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Quinone-Pyrrole Dyad Based Polymers for Organic Batteries: From Design to Application
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. (Nanoteknologi och Funktionella Material)
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. , p. 73
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1483
Keywords [en]
Organic battery, conducting polymer, quinone, polypyrrole, spectroelectrochemistry, conductance
National Category
Nano Technology
Identifiers
URN: urn:nbn:se:uu:diva-316492ISBN: 978-91-554-9832-0 (print)OAI: oai:DiVA.org:uu-316492DiVA, id: diva2:1077955
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
List of papers
1. Probing Polymer-Pendant Interactions in the Conducting Redox Polymer Poly(pyrrol-3-ylhydroquinone)
Open this publication in new window or tab >>Probing Polymer-Pendant Interactions in the Conducting Redox Polymer Poly(pyrrol-3-ylhydroquinone)
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2014 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 118, no 41, p. 23499-23508Article 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.

National Category
Physical Chemistry Engineering and Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-230486 (URN)10.1021/jp506821z (DOI)000343333600007 ()
Available from: 2014-09-10 Created: 2014-08-26 Last updated: 2017-12-05Bibliographically approved
2. Polymer–Pendant Interactions in Poly(pyrrol-3-ylhydroquinone): A Solution for the Use of Conducting Polymers at Stable Conditions
Open this publication in new window or tab >>Polymer–Pendant Interactions in Poly(pyrrol-3-ylhydroquinone): A Solution for the Use of Conducting Polymers at Stable Conditions
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2013 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 117, no 45, p. 23558-23567Article in journal (Refereed) Published
Abstract [en]

While various organic molecules have been suggested as environmentally friendly alternatives to inorganic electrode materials for lithium ion batteries, most of them suffer from slow kinetics as well as capacity fading due to dissolution. Herein we present the synthesis of poly(pyrrol-3-ylhydroquinone) (PPyQ), a polypyrrole (PPy) derivative with pending hydroquinone groups, for investigation of the use of a conducting polymer to immobilize redox active quinone units. This strategy eliminates dissolution of the active material while also increasing the conductivity. The quinone pending groups in PPyQ cycle reversibly in the potential region where the polymer backbone is conducting and chemically stable. In situ spectroelectrochemistry on PPyQ films reveals UV/vis transitions inherent to PPy, as well as quinone centered transitions, allowing detailed investigation of the interplay between the polymer doping process and the quinone redox conversion. Intriguingly, it is found that the charging of the PPy backbone halts during the redox reaction of the quinone pending groups. This opens up for the possibility of using PPy at low and constant doping levels while utilizing the charge storage capacity of the quinone pending groups when creating electric energy storage materials based on sustainable and renewable components.

National Category
Physical Chemistry Engineering and Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-210983 (URN)10.1021/jp408567h (DOI)000327110500015 ()
Available from: 2013-11-18 Created: 2013-11-18 Last updated: 2017-12-06Bibliographically approved
3. Hydroquinone–pyrrole dyads with varied linkers
Open this publication in new window or tab >>Hydroquinone–pyrrole dyads with varied linkers
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2016 (English)In: Beilstein Journal of Organic Chemistry, ISSN 2195-951X, E-ISSN 1860-5397, Vol. 12, p. 89-96Article in journal (Refereed) Published
Abstract [en]

A series of pyrroles functionalized in the 3-position with p-dimethoxybenzene via various linkers (CH2, CH2CH2, CH=CH, C≡C) has been synthesized. Their electronic properties have been deduced from 1H NMR, 13C NMR, and UV–vis spectra to detect possible interactions between the two aromatic subunits. The extent of conjugation between the subunits is largely controlled by the nature of the linker, with the largest conjugation found with the trans-ethene linker and the weakest with the aliphatic linkers. DFT calculations revealed substantial changes in the HOMO–LUMO gap that correlated with the extent of conjugation found experimentally. The results of this work are expected to open up for use of the investigated compounds as components of redox-active materials in sustainable, organic electrical energy storage devices.

Keywords
conjugation, heterocycles, hydroquinone, linker effect, pyrrole
National Category
Organic Chemistry Engineering and Technology
Research subject
Chemistry with specialization in Organic Chemistry; Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-276440 (URN)10.3762/bjoc.12.10 (DOI)000368473900001 ()
Funder
Swedish Foundation for Strategic Research Carl Tryggers foundation Stiftelsen Olle Engkvist ByggmästareSweGRIDS - Swedish Centre for Smart Grids and Energy Storage
Available from: 2016-02-12 Created: 2016-02-12 Last updated: 2017-11-30Bibliographically approved
4. Impact of Linker in Polypyrrole/Quinone Conducting Redox Polymers
Open this publication in new window or tab >>Impact of Linker in Polypyrrole/Quinone Conducting Redox Polymers
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2015 (English)In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 5, no 15, p. 11309-11316Article in journal (Refereed) Published
Abstract [en]

Organic conducting redox polymers are being investigated as the active component for secondary battery applications, as they have the potential to solve two of the main problems with small molecule-based organic electrodes for electrical energy storage, viz dissolution of the active compound in the electrolyte, and slow charge transport through the material. Herein we report the synthesis of a series of conducting redox polymers based on polypyrrole with hydroquinone pendant groups that are attached to the backbone via different linkers, and we investigate the impact of the linker on the interaction between the backbone and the pendant groups. For the directly linked polymer, oxidation of the pendant groups leads to a decrease of bipolaron absorbance, as well as a decrease in mass of the polymer film, both of which are reversible. The origin of these effects is discussed in light of the influence of the linker unit, electrolyte polarity, and electrolyte salt. For the longest linkers in the series, no interaction was observed, which was deemed the most beneficial situation for energy storage applications, as the energy storage capacity of the pendant groups can be utilized without disturbing the conductivity of the polymer backbone.

National Category
Physical Chemistry Engineering and Technology Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-230488 (URN)10.1039/c4ra15708g (DOI)000348986900057 ()
Available from: 2014-09-10 Created: 2014-08-26 Last updated: 2017-12-05
5. Synthesis and Characterization of Poly-3-((2,5-hydroquinone)vinyl)-1H-pyrrole: investigation on Backbone/Pendant Interactions in a Conducting Redox Polymer
Open this publication in new window or tab >>Synthesis and Characterization of Poly-3-((2,5-hydroquinone)vinyl)-1H-pyrrole: investigation on Backbone/Pendant Interactions in a Conducting Redox Polymer
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2017 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 19, no 16, p. 10427-10435Article in journal (Refereed) Published
Abstract [en]

We herein report the synthesis and electrochemical characterization of poly-3-((2,5-hydroquinone)vinyl)-1H-pyrrole, consisting of a polypyrrole backbone derivatized at the beta position by a vinyl-hydroquinone pendant group. The structure of the polymer was characterized by solid state NMR spectroscopy. The interactions between the polypyrrole backbone and the oxidized quinone or reduced hydroquinone pendant groups are probed by several in situ methods. In situ attenuated total reflectance-Fourier transform infrared spectroscopy shows spectroscopic response from both the doping of the polymer backbone and the redox activity of the pendant groups. Using an in situ Electrochemical Quartz Crystal Microbalance we reveal that the polymer doping is unaffected by the pendant group redox chemistry, as opposed to previous reports. Despite the continuous doping the electrochemical conversion from the hydroquinone state to the quinone state results in a significant conductance drop, as observed by in situ conductivity measurements using an InterDigitated Array electrode set-up. Twisting of the conducting polymer backbone as a result of a decreased separation between pendant groups due to π-π stacking in the oxidized state is suggested as the cause of this conductance drop.

National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-316490 (URN)10.1039/c6cp08736a (DOI)000400117700025 ()28379225 (PubMedID)
Funder
Swedish Foundation for Strategic Research Swedish Research CouncilCarl Tryggers foundation Stiftelsen Olle Engkvist ByggmästareSwedish Energy AgencyEU, Horizon 2020, 644631
Available from: 2017-03-01 Created: 2017-03-01 Last updated: 2017-11-25
6. Potential Tuning in Quinone-pyrrole Dyad Based Conducting Redox Polymers
Open this publication in new window or tab >>Potential Tuning in Quinone-pyrrole Dyad Based Conducting Redox Polymers
(English)Manuscript (preprint) (Other academic)
Abstract [en]

In this study, conducting redox polymers (CRPs), which consist of a polypyrrole conducting polymer (CP) backbone with attached quinone pendant groups (PGs), have been explored as electrode materials for organic batteries. A modular organic synthetic approach allows the assembly of the pyrrole and quinone units into quinone-pyrrole dyads. These dyad monomers were copolymerized electrochemically with pyrrole to yield the CRPs. DFT calculations were used to predict the formal potentials of the dyads, showing excellent agreement with the experimental values of the corresponding CRPs. Moreover, it is shown that the matching between the redox potential of PGs and the conductive region of CPs is an absolute requirement for good performance of these materials. With access to CRP materials with varying quinone formal potentials a prototype of a full organic based battery was constructed by choosing two CRPs with different quinone potentials. A galvanostatic charge-discharge study showed that the cell potentials coincided well with the difference in redox potential between the quinone substituents used in the anode and cathode CRP.

National Category
Nano Technology Organic Chemistry
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-316491 (URN)
Available from: 2017-03-01 Created: 2017-03-01 Last updated: 2017-12-11
7. Mechanistic Investigation of Charge Transport in a Conducting Redox Polymer
Open this publication in new window or tab >>Mechanistic Investigation of Charge Transport in a Conducting Redox Polymer
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

Herein we report a mechanistic study of the charge transport in poly-3-((2,5-hydroquinone)vinyl)-1H-pyrrole by conductance measurements at various temperatures performed in situ during doping of the polypyrrole backbone in contact with an aqueous electrolyte. Charge transport was found to occur by electron hopping with associated electron transfer activation energies in the range of 0.08 – 0.2 eV. In situ EPR experiments indicated polarons as the dominant charge carriers and the charge transport was found to follow a second-order dependence with respect to the number of accumulated charges. Based on the findings two plausible charge transport mechanisms are suggested for the electronic conduction in poly-3-((2,5-hydroquinone)vinyl)-1H-pyrrole.

National Category
Nano Technology
Identifiers
urn:nbn:se:uu:diva-316489 (URN)
Available from: 2017-03-01 Created: 2017-03-01 Last updated: 2017-03-13

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