Unusual Internal Electron Transfer in Conjugated Radical Polymers
Abstract
Abstract Nitroxide‐containing organic radical polymers (ORPs) have captured attention for their high power and fast redox kinetics. Yet a major challenge is the polymer's aliphatic backbone, resulting in a low electronic conductivity. Recent attempts that replace the aliphatic backbone with a conjugated one have not met with success. The reason for this is not understood until now. We examine a family of polythiophenes bearing nitroxide radical groups, showing that while both species are electrochemically active, there exists an internal electron transfer mechanism that interferes with stabilization of the polymer's fully oxidized form. This finding directs the future design of conjugated radical polymers in energy storage and electronics, where careful attention to the redox potential of the backbone relative to the organic radical species is needed.
- Publication Date:
- Research Org.:
- Texas A & M Univ., College Station, TX (United States). Texas A & M Engineering Experiment Station
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Welch Foundation
- OSTI Identifier:
- 1533114
- Alternate Identifier(s):
- OSTI ID: 1378296
- Grant/Contract Number:
- SC0014006; A-1766
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 33; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; conjugated radical polymers; lithium polymer batteries; organic radical polymers polythiophene · TEMPO
Citation Formats
Li, Fei, Gore, Danielle N., Wang, Shaoyang, and Lutkenhaus, Jodie L. Unusual Internal Electron Transfer in Conjugated Radical Polymers. United States: N. p., 2017.
Web. doi:10.1002/anie.201705204.
Li, Fei, Gore, Danielle N., Wang, Shaoyang, & Lutkenhaus, Jodie L. Unusual Internal Electron Transfer in Conjugated Radical Polymers. United States. https://doi.org/10.1002/anie.201705204
Li, Fei, Gore, Danielle N., Wang, Shaoyang, and Lutkenhaus, Jodie L. Fri .
"Unusual Internal Electron Transfer in Conjugated Radical Polymers". United States. https://doi.org/10.1002/anie.201705204. https://www.osti.gov/servlets/purl/1533114.
@article{osti_1533114,
title = {Unusual Internal Electron Transfer in Conjugated Radical Polymers},
author = {Li, Fei and Gore, Danielle N. and Wang, Shaoyang and Lutkenhaus, Jodie L.},
abstractNote = {Abstract Nitroxide‐containing organic radical polymers (ORPs) have captured attention for their high power and fast redox kinetics. Yet a major challenge is the polymer's aliphatic backbone, resulting in a low electronic conductivity. Recent attempts that replace the aliphatic backbone with a conjugated one have not met with success. The reason for this is not understood until now. We examine a family of polythiophenes bearing nitroxide radical groups, showing that while both species are electrochemically active, there exists an internal electron transfer mechanism that interferes with stabilization of the polymer's fully oxidized form. This finding directs the future design of conjugated radical polymers in energy storage and electronics, where careful attention to the redox potential of the backbone relative to the organic radical species is needed.},
doi = {10.1002/anie.201705204},
journal = {Angewandte Chemie (International Edition)},
number = 33,
volume = 56,
place = {United States},
year = {Fri Jun 23 00:00:00 EDT 2017},
month = {Fri Jun 23 00:00:00 EDT 2017}
}
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Works referenced in this record:
Conjugated polymers incorporating pendant functional groups—synthesis and characterisation
journal, January 1997
- Higgins, Simon J.
- Chem. Soc. Rev., Vol. 26, Issue 4
Rechargeable batteries with organic radical cathodes
journal, June 2002
- Nakahara, K.; Iwasa, S.; Satoh, M.
- Chemical Physics Letters, Vol. 359, Issue 5-6, p. 351-354
Organic radical battery with PTMA cathode: Effect of PTMA content on electrochemical properties
journal, May 2008
- Kim, Jae-Kwang; Cheruvally, Gouri; Ahn, Jou-Hyeon
- Journal of Industrial and Engineering Chemistry, Vol. 14, Issue 3
Synthesis and properties of novel TEMPO-contained polypyrrole derivatives as the cathode material of organic radical battery
journal, June 2014
- Xu, Lihuan; Yang, Fang; Su, Chang
- Electrochimica Acta, Vol. 130
Hybrid supercapacitor-battery materials for fast electrochemical charge storage
journal, March 2014
- Vlad, A.; Singh, N.; Rolland, J.
- Scientific Reports, Vol. 4, Issue 1
Ultrathin polyelectrolyte multilayers: in situ ESR/UV-Vis-NIR spectroelectrochemical study of charge carriers formed under oxidation
journal, January 2004
- Rapta, Peter; Lukkari, Jukka; Tarábek, Ján
- Phys. Chem. Chem. Phys., Vol. 6, Issue 2
Superior radical polymer cathode material with a two-electron process redox reaction promoted by graphene
journal, January 2012
- Guo, Wei; Yin, Ya-Xia; Xin, Sen
- Energy Environ. Sci., Vol. 5, Issue 1
A polythiophene derivative bearing TEMPO as a cathode material for rechargeable batteries
journal, December 2011
- Aydın, M.; Esat, B.; Kılıç, Ç.
- European Polymer Journal, Vol. 47, Issue 12
Charge Storage in Decyl- and 3,6,9-Trioxadecyl-Substituted Poly(dithieno[3,2- b :2,3- d ]pyrrole) Electrodes
journal, December 2013
- Mike, Jared F.; Shao, Lin; Jeon, Ju-Won
- Macromolecules, Vol. 47, Issue 1
Organic Radical Battery Approaching Practical Use
journal, March 2011
- Nakahara, Kentaro; Oyaizu, Kenichi; Nishide, Hiroyuki
- Chemistry Letters, Vol. 40, Issue 3
Conductive characteristics of radical-bearing polythiophenes using a microcomb-shaped electrode
journal, January 2007
- Tanaka, Manabu; Hatta, Kaoru; Edura, Tomohiko
- Polymers for Advanced Technologies, Vol. 18, Issue 11
Electropolymerized Polythiophenes Bearing Pendant Nitroxide Radicals
journal, February 2016
- Li, Fei; Zhang, Yanpu; Kwon, Se Ra
- ACS Macro Letters, Vol. 5, Issue 3
Syntheses and Electrochemical Characterization of Low Oxidation Potential Nitrogen Analogs of Pedot as Electrochromic Materials
journal, January 2016
- Hacioglu, Serife O.; Yiğit, Deniz; Ermis, Emel
- Journal of The Electrochemical Society, Vol. 163, Issue 10
Electrochemically Active Polymers for Electrochemical Energy Storage: Opportunities and Challenges
journal, August 2013
- Mike, Jared F.; Lutkenhaus, Jodie L.
- ACS Macro Letters, Vol. 2, Issue 9
Thianthrene-functionalized polynorbornenes as high-voltage materials for organic cathode-based dual-ion batteries
journal, January 2015
- Speer, Martin E.; Kolek, Martin; Jassoy, Jean Jacques
- Chemical Communications, Vol. 51, Issue 83
Poly(Thiophene): A Stable Polymer Cathode Material
journal, January 1984
- Kaufman, J. H.
- Journal of The Electrochemical Society, Vol. 131, Issue 9
Radical Polymers for Organic Electronic Devices: A Radical Departure from Conjugated Polymers?
journal, June 2009
- Oyaizu, Kenichi; Nishide, Hiroyuki
- Advanced Materials, Vol. 21, Issue 22
In Situ ESR/UV−vis−NIR and ATR-FTIR Spectroelectrochemical Studies on the p-Doping of Copolymers of 3-Methylthiophene and 3-Hexylthiophene
journal, February 2009
- Cházaro-Ruiz, Luis F.; Kellenberger, Andrea; Dunsch, Lothar
- The Journal of Physical Chemistry B, Vol. 113, Issue 8
Porous polythiophene as a cathode material for lithium batteries with high capacity and good cycling stability
journal, January 2012
- Liu, Li; Tian, Fanghua; Wang, Xingyan
- Reactive and Functional Polymers, Vol. 72, Issue 1
The electrochemical performance of polythiophene synthesized by chemical method as the polymer battery electrode
journal, April 2004
- Ryu, Kwang Sun; Lee, Youngil; Han, Kyoo-Seung
- Materials Chemistry and Physics, Vol. 84, Issue 2-3
Electron-Transfer Kinetics of Nitroxide Radicals as an Electrode-Active Material
journal, December 2004
- Suga, Takeo; Pu, Yong-Jin; Oyaizu, Kenichi
- Bulletin of the Chemical Society of Japan, Vol. 77, Issue 12
Polymer-Based Organic Batteries
journal, August 2016
- Muench, Simon; Wild, Andreas; Friebe, Christian
- Chemical Reviews, Vol. 116, Issue 16
Characterization, properties and doping of poly(3-alkylthiophene-2,5-diyl)s, P3RThs (R = n-C6H13, n-C18H17, n-C12H25), prepared by using zero-valent nickel complex
journal, May 1994
- Miyazaki, Yuichi; Yamamoto, Takakazu
- Synthetic Metals, Vol. 64, Issue 1
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journal, January 2020
- Lau, Vincent Wing‐hei; Moudrakovski, Igor; Yang, Junghoon
- Angewandte Chemie International Edition, Vol. 59, Issue 10
Diblock copolymers consisting of a redox polymer block based on a stable radical linked to an electrically conducting polymer block as cathode materials for organic radical batteries
journal, January 2019
- Hergué, Noémie; Ernould, Bruno; Minoia, Andrea
- Polymer Chemistry, Vol. 10, Issue 20
Polynitroxide-grafted-graphene: a superior cathode for lithium ion batteries with enhanced charge hopping transportation
journal, January 2019
- Lu, Chengyi; Pan, Guang; Huang, Qiaogao
- Journal of Materials Chemistry A, Vol. 7, Issue 9
Chain rigidity modification to promote the electrochemical performance of polymeric battery electrode materials
journal, January 2019
- Niu, Zhihui; Wu, Huaxi; Liu, Lei
- Journal of Materials Chemistry A, Vol. 7, Issue 17
Uncovering the Shuttle Effect in Organic Batteries and Counter‐Strategies Thereof: A Case Study of the N , N′ ‐Dimethylphenazine Cathode
journal, January 2020
- Lau, Vincent Wing‐hei; Moudrakovski, Igor; Yang, Junghoon
- Angewandte Chemie, Vol. 132, Issue 10