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Oka, K., Strietzel, C., Emanuelsson, R., Nishide, H., Oyaizu, K., Strömme, M. & Sjödin, M. (2019). Characterization of PEDOT-Quinone conducting redox polymers in water-in-salt electrolytes for safe and high-energy Li-ion batteries. Electrochemistry communications, 105, Article ID 106489.
Open this publication in new window or tab >>Characterization of PEDOT-Quinone conducting redox polymers in water-in-salt electrolytes for safe and high-energy Li-ion batteries
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2019 (English)In: Electrochemistry communications, ISSN 1388-2481, E-ISSN 1873-1902, Vol. 105, article id 106489Article in journal (Refereed) Published
Abstract [en]

Li-ion batteries (LIBs) raise safety and environmental concerns, which mostly arise from their toxic and flammable electrolytes and the extraction of limited material resources by mining. Recently, water-in-salt electrolytes (WiSEs), in which a large amount of lithium salt is dissolved in water, have been proposed to allow for assembling safe and high-voltage (>3.0 V) aqueous LIBs. In addition, organic materials derived from abundant building blocks and their tunable properties could provide safe and sustainable replacements for inorganic cathode materials. In the current work, the electrochemical properties of a conducting redox polymer based on poly(3,4-ethylenedioxythiophene) (PEDOT) with hydroquinone (HQ) pendant groups have been characterized in WiSEs. The quinone redox reaction occurs within the potential region where the polymer is conducting, and fast redox conversion that involves lithium cycling during pendant group redox conversion was observed. These properties make conducting redox polymers promising candidates as cathode-active materials for safe and high-energy aqueous LIBs. An organic-based aqueous LIB, with a HQ-PEDOT as a cathode, Li4Ti5O12 (LTO) as an anode, and ca. 15 m lithium bis(trifluoromethanesulfonyl)imide water/dimethyl carbonate (DMC) as electrolyte, yielded an output voltage of 1.35 V and high rate capabilities up to 500C.

Place, publisher, year, edition, pages
Elsevier, 2019
Keywords
Conducting redox polymer, Organic electronics, Renewable energy storage, Lithium ion battery, Water-in-salt electrolyte, Quinone
National Category
Nano Technology Materials Chemistry
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-389513 (URN)10.1016/j.elecom.2019.106489 (DOI)000484833800003 ()
Funder
Carl Tryggers foundation Swedish Research CouncilSwedish Research Council FormasSweGRIDS - Swedish Centre for Smart Grids and Energy Storage
Available from: 2019-07-16 Created: 2019-07-16 Last updated: 2019-10-17Bibliographically approved
Sjödin, M. (2019). ConductingRedox polymer Batteries. In: Waseda University (Ed.), Waseda conference on Future Battery Materials 2019: . Paper presented at Waseda conference on Future Battery Materials. 5-7/3 2019 Waseda University, Tokyo, Japan. Tokyo: Waseda University
Open this publication in new window or tab >>ConductingRedox polymer Batteries
2019 (English)In: Waseda conference on Future Battery Materials 2019 / [ed] Waseda University, Tokyo: Waseda University , 2019Conference paper, Oral presentation with published abstract (Other academic)
Place, publisher, year, edition, pages
Tokyo: Waseda University, 2019
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-378953 (URN)
Conference
Waseda conference on Future Battery Materials. 5-7/3 2019 Waseda University, Tokyo, Japan
Available from: 2019-03-11 Created: 2019-03-11 Last updated: 2019-05-09
Åkerlund, L., Emanuelsson, R., Hernández, G., Ruipérez, F., Casado, N., Brandell, D., . . . Sjödin, M. (2019). In situ Investigations of a Proton Trap Material: A PEDOT-Based Copolymer with Hydroquinone and Pyridine Side Groups Having Robust Cyclability in Organic Electrolytes and Ionic Liquids. ACS Applied Energy Materials, 2(6), 4486-4495
Open this publication in new window or tab >>In situ Investigations of a Proton Trap Material: A PEDOT-Based Copolymer with Hydroquinone and Pyridine Side Groups Having Robust Cyclability in Organic Electrolytes and Ionic Liquids
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2019 (English)In: ACS Applied Energy Materials, ISSN 2574-0962, Vol. 2, no 6, p. 4486-4495Article in journal (Refereed) Published
Abstract [en]

A conducting redox polymer based on PEDOT with hydroquinone and pyridine pendant groups is reported and characterized as a proton trap material. The proton trap functionality, where protons are transferred from the hydroquinone to the pyridine sites, allows for utilization of the inherently high redox potential of the hydroquinone pendant group (3.3 V versus Li0/+) and sustains this reaction by trapping the protons within the polymer, resulting in proton cycling in an aprotic electrolyte. By disconnecting the cycling ion of the anode from the cathode, the choice of anode and electrolyte can be extensively varied and the proton trap copolymer can be used as cathode material for all-organic or metal-organic batteries. In this study, a stable and nonvolatile ionic liquid was introduced as electrolyte media, leading to enhanced cycling stability of the proton trap compared to cycling in acetonitrile, which is attributed to the decreased basicity of the solvent. Various in situ methods allowed for in-depth characterization of the polymer’s properties based on its electronic transitions (UV–vis), temperature-dependent conductivity (bipotentiostatic CV-measurements), and mass change (EQCM) during the redox cycle. Furthermore, FTIR combined with quantum chemical calculations indicate that hydrogen bonding interactions are present for all the hydroquinone and quinone states, explaining the reversible behavior of the copolymer in aprotic electrolytes, both in three-electrode setup and in battery devices. These results demonstrate the proton trap concept as an interesting strategy for high potential organic energy storage materials.

Keywords
conducting redox polymer, organic electronics, renewable energy storage, proton trap, quinone, in situ
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-389514 (URN)10.1021/acsaem.9b00735 (DOI)000473116600063 ()
Funder
SweGRIDS - Swedish Centre for Smart Grids and Energy StorageSwedish Energy AgencyCarl Tryggers foundation , CTS 17:414Stiftelsen Olle Engkvist ByggmästareSwedish Research Council Formas, 2018-00744Swedish Research Council Formas, 2016-00838
Available from: 2019-07-16 Created: 2019-07-16 Last updated: 2019-09-13Bibliographically approved
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
Wang, H., Emanuelsson, R., Liu, H., Edström, K., Mamedov, F., Strömme, M. & Sjödin, M. (2019). Redox-State-Dependent Interplay between Pendant Group and Conducting Polymer Backbone in Quinone-Based Conducting Redox Polymers for Lithium Ion Batteries. ACS Applied Energy Materials, 2(10), 7162-7170
Open this publication in new window or tab >>Redox-State-Dependent Interplay between Pendant Group and Conducting Polymer Backbone in Quinone-Based Conducting Redox Polymers for Lithium Ion Batteries
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2019 (English)In: ACS Applied Energy Materials, E-ISSN 2574-0962, Vol. 2, no 10, p. 7162-7170Article in journal (Refereed) Published
Abstract [en]

Conducting redox polymers (CRPs) have attracted increased interest in recent years because of the possibility of combining the favorable electron-transport properties of conducting polymers with the additional functionality provided by the redox active pendant groups (PGs). Herein we present a series of quinone-substituted PEDOT-CRPs where the quinone PGs have been substituted by electron-withdrawing substituents. Introducing electron-withdrawing substituents leads to an increase of the quinone formal potential, making, for example, CF3-substituted CRPs, a promising high-voltage cathode material for lithium ion batteries with a well-defined charge/discharge plateau around 3 V vs Li+/Li0. Interestingly, we find a shift in conductance onset potential concomitant with the quinone formal potential shift, indicating that the polymer backbone conductance is intimately associated with the PG redox chemistry. Through in situ UV–vis, electron paramagnetic resonance (EPR), and electrochemical quartz crystal microbalance experiments as well as by experiments in lithium- and tert-butyl-ammonium-based electrolytes, we show that the conductance delay is caused by the reduced lithiated quinone state, most likely by localizing the polaron charge carrier as indicated by EPR and UV–vis experiments.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-394121 (URN)10.1021/acsaem.9b01130 (DOI)000502688800024 ()
Available from: 2019-10-03 Created: 2019-10-03 Last updated: 2020-03-05Bibliographically approved
Xu, X., Makaraviciute, A., Kumar, S., Wen, C., Sjödin, M., Abdurakhmanov, E., . . . Zhang, Z. (2019). Structural Changes of Mercaptohexanol Self-assembled Monolayers on Gold and their Influence on Impedimetric Aptamer Sensors. Analytical Chemistry, 91(22), 14697-14704
Open this publication in new window or tab >>Structural Changes of Mercaptohexanol Self-assembled Monolayers on Gold and their Influence on Impedimetric Aptamer Sensors
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2019 (English)In: Analytical Chemistry, ISSN 0003-2700, E-ISSN 1520-6882, Vol. 91, no 22, p. 14697-14704Article in journal (Refereed) Published
Abstract [en]

Despite a large number of publications describing biosensors based on electrochemical impedance spectroscopy (EIS), little attention has been paid to the stability and reproducibility issues of the sensor interfaces. In this work, the stability and reproducibility of faradaic EIS analyses on the aptamer/mercaptohexanol (MCH) self-assembled monolayer (SAM) functionalized gold surfaces in ferri- and ferrocyanide solution were systematically evaluated prior to and after the aptamer-probe DNA hybridization. It is shown that the EIS data exhibited significant drift, and this significantly affected the reproducibility of the EIS signal of the hybridization. As a result, no significant difference between the charge transfer resistance (RCT) changes induced by the aptamer-target DNA hybridization and that caused by the drift could be identified. A conditioning of the electrode in the measurement solution for more than 12 hours was required to reach a stable RCT baseline prior to the aptamer-probe DNA hybridization. The monitored drift in RCT and CDL during the conditioning suggests that the MCH SAM on the gold surface reorganized to a thinner but more closely packed layer. We also observed that the hot binding buffer used in the following aptamer-probe DNA hybridization process could induce additional MCH and aptamer reorganization thus further drift in RCT. As a result, the RCT change caused by the aptamer-probe DNA hybridization was less than that caused by the hot binding buffer (blank control experiment). Therefore, it is suggested that the use of high temperature in the EIS measurement should be carefully evaluated or avoided. This work provides practical guidelines for the EIS measurements. Moreover, since SAM functionalized gold electrodes are widely used in biosensors, e.g., DNA sensors, an improved understanding of the origin of the observed drift is very important for the development of well-functioning and reproducible biosensors.

National Category
Analytical Chemistry
Identifiers
urn:nbn:se:uu:diva-397690 (URN)10.1021/acs.analchem.9b03946 (DOI)000498280100072 ()31650834 (PubMedID)
Funder
Swedish Foundation for Strategic Research , ICA 12-0047Swedish Foundation for Strategic Research , FFL15-0174Swedish Research Council, VR 2014-5588Knut and Alice Wallenberg Foundation, Wallenberg Academy Fellow Program
Available from: 2019-11-22 Created: 2019-11-22 Last updated: 2020-01-13Bibliographically approved
Strietzel, C., Emanuelsson, R., Strömme, M. & Sjödin, M. (2018). Conducting Redox Polymer Batteries. In: : . Paper presented at Electronic Processes in Organic Materials (GRC).
Open this publication in new window or tab >>Conducting Redox Polymer Batteries
2018 (English)Conference paper, Poster (with or without abstract) (Refereed)
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-364962 (URN)
Conference
Electronic Processes in Organic Materials (GRC)
Funder
SweGRIDS - Swedish Centre for Smart Grids and Energy Storage
Available from: 2018-11-07 Created: 2018-11-07 Last updated: 2018-11-07
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
Wang, H., Emanuelsson, R., Sjödin, M. & Strömme, M. (2018). Electrochemical Performance of Electron Withdrawing Group Substituted Benzoquinone and Benzoquinone-Functionalized Poly(3,4-ethylenedioxythiophene) Conducting Redox Polymer. In: MRS (Ed.), MRS Fall meeting 2018: In Situ/Operando Analysis of Electrochemical Materials and Interfaces. Paper presented at MRS Fall meeting 2018. Boston November 2018. Boston, Article ID CM03.09.03.
Open this publication in new window or tab >>Electrochemical Performance of Electron Withdrawing Group Substituted Benzoquinone and Benzoquinone-Functionalized Poly(3,4-ethylenedioxythiophene) Conducting Redox Polymer
2018 (English)In: MRS Fall meeting 2018: In Situ/Operando Analysis of Electrochemical Materials and Interfaces / [ed] MRS, Boston, 2018, article id CM03.09.03Conference paper, Published paper (Refereed)
Abstract [en]

Conducting redox polymers have been investigate massively as an efficient cathode material. Herein we synthesis a series of quinone substituted PEDOT conducting redox polymers and investigate the effect of electron withdrawing substitutions on the redox potential of quinone in the PEDOT backbone in two electrolyte 0.1M LiClO4/MeCN a. Elelctron withdrawing substitutions leads to an increase of the redox potential of quinone in LiClO4/MeCN . The conductivity of PEDOT backbone is hindered by the lithiated reduced quinone. In-situ uv-vis and EQCM is used to probe the exact PEDOT doping onset potential, confirming that conductivity of quinone is hindered by lithiated reduced quinone. In situ EQCM proves that mass change in the PEDOT doping region involves cation repulsion and dopants anion uptaken.

Place, publisher, year, edition, pages
Boston: , 2018
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-366561 (URN)
Conference
MRS Fall meeting 2018. Boston November 2018
Available from: 2018-11-21 Created: 2018-11-21 Last updated: 2019-03-07Bibliographically approved
Sterby, M., Emanuelsson, R., Strömme, M. & Sjödin, M. (2018). Electronic properties of a PEDOT/Quinone Conducting Redox Polymer. In: : . Paper presented at Gordon Research Conference and Seminar: Electronic Processes in Organic Materials.
Open this publication in new window or tab >>Electronic properties of a PEDOT/Quinone Conducting Redox Polymer
2018 (English)Conference paper, Poster (with or without abstract) (Other academic)
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.

Keywords
PEDOT, Conducting Redox Polymer, Gordon Research, Battery, Electronic
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-363671 (URN)
Conference
Gordon Research Conference and Seminar: Electronic Processes in Organic Materials
Available from: 2018-10-19 Created: 2018-10-19 Last updated: 2018-10-23
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0003-4126-4347

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