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Effect of the Linker in Terephthalate-Functionalized Conducting Redox Polymers
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. (Nanotechnology and Functional Materials)
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.ORCID iD: 0000-0002-9092-261X
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. (Nanoteknologi och funktionella material)
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2016 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 222, p. 149-155Article in journal (Refereed) Published
Abstract [en]

Abstract The combination of high capacity redox active pendent groups and conducting polymers, realized in conducting redox polymers (CRPs), provides materials with high charge storage capacity that are electronically conducting which makes CRPs attractive for electrical energy storage applications. In this report, six polythiophene and poly(3,4-ethylenedioxythiophene)(PEDOT)-based CRPs with a diethyl terephthalate unit covalently bound to the polymer chain by various linkers have been synthesized and characterized electrochemically. The effects of the choice of polymer backbone and of the nature of the link on the electrochemistry, and in particular the cycling stability of these polymers, are discussed. All CRPs show both the doping of the polymer backbone as well as the redox behavior of the pendent groups and the redox potential of the pendent groups in the CRPs is close to that of corresponding monomer, indicating insignificant interaction between the pendant and the polymer backbone. While all CRPs show various degrees of charge decay upon electrochemical redox conversion, the PEDOT-based CRPs show significantly improved stability compared to the polythiophene counterparts. Moreover, we show that by the right choice of link the cycling stability of diethyl terephthalate substituted PEDOT-based CRPs can be significantly improved.

Place, publisher, year, edition, pages
2016. Vol. 222, p. 149-155
Keywords [en]
conducting redox polymers, PEDOT, polythiophene, terephthalate
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
URN: urn:nbn:se:uu:diva-310464DOI: 10.1016/j.electacta.2016.10.183ISI: 000392566200018OAI: oai:DiVA.org:uu-310464DiVA, id: diva2:1057033
Funder
Swedish Foundation for Strategic Research Swedish Research CouncilCarl Tryggers foundation Stiftelsen Olle Engkvist ByggmästareSwedish Energy AgencyEU, European Research Council, 644631Available from: 2016-12-16 Created: 2016-12-16 Last updated: 2017-11-29Bibliographically approved
In thesis
1. Conducting Redox Polymers for Electrode Materials: Synthetic Strategies and Electrochemical Properties
Open this publication in new window or tab >>Conducting Redox Polymers for Electrode Materials: Synthetic Strategies and Electrochemical Properties
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Organic electrode materials represent an intriguing alternative to their inorganic counterparts due to their sustainable and environmental-friendly properties. Their plastic character allows for the realization of light-weight, versatile and disposable devices for energy storage. Conducting redox polymers (CRPs) are one type of the organic electrode materials involved, which consist of a π-conjugated polymer backbone and covalently attached redox units, the so-called pendant. The polymer backbone can provide conductivity while it is oxidized or reduced (i. e., p- or n-doped) and the concurrent redox chemistry of the pendant provides charge capacity. The combination of these two components enables CRPs to provide both high charge capacity and high power capability. This dyad polymeric framework provides a solution to the two main problems associated with organic electrode materials based on small molecules: the dissolution of the active material in the electrolyte, and the sluggish charge transport within the material. This thesis introduces a general synthetic strategy to obtain the monomeric CRPs building blocks, followed by electrochemical polymerization to afford the active CRPs material. The choice of pendant and of polymer backbone depends on the potential match between these two components, i.e. the redox reaction of the pendant and the doping of backbone occurring within the same potential region. In the thesis, terephthalate and polythiophene were selected as the pendant and polymer backbone respectively, to get access to low potential CRPs. It was found that the presence of a non-conjugated linker between polymer backbone and pendant is essential for the polymerizability of the monomers as well as for the preservation of individual redox activities. The resulting CRPs exhibited fast charge transport within the polymer film and low activation barriers for charge propagation. These low potential CRPs were designed as the anode materials for energy storage applications. The combination of redox active pendant as charge carrier and a conductive polymer backbone reveals new insights into the requirements of organic matter based electrical energy storage materials.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. p. 83
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1604
Keywords
Organic electrode material, Energy storage, Conducting redox polymer, Polythiophene, Terephthalate, PEDOT
National Category
Nano Technology Organic Chemistry Physical Chemistry Polymer Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-334562 (URN)978-91-513-0168-6 (ISBN)
Public defence
2018-01-19, B41, BMC, Husargatan, Uppsala, 09:15 (English)
Opponent
Supervisors
Funder
SweGRIDS - Swedish Centre for Smart Grids and Energy StorageSwedish Research CouncilSwedish Foundation for Strategic Research
Available from: 2017-12-21 Created: 2017-11-23 Last updated: 2018-03-08

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