Quantifying internal charge transfer and mixed ion-electron transfer in conjugated radical polymers
Abstract
Macromolecular radicals are receiving growing interest as functional materials in energy storage devices and in electronics. With the need for enhanced conductivity, researchers have turned to macromolecular radicals bearing conjugated backbones, but results thus far have yielded conjugated radical polymers that are inferior in comparison to their non-conjugated partners. The emerging explanation is that the radical unit and the conjugated backbone (both being redox active) transfer electrons between each other, essentially “quenching” conductivity or capacity. Here, the internal charge transfer process is quantified using a polythiophene loaded with 0, 25, or 100% nitroxide radicals (2,2,6,6-tetramethyl-1-piperidinyloxy [TEMPO]). Importantly, deconvolution of the cyclic voltammograms shows mixed faradaic and non-faradaic contributions that contribute to the internal charge transfer process. Further, mixed ion-electron transfer is determined for the 100% TEMPO-loaded conjugated radical polymer, from which it is estimated that one triflate anion and one propylene carbone molecule are exchanged for every electron. Although these findings indicate the reason behind their poor conductivity and capacity, they point to how these materials might be used as voltage regulators in the future.
- Authors:
-
[4]
- Artie McFerrin Department of Chemical Engineering;Texas A&M University;College Station;USA
- Department of Materials Science and Engineering;Texas A&M University;College Station;USA
- Materials Science and Engineering;Cornell University;Ithaca;USA
- Artie McFerrin Department of Chemical Engineering;Texas A&M University;College Station;USA;Department of Materials Science and Engineering
- Publication Date:
- Research Org.:
- Texas A & M Univ., College Station, TX (United States); Cornell Univ., Ithaca, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1658637
- Alternate Identifier(s):
- OSTI ID: 1706079
- Grant/Contract Number:
- SC0014006; SC0014336
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 36; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Wang, Shaoyang, Easley, Alexandra D., Thakur, Ratul M., Ma, Ting, Yun, Junyeong, Zhang, Yiren, Ober, Christopher K., and Lutkenhaus, Jodie L. Quantifying internal charge transfer and mixed ion-electron transfer in conjugated radical polymers. United Kingdom: N. p., 2020.
Web. doi:10.1039/d0sc03567j.
Wang, Shaoyang, Easley, Alexandra D., Thakur, Ratul M., Ma, Ting, Yun, Junyeong, Zhang, Yiren, Ober, Christopher K., & Lutkenhaus, Jodie L. Quantifying internal charge transfer and mixed ion-electron transfer in conjugated radical polymers. United Kingdom. https://doi.org/10.1039/d0sc03567j
Wang, Shaoyang, Easley, Alexandra D., Thakur, Ratul M., Ma, Ting, Yun, Junyeong, Zhang, Yiren, Ober, Christopher K., and Lutkenhaus, Jodie L. Wed .
"Quantifying internal charge transfer and mixed ion-electron transfer in conjugated radical polymers". United Kingdom. https://doi.org/10.1039/d0sc03567j.
@article{osti_1658637,
title = {Quantifying internal charge transfer and mixed ion-electron transfer in conjugated radical polymers},
author = {Wang, Shaoyang and Easley, Alexandra D. and Thakur, Ratul M. and Ma, Ting and Yun, Junyeong and Zhang, Yiren and Ober, Christopher K. and Lutkenhaus, Jodie L.},
abstractNote = {Macromolecular radicals are receiving growing interest as functional materials in energy storage devices and in electronics. With the need for enhanced conductivity, researchers have turned to macromolecular radicals bearing conjugated backbones, but results thus far have yielded conjugated radical polymers that are inferior in comparison to their non-conjugated partners. The emerging explanation is that the radical unit and the conjugated backbone (both being redox active) transfer electrons between each other, essentially “quenching” conductivity or capacity. Here, the internal charge transfer process is quantified using a polythiophene loaded with 0, 25, or 100% nitroxide radicals (2,2,6,6-tetramethyl-1-piperidinyloxy [TEMPO]). Importantly, deconvolution of the cyclic voltammograms shows mixed faradaic and non-faradaic contributions that contribute to the internal charge transfer process. Further, mixed ion-electron transfer is determined for the 100% TEMPO-loaded conjugated radical polymer, from which it is estimated that one triflate anion and one propylene carbone molecule are exchanged for every electron. Although these findings indicate the reason behind their poor conductivity and capacity, they point to how these materials might be used as voltage regulators in the future.},
doi = {10.1039/d0sc03567j},
journal = {Chemical Science},
number = 36,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {1}
}
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