPs are also explored by taking advantage of their redox potentials to catalyze chemical reactions in solution. This RAP electrocatalysis is investigated for catalyzing reactions such as peroxide formation in varied lithium environments. For these studies, a combination of experimental techniques including cyclic voltammetry, potential-controlled electrolysis, spectro-electrochemistry, and Galvanostatic cycling were used to characterize RAP and RAC reactivity. In sum, this dissertation elucidates the electrochemical properties of varied macromolecular architectures for use in the field of energy storage.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2021-05-01","The student, Elena Montoto Blanco, accepted the attached license on 2019-01-08 at 08:53.","The student, Elena Montoto Blanco, submitted this Dissertation for approval on 2019-01-08 at 09:07.","This Dissertation was approved for publication on 2019-01-08 at 14:39.","DSpace SAF Submission Ingestion Package generated from Vireo submission #13350 on 2019-11-26 at 13:59:15","Made available in DSpace on 2019-11-26T20:56:43Z (GMT). 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The main polymers of interest evaluated contain viologen, ferrocene, and cyclopropenium-based pendant groups. The introduction of crosslinked versions of these polymers, called redox active colloids (RACs), that can be fully excluded from crossing porous membranes are introduced as morphologically controlled redox active material. Importantly, prototype flow battery testing of these RAPs as catholyte/anolyte pairs are investigated for demonstrating their potential use in enabling next-generation nonaqueous redox flow batteries. Alternative applications for these RAPs are also explored by taking advantage of their redox potentials to catalyze chemical reactions in solution. This RAP electrocatalysis is investigated for catalyzing reactions such as peroxide formation in varied lithium environments. For these studies, a combination of experimental techniques including cyclic voltammetry, potential-controlled electrolysis, spectro-electrochemistry, and Galvanostatic cycling were used to characterize RAP and RAC reactivity. In sum, this dissertation elucidates the electrochemical properties of varied macromolecular architectures for use in the field of energy storage.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2021-05-01","The student, Elena Montoto Blanco, accepted the attached license on 2019-01-08 at 08:53.","The student, Elena Montoto Blanco, submitted this Dissertation for approval on 2019-01-08 at 09:07.","This Dissertation was approved for publication on 2019-01-08 at 14:39.","DSpace SAF Submission Ingestion Package generated from Vireo submission #13350 on 2019-11-26 at 13:59:15","Made available in DSpace on 2019-11-26T20:56:43Z (GMT). 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