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Probing Polymer-Pendant Interactions in the Conducting Redox Polymer Poly(pyrrol-3-ylhydroquinone)
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. (Nanoteknologi och Funktionella Material)
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.ORCID iD: 0000-0002-5496-9664
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Synthetical Organic Chemistry.ORCID iD: 0000-0002-9092-261X
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2014 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 118, no 41, 23499-23508 p.Article in journal (Refereed) Published
Abstract [en]

Conducting polymers with redox active pendant groups show properties typical of both conducting polymers (i.e., capacitive charging and intrinsic conductivity) and redox polymers (i.e., electrochemical surface response at the formal potential of the pendant groups). The two components can also exert significant interaction on each other during their separate electrochemical reactions. In poly(pyrrol-3-ylhydroquinone), a polypyrrole derivative functionalized with hydroquinone units, the redox conversion of the pendant groups has a large impact on the polymer backbone. This interaction is manifested by a loss of bipolaron states during the hydroquinone oxidation, leading to a decreasing p-doping level with increasing potential, something which, to the best of our knowledge, has never been observed for a conducting polymer. Another effect is a contraction of the polymer film, and subsequent mass loss due to solvent expulsion upon hydroquinone oxidation, which counteracts the normal swelling of polypyrrole with increased potential. The conducting redox polymer under investigation has been synthesized via two routes, leading to different fractions of subunits bearing redox active hydroquinone groups. While the redox potentials are unaffected by the synthesis route, the backbone/pendant group interaction varies notably depending on the degree of quinone functionalization. This type of polymers could find use in, e.g., organic energy storage materials, since the polymer backbone both increases the electronic conductivity and prevents dissolution of the active material, as well as in actuator application, due to polymer contraction over the relatively narrow potential region where the pendant group redox chemistry occurs.

Place, publisher, year, edition, pages
2014. Vol. 118, no 41, 23499-23508 p.
National Category
Physical Chemistry Engineering and Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
URN: urn:nbn:se:uu:diva-230486DOI: 10.1021/jp506821zISI: 000343333600007OAI: oai:DiVA.org:uu-230486DiVA: diva2:745477
Available from: 2014-09-10 Created: 2014-08-26 Last updated: 2017-12-05Bibliographically approved
In thesis
1. Conducting Redox Polymers for Electrical Energy Storage: Backbone - Substituent Interactions in Quinone Polypyrrole Model Systems
Open this publication in new window or tab >>Conducting Redox Polymers for Electrical Energy Storage: Backbone - Substituent Interactions in Quinone Polypyrrole Model Systems
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Organic electrical energy storage (EES) is a growing field of research that is expected to play an important role in the future, as the need for sustainable EES increases. Conducting redox polymers (CRPs), i.e. conducting polymers with incorporated redox active moieties e.g. as pendant groups (PGs), are proposed as a promising class of compounds for this purpose. Redox cycling of the PGs can be utilized for high charge storage capacity, while the conducting polymer backbone provides fast charge transport through the material. Some of the major challenges with small-molecule systems for EES could be solved by using CRPs, e.g. capacity fading due to dissolution of the active compound, and high resistance due to slow charge transport between molecules. The latter issue is often solved by adding large amounts of conducting additives to the active material, drastically lowering the specific capacity. In this project, CRPs are shown to be able to function in battery cells without any additives, making both high capacity and high power possible. Although several CRPs have been reported in the literature, very few detailed studies have been conducted on the electrochemical processes of the two systems (i.e. the conducting polymer backbone and the redox active PGs). An important factor to consider in CRP design is the possibility for interaction between the two redox systems, which could be either beneficial or detrimental to the function as EES material. In this thesis, CRP model systems composed of hydroquinone functionalized polypyrrole have been studied, and they exhibit separate redox reactions for the PGs and the backbone, overlapping in potential. Significant interaction between them was observed, as oxidation of the PGs has severe impact on the backbone: When the oxidized and hydrophobic p-benzoquinone PGs are formed, they pack and force the polymer backbone to twist, localizing the bipolarons, and decreasing the conductivity. This is accompanied by a contraction of the polymer film and expulsion of electrolyte. Overall, the interaction in these polymers is destructive for their EES function, and it could be eliminated by introduction of a long linker unit between the PGs and the backbone.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2014. 72 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1177
Keyword
Organic energy storage, Hydroquinone polymers, Functionalized polypyrrole, Spectroelectrochemistry, Electrochemical quartz crystal microbalance, In situ conductivity
National Category
Nano Technology
Identifiers
urn:nbn:se:uu:diva-230647 (URN)978-91-554-9033-1 (ISBN)
Public defence
2014-10-30, Polhemssalen, Ångströmslaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:30 (English)
Opponent
Supervisors
Available from: 2014-10-03 Created: 2014-08-27 Last updated: 2015-01-23Bibliographically approved
2. Quinone-Pyrrole Dyad Based Polymers for Organic Batteries: From Design to Application
Open this publication in new window or tab >>Quinone-Pyrrole Dyad Based Polymers for Organic Batteries: From Design to Application
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Organic electrode materials are finding increasing use in energy storage devices due to their attractive properties that allow building of flexible and low weight devices in an environmentally friendlier manner than traditional alternatives. Among these organic electrode materials, conducting redox polymers (CRPs), consisting of conducing polymer (CP) with covalently attached redox active pendant groups (PG), have attracted our interests. This is due to the advantageous synergy between CP and PG, e.g. electronic conductivity, high stability and large charge storage capacity. In this thesis polypyrrole has been selected as CP and quinones as PGs. A series of quinone-pyrrole dyad polymers has been synthesized with a variety of quinone substituents, demonstrating the adjustability of quinone formal potentials by choice of substituents. Importantly, in this series we show that the CP-PG redox match, i.e. that the formal potential of the PG is within the conducting region of the CP, is a requirement for fast charge transfer from the electrode to the PGs. Moreover, a series of quinone-pyrrole dyad polymers with various linkers was synthesized, showing that the choice of linker has a pronounced impact on the interactions between the PG and CP. In addition, the temperature dependence of conductance during doping of the polymers reveals the charge transport mechanism. To summarize, the adjustability of the quinone formal potential as well as the fast charge transport in the bulk material ensures the applicability of the CRPs as electrode materials in organic batteries.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. 73 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1483
Keyword
Organic battery, conducting polymer, quinone, polypyrrole, spectroelectrochemistry, conductance
National Category
Nano Technology
Identifiers
urn:nbn:se:uu:diva-316492 (URN)978-91-554-9832-0 (ISBN)
Public defence
2017-04-21, Polhemsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2017-03-30 Created: 2017-03-01 Last updated: 2017-04-18

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Karlsson, ChristofferHuang, HaoStrømme, MariaGogoll, AdolfSjödin, Martin

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