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A crosslinked conducting polymer with well-defined proton trap function for reversible proton cycling in aprotic environments
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials. (Nanoteknologi och Funktionella Material)ORCID iD: 0000-0002-8801-2983
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.ORCID iD: 0000-0002-4726-4121
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.ORCID iD: 0000-0002-2004-5869
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.ORCID iD: 0000-0002-5496-9664
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2020 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, E-ISSN 2050-7496, Vol. 8, no 24, p. 12114-12123Article in journal (Refereed) Published
Abstract [en]

In this paper, a well-defined proton trap material containing a hydroquinone unit flanked by two pyridine proton acceptors is presented. In combination with a terthiophene trimer, based on 3,4-ethylenedioxythiophene and 3,4-propylenedioxythiophene units, a conducting material with reversible redox properties is obtained. We apply post-deposition polymerization of the functionalized terthiophene trimer to provide a conducting polymer, which allows investigation of the electrochemical properties of the proton trap material. In situ studies concerning conductance measurements, mass uptake, electronic transitions and bonding vibrations indicate stable internal proton cycling between the hydroquinone and the pyridine functionality without affecting the conductivity or the doping process. The theoretical capacity of 42 mA h g−1, based on the pendant group redox conversion, can be achieved in a three electrode setup by potential step charging (25 s) at 0.5 V vs. Fc0/+ with subsequent discharging at 2C (0.5–0 V vs. Fc0/+). The total theoretical capacity available, including the contribution from the backbone, is 84 mA h g−1 and coin cell batteries with the conducting redox polymer as cathode material (without any additive) vs. lithium foil as anode showed a discharge capacity of 81 mA h g−1 (97% of the theoretical capacity) already from the first cycle (2.5–3.8 V vs. Li0/+ at 2C). The capacity was maintained during prolonged cycling and showed a capacity retention of 99% after 100 cycles and 98% after 200 cycles indicating high stability of this organic cathode material when applied in a battery configuration.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2020. Vol. 8, no 24, p. 12114-12123
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
URN: urn:nbn:se:uu:diva-414279DOI: 10.1039/D0TA03343JISI: 000542473000019OAI: oai:DiVA.org:uu-414279DiVA, id: diva2:1446475
Funder
Swedish Energy AgencyCarl Tryggers foundation Olle Engkvists stiftelseÅForsk (Ångpanneföreningen's Foundation for Research and Development)Swedish Research Council FormasStandUpAvailable from: 2020-06-24 Created: 2020-06-24 Last updated: 2023-12-04Bibliographically approved
In thesis
1. Electrochemical characterizations of conducting redox polymers with proton traps: Enabling proton cycling in aprotic systems for high potential energy storage
Open this publication in new window or tab >>Electrochemical characterizations of conducting redox polymers with proton traps: Enabling proton cycling in aprotic systems for high potential energy storage
2021 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Floods, droughts and unpredictable weather could be the new reality for millions of people in a near future, unless we drastically decrease our greenhouse gas emissions to prevent the global average temperature from increasing even further. Material innovations will most certainly be essential for many of the technical solutions needed in order to tackle environmental issues. One major challenge is how to deal with the massive energy demand, following the average lifestyle of today, in a way that is both reliable and sustainable. Renewable energy sources have a varying output over time, hence cannot meet the demand for electricity by themselves. To buffer between demand and production, new ways to store the renewably produced energy are crucial. From a life cycle aspect conventional battery types are far from sustainable, and, with the increasing number of electronic devices for numerous applications, we need new options.

This thesis explores conducting redox polymers (CRPs), which can be utilized as organic cathode materials in high potential energy storage. Hydroquinone (HQ) was applied as the capacity carrying pendant group, and by the introduction of a proton trap functionality the high reduction potential of quinone-proton cycling was achieved also in aprotic electrolytes. The high reduction potential allows for redox matching with the polymer backbone, crucial for CRPs to work as energy storage materials without any additives, and this was studied by in situ conductance with IDA. In situ EQCM was applied in order to examine the cycling chemistry, and the constant mass uptake during the full oxidation cycle (and reverse during the reduction cycle) indicated uptake of charge compensating ions. Further, the proton trap functionality and its effectiveness were investigated by compositional variation, FTIR and variation of electrolyte. In situ UV/Vis was applied in order to study the electronic transitions of the bandgap, the charge carriers and the pendant group redox conversion.

The results presented introduce a new route for utilizing protonated forms of quinones as capacity carriers in aprotic media, by incorporating a proton trap in the material. The battery prototypes point to the versatility of the proton trap materials, having reversible proton cycling also when the electrolyte contains metal salts. With dual-ion type batteries the cycling chemistry of the anode is disconnected from the cathode, which allows for free choice of anode material.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2021. p. 79
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 2026
Keywords
Conducting redox polymers, Proton trap, Quinones, Organic energy storage, Organic batteries
National Category
Engineering and Technology Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-438906 (URN)978-91-513-1175-3 (ISBN)
Public defence
2021-05-20, Polhemsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:30 (English)
Opponent
Supervisors
Available from: 2021-04-29 Created: 2021-03-28 Last updated: 2021-05-25Bibliographically approved

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Åkerlund, LisaEmanuelsson, RikardHernández, GuiomarStrømme, MariaSjödin, Martin

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