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  • 1.
    Emanuelsson, Rikard
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sterby, Mia
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Strømme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sjödin, Martin
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    An All-Organic Proton Battery2017Inngår i: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 139, nr 13, s. 4828-4834Artikkel i tidsskrift (Fagfellevurdert)
    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.

  • 2.
    Huang, Hao
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sterby, Mia
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Strömme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sjödin, Martin
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Quinone Based Conducting Redox Polymer for Energy Storage2017Konferansepaper (Fagfellevurdert)
  • 3.
    Sjödin, Martin
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sterby, Mia
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Huang, Hao
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Huang, Xiao
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Organisk kemi.
    Gogoll, A
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Organisk kemi.
    Strömme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Quinone-Substituted Conducting Polymers as Electrode Materials for All-Organic Proton Batteries2018Konferansepaper (Fagfellevurdert)
  • 4.
    Sjödin, Martin
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sterby, Mia
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Huang, Hao
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Wang, Huan
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Strömme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Conducting Redox Polymer Batteries2018Konferansepaper (Fagfellevurdert)
  • 5.
    Sjödin, Martin
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sterby, Mia
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Strietzel, Christian
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Yang, Li
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Huang, Hao
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Wang, Huan
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Huang, Xiao
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Organisk kemi.
    Gogoll, A
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Organisk kemi.
    Strömme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Conducting Redox Polymer Based Batteries2017Konferansepaper (Fagfellevurdert)
  • 6.
    Sjödin, Martin
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sterby, Mia
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Åkerlund, Lisa
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Huang, Hao
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Huang, Xiao
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Organisk kemi.
    Gogoll, Adolf
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Organisk kemi.
    Strömme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Organic Batteries Based on Quinone-Substituted Conducting Polymers2017Konferansepaper (Fagfellevurdert)
  • 7.
    Sjödin, Martin
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Wang, Huan
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Åkerlund, Lisa
    Sterby, Mia
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Huang, Hao
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Gogoll, A
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Organisk kemi.
    Strömme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Organiska batterier för hållbar och ökad energi-effektivitet i lokal energilagring2018Konferansepaper (Annet vitenskapelig)
  • 8.
    Sterby, Mia
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Electrochemical Characterizations of Conducting Redox Polymers: Electron Transport in PEDOT/Quinone Systems2019Doktoravhandling, med artikler (Annet vitenskapelig)
    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.

    Delarbeid
    1. Characterization of PEDOT-Quinone Conducting Redox Polymers for Water Based Secondary Batteries
    Åpne denne publikasjonen i ny fane eller vindu >>Characterization of PEDOT-Quinone Conducting Redox Polymers for Water Based Secondary Batteries
    Vise andre…
    2017 (engelsk)Inngår i: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 235, s. 356-364Artikkel i tidsskrift (Fagfellevurdert) 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.

    Emneord
    Conducting Redox Polymer, Quinone, Organic Batteries, Proton Batteries, Redox Matching
    HSV kategori
    Forskningsprogram
    Teknisk fysik med inriktning mot nanoteknologi och funktionella material
    Identifikatorer
    urn:nbn:se:uu:diva-319049 (URN)10.1016/j.electacta.2017.03.068 (DOI)000398330200042 ()
    Forskningsfinansiär
    Swedish Foundation for Strategic Research Swedish Research CouncilCarl Tryggers foundation Swedish Energy AgencyEU, Horizon 2020, 644631
    Tilgjengelig fra: 2017-03-30 Laget: 2017-03-30 Sist oppdatert: 2019-05-09bibliografisk kontrollert
    2. An All-Organic Proton Battery
    Åpne denne publikasjonen i ny fane eller vindu >>An All-Organic Proton Battery
    2017 (engelsk)Inngår i: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 139, nr 13, s. 4828-4834Artikkel i tidsskrift (Fagfellevurdert) 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.

    Emneord
    rechargeable lithium batteries, li-ion batteries, electrode materials, energy-storage, cathode, anode, salt, electrochemistry, derivatives, polymer
    HSV kategori
    Forskningsprogram
    Teknisk fysik med inriktning mot nanoteknologi och funktionella material
    Identifikatorer
    urn:nbn:se:uu:diva-319048 (URN)10.1021/jacs.7b00159 (DOI)000398764000036 ()28293954 (PubMedID)
    Forskningsfinansiär
    Swedish Foundation for Strategic Research Swedish Research CouncilCarl Tryggers foundation Swedish Energy AgencyEU, Horizon 2020, H2020/2014-2020 644631
    Tilgjengelig fra: 2017-03-30 Laget: 2017-03-30 Sist oppdatert: 2019-05-09bibliografisk kontrollert
    3. Investigating electron transport in a PEDOT/Quinone conducting redox polymer with in situ methods
    Åpne denne publikasjonen i ny fane eller vindu >>Investigating electron transport in a PEDOT/Quinone conducting redox polymer with in situ methods
    Vise andre…
    2019 (engelsk)Inngår i: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 308, s. 277-284Artikkel i tidsskrift (Fagfellevurdert) 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.

    Emneord
    Conducting Redox Polymer, PEDOT, Quinone, Temperature dependence
    HSV kategori
    Forskningsprogram
    Teknisk fysik med inriktning mot nanoteknologi och funktionella material
    Identifikatorer
    urn:nbn:se:uu:diva-383025 (URN)10.1016/j.electacta.2019.03.207 (DOI)000466713100030 ()
    Forskningsfinansiär
    Carl Tryggers foundation Swedish Energy AgencySwedish Research CouncilStiftelsen Olle Engkvist ByggmästareSwedish Research Council Formas
    Tilgjengelig fra: 2019-05-07 Laget: 2019-05-07 Sist oppdatert: 2019-06-10bibliografisk kontrollert
    4. Post-Deposition Polymerization: A Method for Circumventing Processing of Insoluble Conducting Polymers
    Åpne denne publikasjonen i ny fane eller vindu >>Post-Deposition Polymerization: A Method for Circumventing Processing of Insoluble Conducting Polymers
    Vise andre…
    (engelsk)Manuskript (preprint) (Annet (populærvitenskap, debatt, mm))
    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.

    Emneord
    Conducting Polymer, PEDOT, polymerization
    HSV kategori
    Forskningsprogram
    Teknisk fysik med inriktning mot nanoteknologi och funktionella material
    Identifikatorer
    urn:nbn:se:uu:diva-383028 (URN)
    Tilgjengelig fra: 2019-05-09 Laget: 2019-05-09 Sist oppdatert: 2019-05-16
  • 9.
    Sterby, Mia
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Huang, Xiao
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Organisk kemi.
    Gogoll, Adolf
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Organisk kemi.
    Strömme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sjödin, Martin
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Characterization of PEDOT-Quinone Conducting Redox Polymers for Water Based Secondary Batteries2017Inngår i: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 235, s. 356-364Artikkel i tidsskrift (Fagfellevurdert)
    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.

  • 10.
    Sterby, Mia
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Mamedov, Fikret
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - Ångström, Molekylär biomimetik.
    Strömme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sjödin, Martin
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Investigating electron transport in a PEDOT/Quinone conducting redox polymer with in situ methods2019Inngår i: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 308, s. 277-284Artikkel i tidsskrift (Fagfellevurdert)
    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.

  • 11.
    Sterby, Mia
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Strömme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sjödin, Martin
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Electronic properties of a PEDOT/Quinone Conducting Redox Polymer2018Konferansepaper (Annet vitenskapelig)
    Abstract [en]

    Organic materials can be used to ensure sustainable electrical energy storage, thus avoiding the use of inorganic materials that are inherently non-renewable and associated with large energy consumptions in their mining and refining. To ensure sufficient conductivity, most organic batteries researched on today use conducting additives since organic molecules, in general, are insulating. A different approach is to use conducting redox polymers (CRPs). CRPs consist of a redox active pendant group attached to a conducting polymer backbone.

     

    The present work focuses on characterizing a cathode material for water based batteries. The material consists of 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 photosynthesis and in respiration.

     

    Redox matching (i.e. the redox reaction of the pendant group occurring at a potential where the polymer is conducting) between the conducting polymer and the pendant group is crucial for CRPs since the electrons stored in the pendant groups have to travel through the polymer to the current collector. From in situ conductance measurements we have previously shown that redox matching exists in the studied CRP.2 In this work we present studies of the redox matched CRP showing a non-activated electron transport through the polymer backbone, an activated process for the quinone redox conversion, and indication of polarons being the dominant charge carrier. The reorganization energy of the quinone as well as ion mobility through the polymer will also 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.

    2. Sterby, M.; Emanuelsson, R.; Huang, X.; Gogoll, A.; Strømme, M.; Sjödin, M., Characterization of PEDOT-Quinone Conducting Redox Polymers for Water Based Secondary Batteries. Electrochim. Acta 2017, 235, 356–364.

  • 12.
    Sterby, Mia
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Strömme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sjödin, Martin
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    In Situ Methods for Understanding Charge Transport in a Conducting Redox Polymer2018Inngår i: Materials Research Society. Fall meeting 2018. Boston: Excitons, Electrons and Ions in Organic Materials / [ed] MRS, Boston, 2018, artikkel-id EP05.01.07Konferansepaper (Fagfellevurdert)
    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.

  • 13.
    Sterby, Mia
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Strømme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Gogoll, Adolf
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Organisk kemi.
    Sjödin, Martin
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Characterization of a PEDOT/Quinone Conducting Redox Polymer2016Konferansepaper (Annet vitenskapelig)
    Abstract [en]

    Organic materials can be used to ensure sustainable electrical energy storage, thus avoiding the use of inorganic materials that are inherently non-renewable and associated with large energy consumptions in their mining and refining. One category of organic energy storage materials consists of conducting redox polymers (CRPs). They include a conducting polymer backbone (CP), a redox active pendant group (PG), and a linker attaching the PG to the CP. The present work involves the CP poly(3,4-ethylenedioxythiophene) (PEDOT) and a quinone PG in acidic water solution. Quinones constitute an attractive class of molecules as they show reversible redox chemistry in several electrolyte systems, possess a high charge storage capacity and are naturally occurring e.g. in the electron transport chains in respiration and in photosynthesis. The CRP studied is characterized by cyclic voltammetry as well as by EQCM, in-situ conductance, and in-situ spectroscopic methods. In this work we present the formal potential of the quinone, the rate constant for electron transport in the polymer, mass changes during electrochemical redox conversion in different potential regions, and conductance data providing support for a CP-mediated electron transport through the material. Based on the results the electron and ion transport during electrochemical redox conversion will be discussed.                                                                                              

  • 14.
    Sterby, Mia
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Strømme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Gogoll, Adolf
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Organisk kemi.
    Sjödin, Martin
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Linker Effect in PEDOT/Quinone Organic Battery Materials2016Konferansepaper (Fagfellevurdert)
    Abstract [en]

    One way to ensure sustainable electrical energy storage is to use organic materials. Organic materials can be made from renewable resources and thus the use of limited resources needed for inorganic materials is avoided. Conducting redox polymers (CRPs) are one type of organic material that can be used in e.g. batteries. CRPs consist of a conducting polymer backbone, a redox active pendant group, and a linker connecting the pendant group to the polymer. The present work focuses on the well-studied conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) with quinone pendant groups in water based systems. Quinones constitute a class of redox active molecules used in nature e.g. for electron transport in photosynthesis and in respiration. Although the third unit, the linker, is a passive part in the system it can greatly impact the behavior of the resulting CRP. In this report we present scan rate dependent voltammetric data as well as EQCM and in-situ conductance on two CRPs differing only by two CH2 groups in the linker. Figure 1 shows molecular structure, CV, and EQCM data of I and II indicating the significant influence that the minor difference in the linking unit has on the redox chemistry in these systems.

  • 15.
    Sterby, Mia
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Strømme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sjödin, Martin
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Electrochemical Characterization of Conducting Redox Polymers – Redox Matching and Mass Transport2017Konferansepaper (Fagfellevurdert)
    Abstract [en]

    In order to provide society with sustainable electrical energy storage technologies, organic based batteries is an attractive target. Making batteries with materials from renewable resources would ensure production without the use of non-renewable inorganic materials that have to be acquired through energy consuming mining. To ensure sufficient conductivity, most organic batteries researched on today use conducting additives since organic molecules, in general, are insulating. A different approach is to use conducting redox polymers (CRPs). They utilize a conducting polymer as a backbone for good conductivity and redox active pendant groups to ensure high charge storage capacity and a well-defined redox process. The polymer backbone used in the present work is poly(3,4-ethylenedioxythiophene) while quinones are used as pendant groups. In an all-organic battery the two electrodes will have quinones with different redox potentials, resulting in a voltage difference between the electrodes. This work focuses on characterizing the cathode material in water electrolytes. The CRPs are studied with regard to conductivity and mass transport, by in situ conductance as well as electrochemical quartz crystal microbalance experiments. Redox matching between the conducting polymer and the pendant group is evident from in situ conductance measurements. From EQCM measurements it is evident that during the hydroquinone/quinone redox conversion only protons are cycled in and out of the CRP.

  • 16.
    Sterby, Mia
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Strømme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sjödin, Martin
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Electrochemical Properties of a PEDOT-Based Conducting Redox Polymer2017Konferansepaper (Fagfellevurdert)
    Abstract [en]

    Organic molecules are generally insulating and to ensure electrical conductivity when organic matter is used as electrode materials, conducting additives are commonly used. Another approach is to use conducting polymers as a backbone to which the capacity carrying redox active pendant groups are attached. In this work we employed poly(3,4-ethylenedioxythiophene) (PEDOT) with different quinone moieties as pendant groups, forming conducting redox polymers (CRPs). By using quinones with different redox potentials, CRPs can be used as electrode materials in all-organic batteries where the difference in formal potential between the quinone redox reactions determines the cell-potential of the battery. To avoid the use of flammable and harmful organic electrolytes we used acidic water based electrolytes in the characterization of these polymers, including in situ conductance, electrochemical quartz crystal microbalance measurements, and cyclic voltammetry. The results from polymers carrying different quinones will be presented. For example: in situ conductance measurements of benzoquinone substituted CRPs show that redox matching is evident, i.e. the quinone pendant group has its redox reaction occurring in a potential window where the polymer is conducting (Figure 1). The polymers also show fast kinetics and during the quinone redox conversion only protons seem to be cycled in and out of the CRPs.

  • 17.
    Sterby, Mia
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Strietzel, Christian
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Strömme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material. Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Fasta tillståndets fysik.
    Sjödin, Martin
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Post-Deposition Polymerization: A Method for Circumventing Processing of Insoluble Conducting PolymersManuskript (preprint) (Annet (populærvitenskap, debatt, mm))
    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.

  • 18.
    Strietzel, Christian
    et al.
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sterby, Mia
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Emanuelsson, Rikard
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Strömme, Maria
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Sjödin, Martin
    Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Tekniska sektionen, Institutionen för teknikvetenskaper, Nanoteknologi och funktionella material.
    Binder- and conducting additive free organic electrode materials – Post-deposition polymerization of conducting redox oligomers 2019Inngår i: Organic Battery Days 2019, Jena, 2019, artikkel-id P43Konferansepaper (Fagfellevurdert)
1 - 18 of 18
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