Structure-Property Relationships for Mixed Ion- and Electron-Conducting Polymer Systems

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DURBIN-DISSERTATION-2023.pdf (26.33 MB)
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Durbin, Marlow Monnig
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School of Chemical and Biomolecular Engineering
School established in 1901 as the School of Chemical Engineering; in 2003, renamed School of Chemical and Biomolecular Engineering
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https://hdl.handle.net/1853/72775
Abstract
Mixed ion- and electron-conducting polymers are an emerging class of functional materials combining mechanical softness and pliability with electrochemical functionality. The possibility of building devices from “plastic electronics” has spurred great interest in the fields of electrochemical energy storage, bio-integrated electronics, and analog computing. In this thesis, a “polymer science” approach is taken in combination with prior synthetic efforts to improve fundamental understanding of how the chemical and physical structure of mixed conducting polymers results in their diverse electrochemical, spectroscopic, and mechanical properties. We begin with a family of poly (3,4-propylenedioxythiophene) (“ProDOT”) polymers and copolymers, functionalized with aliphatic and/or polar oligo(ether) side chains of varying length and linearity for redox activity in organic electrolytes. Based on the redox and swelling behavior of three P(ProDOT)s, we illustrate that passive (bias-free) swelling of such P(ProDOT) films is principally driven by surface polarity, while side-chain free volume dictates the materials’ active swelling under applied electrochemical potentials by directing ion “flow” (sorption/desorption). We next study the effects of electrochemical cycling on ProDOT solid-state ordering as a function of side chain linearity. Electrochemical doping is found to enhance structural coherence in the lamellar/side-chain direction in P(ProDOT) polymers cycled in organic electrolytes, suggesting that the combined effects of electrochemical oxidation and counter-ion insertion substantially re-order these polymers. We go on to explore the phase behavior of multiple binary semiconductor:ion conductor blend systems with redox activity in aqueous and/or organic electrolytes, showing that careful manipulation of solution processing parameters may result in blend systems with altered redox activity compared to their neat components. With the design rules developed here, one can readily envision innovations in mixed ion-/electron-conducting polymer systems that bring the field closer to engineering “materials on demand” for varied applications.
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2023-07-30
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