Role of Side-Chain Free Volume on the Electrochemical Behavior of Poly(propylenedioxythiophenes)
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- School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
- School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
- Department of Chemical and Environmental Engineering, The University of Arizona, Tucson, Arizona 85721-0012, United States
- School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States, School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
- School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
Mixed ionic/electronic conducting polymers are versatile systems for, e.g., energy storage, heat management (exploiting electrochromism), and biosensing, all of which require electrochemical doping, i.e., the electrochemical oxidation or reduction of their macromolecular backbones. Electrochemical doping is achieved via electro-injection of charges (i.e., electronic carriers), stabilized via migration of counterions from a supporting electrolyte. Since the choice of the polymer side-chain functionalization influences electrolyte and/or ion sorption and desorption, it in turn affects redox properties, and, thus, electrochemically induced mixed conduction. However, our understanding of how side-chain versus backbone design can increase ion flow while retaining high electronic transport remains limited. Hence, heuristic design approaches have typically been followed. Herein, we consider the redox and swelling behavior of three poly(propylenedioxythiophene) derivatives, P(ProDOT)s, substituted with different side-chain motifs, and demonstrate that passive swelling is controlled by the surface polarity of P(ProDOT) films. In contrast, active swelling under operando conditions (i.e., under an applied bias) is dictated by the local side-chain free volume on the length scale of a monomer unit. Such insights deliver important design criteria toward durable soft electrochemical systems for diverse energy and biosensing platforms and new understanding into electrochemical conditioning (“break-in”) in many conducting polymers.
- Research Organization:
- Georgia Institute of Technology, Atlanta, GA (United States); Univ. of Arizona, Tucson, AZ (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Soft PhotoElectroChemical Systems (SPECS)
- Sponsoring Organization:
- USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Science Foundation (NSF); US Department of the Navy, Office of Naval Research (ONR)
- Grant/Contract Number:
- SC0023411; ECCS1542174; N00014-20-1-2129; N00014-22-1-2185
- OSTI ID:
- 2323370
- Alternate ID(s):
- OSTI ID: 2324999
- Journal Information:
- Chemistry of Materials, Journal Name: Chemistry of Materials Vol. 36 Journal Issue: 6; ISSN 0897-4756
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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