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Electrochemical Characterizations of Conducting Redox Polymers: Electron Transport in PEDOT/Quinone Systems
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.ORCID iD: 0000-0002-0036-9911
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Organic electrode materials for rechargeable batteries have caught increasing attention since they can be used in new innovative applications such as flexible electronics and smart fabrics. They can provide safer and more environmentally friendly devices than traditional batteries made from metals. Conducting polymers constitute an interesting class of organic electrode materials that have been thoroughly studied for battery applications. They have high conductivity but are heavy relative to their energy storage ability and will hence form batteries with low weight capacity. Quinones, on the other hand, are low weight molecules that participate in electron transport in both animals and plants. They could provide batteries with high capacity but are easily dissolved in the electrolyte and have low conductivity. These two constituents can be combined into a conducting redox polymer that has both high conductivity and high capacity. In the present work, the conducting polymer PEDOT and the simplest quinone, benzoquinone, are covalently attached and form the conducting redox polymer used for most studies in this thesis. The charge transport mechanism is investigated by in situ conductivity measurements and is found to mainly be governed by band transport. Other properties such as packing, kinetics, mass changes, and spectral changes are also studied. A polymerization technique is also analyzed, that allows for polymerization from a deposited layer. Lastly, two different types of batteries using conducting redox polymers are constructed. The thesis gives insight into the fundamental properties of conducting redox polymers and paves the way for the future of organic electronics.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2019. , p. 59
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1819
Keywords [en]
Conducting Redox Polymer, PEDOT, Quinone, Charge transport, Conductivity, Organic Battery
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
URN: urn:nbn:se:uu:diva-383026ISBN: 978-91-513-0674-2 (print)OAI: oai:DiVA.org:uu-383026DiVA, id: diva2:1314519
Public defence
2019-08-30, Häggsalen, 10132, Ångström, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2019-06-10 Created: 2019-05-09 Last updated: 2019-08-23
List of papers
1. Characterization of PEDOT-Quinone Conducting Redox Polymers for Water Based Secondary Batteries
Open this publication in new window or tab >>Characterization of PEDOT-Quinone Conducting Redox Polymers for Water Based Secondary Batteries
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2017 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 235, p. 356-364Article in journal (Refereed) Published
Abstract [en]

Lithium-ion technologies show great promise to meet the demands that the transition towards renewable energy sources and the electrification of the transport sector put forward. However, concerns regarding lithium-ion batteries, including limited material resources, high energy consumption during production, and flammable electrolytes, necessitate research on alternative technologies for electrochemical energy storage. Organic materials derived from abundant building blocks and with tunable properties, together with water based electrolytes, could provide safe, inexpensive and sustainable alternatives. In this study, two conducting redox polymers based on poly(3,4-ethylenedioxythiophene) (PEDOT) and a hydroquinone pendant group have been synthesized and characterized in an acidic aqueous electrolyte. The polymers were characterized with regards to kinetics, pH dependence, and mass changes during oxidation and reduction, as well as their conductance. Both polymers show redox matching, i.e. the quinone redox reaction occurs within the potential region where the polymer is conducting, and fast redox conversion that involves proton cycling during pendant group redox conversion. These properties make the presented materials promising candidates as electrode materials for water based all-organic batteries.

Keywords
Conducting Redox Polymer, Quinone, Organic Batteries, Proton Batteries, Redox Matching
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-319049 (URN)10.1016/j.electacta.2017.03.068 (DOI)000398330200042 ()
Funder
Swedish Foundation for Strategic Research Swedish Research CouncilCarl Tryggers foundation Swedish Energy AgencyEU, Horizon 2020, 644631
Available from: 2017-03-30 Created: 2017-03-30 Last updated: 2019-05-09Bibliographically approved
2. An All-Organic Proton Battery
Open this publication in new window or tab >>An All-Organic Proton Battery
2017 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 139, no 13, p. 4828-4834Article in journal (Refereed) Published
Abstract [en]

Rechargeable batteries that use organic matter as. the capacity-carrying material have previously been considered a technology for the future. Earlier batteries in which both the anode and cathode consisted of organic material required significant amounts of conductive additives and were often based on metal-ion electrolytes containing Li+ or Na+. However, we have used conducting poly(3,4-ethylenedioxythiophene) (PEDOT), functionalized with anthraquinone (PEDQT-AQ) or, benzonquinone (PEDOT-BQ) pendant groups as the negative and positive electrode materials, respectively, to make an all-organic proton battery devoid of metals. The electrolyte consists of a proton donor and acceptor slurry containing substituted pyridinium triflates and the corresponding pyridine base. This slurry allows the 2e(-)/2H(+) quinone/hydroquinone redox reactions while suppressing proton reduction in the battery cell. By using strong (acidic) proton donors, the formal potential of the quinone redox reactions is tuned into the potential region in which the PEDOT backbone is conductive, thus eliminating the need for conducting additives. In this all-organic proton battery cell, PEDOT-AQ and PEDOT-BQ deliver 103 and 120 mAh g(-1), which correspond to 78% and 75%, respectively, of the theoretical specific capacity of the materials at an average cell potential of 0.5 V. We show that PEDOT-BQ determines the cycling stability of the device while PEDOT-AQ provides excellent reversibility for at least 1000 cycles. This proof-of-concept shows the feasibility of assembling all organic proton batteries which require no conductive additives and also reveals where the challenges and opportunities lie on the path to producing plastic batteries.

Keywords
rechargeable lithium batteries, li-ion batteries, electrode materials, energy-storage, cathode, anode, salt, electrochemistry, derivatives, polymer
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-319048 (URN)10.1021/jacs.7b00159 (DOI)000398764000036 ()28293954 (PubMedID)
Funder
Swedish Foundation for Strategic Research Swedish Research CouncilCarl Tryggers foundation Swedish Energy AgencyEU, Horizon 2020, H2020/2014-2020 644631
Available from: 2017-03-30 Created: 2017-03-30 Last updated: 2019-05-09Bibliographically approved
3. Investigating electron transport in a PEDOT/Quinone conducting redox polymer with in situ methods
Open this publication in new window or tab >>Investigating electron transport in a PEDOT/Quinone conducting redox polymer with in situ methods
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2019 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 308, p. 277-284Article in journal (Refereed) Published
Abstract [en]

A conducting redox polymer is investigated in acidic electrolyte using various in situ methods, including electron paramagnetic resonance (EPR), UV–vis spectroscopy, and conductance measurements. The quinone redox active pendant group has a formal potential of 0.67 V (vs. standard hydrogen electrode) where a 2e2H process occurs. By analyzing the rate constant at different temperatures, the rate-limiting step in the redox reaction was found to be a thermally activated process with an activation energy of 0.3 eV. The electron transport through the conducting polymerwas found to be non-thermally activated and, hence, not redox rate-limiting. This is also the first time a negative temperature dependence has been reported for a conducting redox polymer in the same potential region where the redox active pendant group has its formal potential. EPR and conductance data indicated that the conductivity is governed by both polarons and bipolarons but their ratio is shifting during oxidation and reduction of the polymer.

Keywords
Conducting Redox Polymer, PEDOT, Quinone, Temperature dependence
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-383025 (URN)10.1016/j.electacta.2019.03.207 (DOI)000466713100030 ()
Funder
Carl Tryggers foundation Swedish Energy AgencySwedish Research CouncilStiftelsen Olle Engkvist ByggmästareSwedish Research Council Formas
Available from: 2019-05-07 Created: 2019-05-07 Last updated: 2019-06-10Bibliographically approved
4. Post-Deposition Polymerization: A Method for Circumventing Processing of Insoluble Conducting Polymers
Open this publication in new window or tab >>Post-Deposition Polymerization: A Method for Circumventing Processing of Insoluble Conducting Polymers
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(English)Manuscript (preprint) (Other (popular science, discussion, etc.))
Abstract [en]

A method, termed post-deposition polymerization, for the synthesis of conducting polymers is presented, which enables solid state polymerization of oligomeric layers by oxidative polymerization. The method was developed as a general tool for the preparation of conducting polymer layers that allows for industrially viable solution-processing methods to be used for substrate coating. We use trimer building blocks based on 3,4-ethylenedioxythiophene (EDOT) in the processing step, and show that the resulting trimer layer has innate conductivity when oxidized, which presumably is instrumental for successful polymerization of the solid layer. As judged by in situ conductance measurement during oxidative polymerization of the trimer layer, the layer-conductivity is greatly increased as a result of polymerization. Successful solid state polymerization was also confirmed by the irreversible spectral changes, monitored in-situ during polymerization, resulting in signature spectral transitions of conducting polymers from an initial spectrum derived solely from trimer absorption. From the in situ determined mass changes we estimate the swelling during post-deposition polymerization as well as the average polymer length. Electrochemical characterization of the resulting polymer show fast redox conversion as well as non-activated electron transport through the material indicating that the post-deposition polymerization-generated polymer indeed show promising properties. We believe that the post-deposition polymerization method will enable investigations, currently hampered by limited processability, of interesting families of conducting polymer materials.

Keywords
Conducting Polymer, PEDOT, polymerization
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-383028 (URN)
Available from: 2019-05-09 Created: 2019-05-09 Last updated: 2019-05-16

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