Systematic study of redox-active polymers for energy storage: Exploring structural modulation, electrolyte interactions and programmable degradation

The development of sustainable energy storage solutions necessitates innovative materials that offer high efficiency, stability, and recyclability. Redox-active polymers (RAPs) are a promising alternative to traditional small-molecule redox species due to their modularity, tunability, and potential for eco-friendly applications. However, their widespread implementation ishindered by key challenges, including electrolyte-induced redox behavior shifts, irreversible degradation, and electrode fouling. This dissertation investigates strategies to overcome these challenges through three interconnected research themes. Chapter 1 provides an overview of RAP limitations and research directions, focusing on: (1) the influence of electrolyte composition on RAP reactivity and charge transport, (2) the development of mesolytic cleavage strategies for controlled polymer degradation, and (3) the design of tunable ferrocene-based RAPs for optimized redox behavior. Chapter 2 explores the potential of mesolytic cleavage using homobenzylic ether linkers to enable programmed RAP degradation, facilitating electrode defouling and active material recovery. Chapter 3 examines the integration of Jeffamine copolymers in ferrocene-containing RAPs, demonstrating tailored redox properties, reduced electrostatic interactions, and enhanced electrochemical stability. By employing electrochemical characterization, spectroelectrochemical analysis, and strategic polymer design, this work advances the understanding and development of next-generation RAPs. The findings presented here contribute to the broader goal of creating sustainable, high-performance materials for energy storage applications, particularly in redox flow batteries.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois Urbana-Champaign

Year dc:date

2025

Author dc:creator

• Ibrahim, Nafisa Aden

Contributors dc:contributor

• Rodríguez-López, Joaquín
• Zimmerman, Steven C
• Diao, Ying
• Shen, Mei

• Redox-active polymers
• electrochemistry
• Mesolytic cleavage

Statement dc:rights

• Copyright 2025 Nafisa Ibrahim

Language dc:language

en, eng

Handle dc:identifier

https://hdl.handle.net/2142/129515

OAI record oai:identifier

https://www.ideals.illinois.edu/oai-pmh?verb=GetRecord&metadataPrefix=etdms&identifier=oai%3Awww.ideals.illinois.edu%3A2142%2F129515