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Strietzel, C., Sterby, M., Emanuelsson, R., Strömme, M. & Sjödin, M. (2019). Binder- and conducting additive free organic electrode materials – Post-deposition polymerization of conducting redox oligomers . In: Organic Battery Days 2019: . Paper presented at Organic Battery Days 2019. Jena 3-5/6 2019. Jena, Article ID P43.
Open this publication in new window or tab >>Binder- and conducting additive free organic electrode materials – Post-deposition polymerization of conducting redox oligomers
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2019 (English)In: Organic Battery Days 2019, Jena, 2019, article id P43Conference paper, Poster (with or without abstract) (Refereed)
Place, publisher, year, edition, pages
Jena: , 2019
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-389541 (URN)
Conference
Organic Battery Days 2019. Jena 3-5/6 2019
Available from: 2019-07-17 Created: 2019-07-17 Last updated: 2019-07-17
Sterby, M. (2019). Electrochemical Characterizations of Conducting Redox Polymers: Electron Transport in PEDOT/Quinone Systems. (Doctoral dissertation). Uppsala: Acta Universitatis Upsaliensis
Open this publication in new window or tab >>Electrochemical Characterizations of Conducting Redox Polymers: Electron Transport in PEDOT/Quinone Systems
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
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:nbn:se:uu:diva-383026 (URN)978-91-513-0674-2 (ISBN)
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
Sterby, M., Emanuelsson, R., Mamedov, F., Strömme, M. & Sjödin, M. (2019). Investigating electron transport in a PEDOT/Quinone conducting redox polymer with in situ methods. Electrochimica Acta, 308, 277-284
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
Sjödin, M., Emanuelsson, R., Sterby, M., Huang, H., Wang, H. & Strömme, M. (2018). Conducting Redox Polymer Batteries. In: : . Paper presented at Americas International Meeting on Electrochemistry and Solid State Science,September 30 – October 4, Cancun, Mexico, 2018.
Open this publication in new window or tab >>Conducting Redox Polymer Batteries
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2018 (English)Conference paper, Oral presentation with published abstract (Refereed)
National Category
Other Materials Engineering
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-365693 (URN)
Conference
Americas International Meeting on Electrochemistry and Solid State Science,September 30 – October 4, Cancun, Mexico, 2018
Available from: 2018-11-12 Created: 2018-11-12 Last updated: 2019-03-06Bibliographically approved
Sterby, M., Emanuelsson, R., Strömme, M. & Sjödin, M. (2018). In Situ Methods for Understanding Charge Transport in a Conducting Redox Polymer. In: MRS (Ed.), Materials Research Society. Fall meeting 2018. Boston: Excitons, Electrons and Ions in Organic Materials. Paper presented at MRS Fall meeting. Boston 2018. Boston, Article ID EP05.01.07.
Open this publication in new window or tab >>In Situ Methods for Understanding Charge Transport in a Conducting Redox Polymer
2018 (English)In: Materials Research Society. Fall meeting 2018. Boston: Excitons, Electrons and Ions in Organic Materials / [ed] MRS, Boston, 2018, article id EP05.01.07Conference paper, Oral presentation only (Refereed)
Abstract [en]

Organic materials can be used to ensure sustainable electrical energy storage, but since organic molecules are generally insulating conducting additives are commonly used to ensure electrical conductivity throughout the material. A different approach is to use conducting redox polymers (CRPs). CRPs consist of a redox active pendant group, used for its high capacity, attached to a conducting polymer backbone. The CRP presented here is aimed to be used as the positive electrode in a water-based organic battery. In this work we employ the well-studied conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) with a quinone pendant group, a combination that we have proven can work in an all-organic proton battery.

1 Quinones constitute an attractive class of molecules as they possess a high charge storage capacity, show reversible redox chemistry, and are naturally occurring, e.g., in the electron transport chains in respiration and in photosynthesis. The aim of the study is to understand the charge transport properties of the CRP. The CRP studied is characterized by various in-situ electrochemical methods including conductance, Quartz Crystal Microbalance (QCM), UV-vis and Electron Paramagnetic Resonance (EPR). Based on the results the electron and ion transport during electrochemical redox conversion will be discussed. 1. Emanuelsson, R.; Sterby, M.; Strømme, M.; Sjödin, M., An All-Organic Proton Battery. J. Am. Chem. Soc. 2017, 139 (13), 4828-4834.

Place, publisher, year, edition, pages
Boston: , 2018
National Category
Engineering and Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-366558 (URN)
Conference
MRS Fall meeting. Boston 2018
Available from: 2018-11-21 Created: 2018-11-21 Last updated: 2019-05-07
Sjödin, M., Emanuelsson, R., Wang, H., Åkerlund, L., Sterby, M., Huang, H., . . . Strömme, M. (2018). Organiska batterier för hållbar och ökad energi-effektivitet i lokal energilagring. In: : . Paper presented at Framtidens Elsystem, 2018, Stockholm, Sweden.
Open this publication in new window or tab >>Organiska batterier för hållbar och ökad energi-effektivitet i lokal energilagring
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2018 (Swedish)Conference paper, Oral presentation with published abstract (Other academic)
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-366423 (URN)
Conference
Framtidens Elsystem, 2018, Stockholm, Sweden
Available from: 2018-11-20 Created: 2018-11-20 Last updated: 2019-03-13Bibliographically approved
Sjödin, M., Emanuelsson, R., Sterby, M., Huang, H., Huang, X., Gogoll, A. & Strömme, M. (2018). Quinone-Substituted Conducting Polymers as Electrode Materials for All-Organic Proton Batteries. In: : . Paper presented at 69th Annual Meeting of the International Society of Electrochemistry, 2 - 7 September 2018 Bologna, Italy. Uppsala
Open this publication in new window or tab >>Quinone-Substituted Conducting Polymers as Electrode Materials for All-Organic Proton Batteries
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2018 (English)Conference paper, Oral presentation with published abstract (Refereed)
Place, publisher, year, edition, pages
Uppsala: , 2018
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-365692 (URN)
Conference
69th Annual Meeting of the International Society of Electrochemistry, 2 - 7 September 2018 Bologna, Italy
Available from: 2018-11-12 Created: 2018-11-12 Last updated: 2019-03-13Bibliographically approved
Emanuelsson, R., Sterby, M., Strømme, M. & Sjödin, M. (2017). An All-Organic Proton Battery. Journal of the American Chemical Society, 139(13), 4828-4834
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
Sterby, M., Emanuelsson, R., Huang, X., Gogoll, A., Strömme, M. & Sjödin, M. (2017). Characterization of PEDOT-Quinone Conducting Redox Polymers for Water Based Secondary Batteries. Electrochimica Acta, 235, 356-364
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
Sjödin, M., Emanuelsson, R., Sterby, M., Strietzel, C., Yang, L., Huang, H., . . . Strömme, M. (2017). Conducting Redox Polymer Based Batteries. In: : . Paper presented at Organic Battery Days, Uppsala, June 8-9, 2017..
Open this publication in new window or tab >>Conducting Redox Polymer Based Batteries
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2017 (English)Conference paper, Oral presentation with published abstract (Refereed)
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-334410 (URN)
Conference
Organic Battery Days, Uppsala, June 8-9, 2017.
Available from: 2017-11-23 Created: 2017-11-23 Last updated: 2017-12-13Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0002-0036-9911

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