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Conducting Redox Polymers for Electrode Materials: Synthetic Strategies and Electrochemical Properties
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Organic electrode materials represent an intriguing alternative to their inorganic counterparts due to their sustainable and environmental-friendly properties. Their plastic character allows for the realization of light-weight, versatile and disposable devices for energy storage. Conducting redox polymers (CRPs) are one type of the organic electrode materials involved, which consist of a π-conjugated polymer backbone and covalently attached redox units, the so-called pendant. The polymer backbone can provide conductivity while it is oxidized or reduced (i. e., p- or n-doped) and the concurrent redox chemistry of the pendant provides charge capacity. The combination of these two components enables CRPs to provide both high charge capacity and high power capability. This dyad polymeric framework provides a solution to the two main problems associated with organic electrode materials based on small molecules: the dissolution of the active material in the electrolyte, and the sluggish charge transport within the material. This thesis introduces a general synthetic strategy to obtain the monomeric CRPs building blocks, followed by electrochemical polymerization to afford the active CRPs material. The choice of pendant and of polymer backbone depends on the potential match between these two components, i.e. the redox reaction of the pendant and the doping of backbone occurring within the same potential region. In the thesis, terephthalate and polythiophene were selected as the pendant and polymer backbone respectively, to get access to low potential CRPs. It was found that the presence of a non-conjugated linker between polymer backbone and pendant is essential for the polymerizability of the monomers as well as for the preservation of individual redox activities. The resulting CRPs exhibited fast charge transport within the polymer film and low activation barriers for charge propagation. These low potential CRPs were designed as the anode materials for energy storage applications. The combination of redox active pendant as charge carrier and a conductive polymer backbone reveals new insights into the requirements of organic matter based electrical energy storage materials.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. , p. 83
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1604
Keywords [en]
Organic electrode material, Energy storage, Conducting redox polymer, Polythiophene, Terephthalate, PEDOT
National Category
Nano Technology Organic Chemistry Physical Chemistry Polymer Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-334562ISBN: 978-91-513-0168-6 (print)OAI: oai:DiVA.org:uu-334562DiVA, id: diva2:1159871
Public defence
2018-01-19, B41, BMC, Husargatan, Uppsala, 09:15 (English)
Opponent
Supervisors
Funder
SweGRIDS - Swedish Centre for Smart Grids and Energy StorageSwedish Research CouncilSwedish Foundation for Strategic Research Available from: 2017-12-21 Created: 2017-11-23 Last updated: 2018-03-08
List of papers
1. Matching Diethyl Terephthalate with n-Doped Conducting Polymers
Open this publication in new window or tab >>Matching Diethyl Terephthalate with n-Doped Conducting Polymers
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2015 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 33, p. 18956-18963Article in journal (Refereed) Published
Abstract [en]

The combination of small, high charge capacity molecules as pendant groups with a conducting polymer backbone having good electronic conductivity upon doping, gives the possibility to design a high capacity conducting redox polymer material for electric energy storage applications. The desired synergetic effect of the two components requires energy matching as well as chemical compatibility of the pendant group and the polymer backbone. Here we investigate the matching of diethyl terephthalate (DeT) with the thiophene-based conducting polymers polythiophene (PT), poly(3,4-ethylenedioxythiophene) (PEDOT), and polyphenylthiophene. We show that a stable and well-defined electrochemical response of DeT is achieved, together with all conducting polymers except for PT in tetrabutylammonium hexafluorophosphate electrolyte, indicating good energy match as well as chemical compatibility between DeT and polymers. By varying the size of ammonium cations in the electrolytes, we further show how this size affects the conductivity and the cycling stability of the polymers and also that the n-doping performance of all conducting polymers can be improved by the use of smaller alkyl ammonium cations. On the basis of these results, we suggest that PEDOT and PT are suitable candidates for a polymer backbone in conducting redox polymers with DeT pendant groups.

National Category
Nano Technology
Identifiers
urn:nbn:se:uu:diva-262423 (URN)10.1021/acs.jpcc.5b05067 (DOI)000360026200015 ()
Funder
Swedish Foundation for Strategic Research Swedish Research CouncilCarl Tryggers foundation Swedish Energy Agency
Available from: 2015-09-17 Created: 2015-09-15 Last updated: 2017-12-04Bibliographically approved
2. Synthesis and Redox Properties of Thiophene Terephthalate Building Blocks for Low-Potential Conducting Redox Polymers
Open this publication in new window or tab >>Synthesis and Redox Properties of Thiophene Terephthalate Building Blocks for Low-Potential Conducting Redox Polymers
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2015 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 49, p. 27247-27254Article in journal (Refereed) Published
Abstract [en]

Terephthalate-substituted thiophene derivatives are promising redox-active components for anode materials in lithium-ion batteries. In this study, we present the synthesis of substituted 2-(thiophen-3-yl)terephthalate derivatives (TTDs) as suitable monomers for thiophene-based conducting redox polymers, along with their characterization by electrochemical and spectroscopic techniques. Density functional theory (DFT) calculations, utilizing the universal solvation model based on solute electron density (SMD), were used to predict both the first and the second reduction potentials of these TTDs. The computational results showed good agreement with the experimental data in nonaqueous acetonitrile solvent, with mean absolute errors of 30 and 40 mV for the first and second reduction steps, respectively. Time-dependent (TD) DFT calculations on TTDs indicated terephthalate local transitions at both 200 and 240 nm and charge-transfer transitions above 300 nm by examination of the involved molecular orbitals.

National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-268481 (URN)10.1021/acs.jpcc.5b08518 (DOI)000366339000008 ()
Funder
Swedish Research Council, VR 621-2011-4423Swedish Foundation for Strategic Research Swedish Energy Agency
Available from: 2015-12-05 Created: 2015-12-05 Last updated: 2017-12-01Bibliographically approved
3. Conducting Redox Polymer Based Anode Materials for High Power Electrical Energy Storage
Open this publication in new window or tab >>Conducting Redox Polymer Based Anode Materials for High Power Electrical Energy Storage
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2016 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 204, p. 270-275Article in journal (Refereed) Published
Abstract [en]

In this report we present the synthesis and characterization of two conducting redox polymers (CRPs) with polythiophene backbone and diethyl terephthalate pendant groups for the use as anode materials in secondary batteries. The materials show excellent rate capability allowing 301,Lm layers to be fully converted within seconds without the use of conductive additives. The high rate capability is traced to the open morphology of the materials that allows for fast ion transport, and to the mediation of electrons through the conducting polymer (CP) backbone. The requirements for the latter are i) that the redox chemistry of the pendant groups and the CP backbone overlaps and ii) that the CP conductivity is not compromised by the presence of the pendant groups. In the CRPs presented herein both these requirements are met and this is thus the first report on successful combination of the redox chemistry of organic redox molecules with the n-doping of conducting polymers.

Keywords
conducting redox polymers, terephthalates, polythiophene, n-doping
National Category
Engineering and Technology
Identifiers
urn:nbn:se:uu:diva-298055 (URN)10.1016/j.electacta.2016.03.163 (DOI)000376136700031 ()
Funder
Swedish Foundation for Strategic Research Swedish Research CouncilCarl Tryggers foundation Stiftelsen Olle Engkvist ByggmästareSwedish Energy AgencyEU, Horizon 2020, 644631
Available from: 2016-07-05 Created: 2016-06-29 Last updated: 2017-11-28Bibliographically approved
4. Effect of the Linker in Terephthalate-Functionalized Conducting Redox Polymers
Open this publication in new window or tab >>Effect of the Linker in Terephthalate-Functionalized Conducting Redox Polymers
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2016 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 222, p. 149-155Article in journal (Refereed) Published
Abstract [en]

Abstract The combination of high capacity redox active pendent groups and conducting polymers, realized in conducting redox polymers (CRPs), provides materials with high charge storage capacity that are electronically conducting which makes CRPs attractive for electrical energy storage applications. In this report, six polythiophene and poly(3,4-ethylenedioxythiophene)(PEDOT)-based CRPs with a diethyl terephthalate unit covalently bound to the polymer chain by various linkers have been synthesized and characterized electrochemically. The effects of the choice of polymer backbone and of the nature of the link on the electrochemistry, and in particular the cycling stability of these polymers, are discussed. All CRPs show both the doping of the polymer backbone as well as the redox behavior of the pendent groups and the redox potential of the pendent groups in the CRPs is close to that of corresponding monomer, indicating insignificant interaction between the pendant and the polymer backbone. While all CRPs show various degrees of charge decay upon electrochemical redox conversion, the PEDOT-based CRPs show significantly improved stability compared to the polythiophene counterparts. Moreover, we show that by the right choice of link the cycling stability of diethyl terephthalate substituted PEDOT-based CRPs can be significantly improved.

Keywords
conducting redox polymers, PEDOT, polythiophene, terephthalate
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-310464 (URN)10.1016/j.electacta.2016.10.183 (DOI)000392566200018 ()
Funder
Swedish Foundation for Strategic Research Swedish Research CouncilCarl Tryggers foundation Stiftelsen Olle Engkvist ByggmästareSwedish Energy AgencyEU, European Research Council, 644631
Available from: 2016-12-16 Created: 2016-12-16 Last updated: 2017-11-29Bibliographically approved
5. A versatile route to polythiophenes with functional pendant groups using alkyne chemistry
Open this publication in new window or tab >>A versatile route to polythiophenes with functional pendant groups using alkyne chemistry
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2016 (English)In: Beilstein Journal of Organic Chemistry, ISSN 2195-951X, E-ISSN 1860-5397, Vol. 12, p. 2682-2688Article in journal (Refereed) Published
Abstract [en]

A new versatile polythiophene building block, 3-(3,4-ethylenedioxythiophene)prop-1-yne (pyEDOT) (3), is prepared from glycidol in four steps in 28% overall yield. pyEDOT features an ethynyl group on its ethylenedioxy bridge, allowing further functionalization by alkyne chemistry. Its usefulness is demonstrated by a series of functionalized polythiophene derivatives that were obtained by pre- and post-electropolymerization transformations, provided by the synthetic ease of the Sonogashira coupling and click chemistry.

Keywords
electropolymerization, functional polymers, polythiophene, Sonogashira coupling, thiophene
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-310098 (URN)10.3762/bjoc.12.265 (DOI)000391506600001 ()
Funder
Swedish Research Council, VR 621-2011-4423 2015-4870Swedish Foundation for Strategic Research Swedish Energy Agency
Available from: 2016-12-09 Created: 2016-12-09 Last updated: 2017-11-29Bibliographically approved
6. Conducting redox polymers with non-activated charge transport properties
Open this publication in new window or tab >>Conducting redox polymers with non-activated charge transport properties
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2017 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 19, no 36, p. 25052-25058Article in journal (Refereed) Published
Abstract [en]

Non-activated charge transport has been demonstrated in terephthalate-functionalized conducting redox polymers. The transition from a temperature-activated conduction mechanism to a residual scattering mechanism was dependent on the doping level. The latter mechanism is associated with apparent negative activation barriers to charge transport and is generally found in polymer materials with a high degree of order. Crystallographic data, however, suggested a low degree of order in this polymer, indicating the existence of interconnected crystal domains in the predominantly amorphous polymer matrix through which the charge was transported. We have thus shown that the addition of bulky pendant groups to conducting polymers does not prevent efficient charge transport via the residual scattering mechanism with low barriers to charge transport.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2017
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-304625 (URN)10.1039/c7cp03939e (DOI)000411606200067 ()28879367 (PubMedID)
Funder
Swedish Research CouncilSwedish Foundation for Strategic Research Stiftelsen Olle Engkvist ByggmästareEU, Horizon 2020, 64431Swedish Energy Agency
Available from: 2016-10-06 Created: 2016-10-06 Last updated: 2018-06-04Bibliographically approved

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Citation style
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  • modern-language-association-8th-edition
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Output format
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