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Conducting Redox Polymers for Electrode Materials Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 1604 Conducting Redox Polymers for Electrode Materials Synthetic Strategies and Electrochemical Properties XIAO HUANG ACTA UNIVERSITATIS UPSALIENSIS ISSN 1651-6214 ISBN 978-91-513-0168-6 UPPSALA urn:nbn:se:uu:diva-334562 2017 Dissertation presented at Uppsala University to be publicly examined in B41, BMC, Husargatan, Uppsala, Friday, 19 January 2018 at 09:15 for the degree of Doctor of Philosophy. The examination will be conducted in English. Faculty examiner: Prof. David Mecerreyes (University of the Basque Country).Berit Olofsson (Stockholm University).Dr. Fredrik Björefors (Strukturkemi).Docent Tom Lindfors (Åbo Akademi University). Abstract Huang, X. 2017. Conducting Redox Polymers for Electrode Materials. Synthetic Strategies and Electrochemical Properties. Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 1604. 83 pp. Uppsala: Acta Universitatis Upsaliensis. ISBN 978-91-513-0168-6. 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. Keywords: Organic electrode material, Energy storage, Conducting redox polymer, Polythiophene, Terephthalate, PEDOT Xiao Huang, Department of Chemistry - BMC, Organic Chemistry, Box 576, Uppsala University, SE-75123 Uppsala, Sweden. © Xiao Huang 2017 ISSN 1651-6214 ISBN 978-91-513-0168-6 urn:nbn:se:uu:diva-334562 (http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-334562) We could choose to live like a candle, flame from the beginning till the end, and bring the warmth and light to our surroundings. List of Papers This thesis is based on the following papers, which are referred to in the text by their Roman numerals. I Yang, L., Huang, X., Gogoll, A., Strømme, M., Sjödin, M. (2015) Matching Diethyl Terephthalate with n-doped Conduct- ing Polymers. The Journal of Physical Chemistry C, 119(33):18956–18963. II Huang, X., Yang, L., Bergquist, J., Strømme, M., Gogoll, A., Sjödin, M. (2015). Synthesis and Redox Properties of Thio- phene Terephthalate Building Blocks for Low-Potential Con- ducting Redox Polymers. The Journal of Physical Chemistry C, 119(49):27247-27254. III Yang, L., Huang X., Gogoll, A., Strømme, M., Sjödin, M. (2016). Conducting Redox Polymer based Anode Materials for High Power Electrical Energy Storage. Electrochimica Acta, 204:270-275. IV Yang, L., Huang X., Gogoll, A., Strømme, M., Sjödin, M. (2016). Effect of the Linker in Terephthalate-Functionalized Conducting Redox Polymers. Electrochimica Acta, 222:149- 155. V Huang, X., Yang, L., Emanuelsson, R., Bergquist, J., Strømme, M., Gogoll, A., Sjödin, M. (2016). A Versatile Route to Poly- thiophenes with Functional Pendant Groups Using Alkyne Chemistry. Beilstein Journal of Organic Chemistry, 12:2682- 2688. VI Yang, L., Huang X., Gogoll, A., Strømme, M., Sjödin, M. (2017). Conducting Redox Polymers with non-Activated Charge Transport properties. Physical Chemistry Chemical Physics, 19:25052-25058. Reprints were made with permission from the respective publishers. My contribution to the included papers Paper I: Participated in the planning of the study and discussion in the data analysis. I provided all the synthetic work and contributed to part of the writ- ing process. Paper II: Participated in the planning of the study and performed all the synthetic work and computations. I wrote the initial manuscript and contrib- uted to the continued writing process. Paper III: Participated in the planning of the study and discussion in the data analysis. I provided all the synthetic work and contributed to part of the writing process. Paper IV: Participated in the planning of the study and discussion in the data analysis. I provided all the synthetic work and contributed to part of the writing process. Paper V: Participated in the design and planning of the study and performed all the synthetic work. I wrote the initial manuscript and contributed to the continued writing process. Paper VI: Participated in the planning of the study and discussion in the data analysis. I provided all the synthetic work and contributed to part of the writing process. Also published Sterby, M., Emanuelsson, R., Huang, X., Gogoll, A., Strømme, M., Sjödin, M. (2017). Characterization of PEDOT-Quinone Conducting Redox Poly- mers for Water Based Secondary Batteries. Electrochimica Acta, 235:356- 364. Huang, X., Yang, Li., Strømme, M., Sjödin M., Gogoll, A. (2016). C-C bond forming and C-N bond forming on 3,4-ethylenedioxythiophene (EDOT): the new synthetic way of building blocks for functionalized PEDOTs. 6th EuCheMS Chemistry Congress, Seville, Spain. Huang, X., Yang, Li., Strømme, M., Sjödin M., Gogoll, A. (2016). 3-(3,4- ethylenedioxythiophene)prop-1-yne (pyEDOT): A new versatile building block for functionalized PEDOTs. 25th Organikerdagarna, Umeå, Sweden. Huang, X., Yang, Li., Strømme, M., Sjödin M., Gogoll, A. (2015). Synthesis and Redox Properties of Thiophene-Terephthalate Building Blocks for Low Potential Conducting Redox Polymers. 66th Annual Meeting of the International Society of Electrochemistry, Taipei, Taiwan. Yang, Li., Huang, X., Strømme, M., Sjödin M., Gogoll, A. (2014). ”Greener” Energy Storage Material – Thiophene-based Terephthalate Redox Polymer. 65th Annual Meeting of the International Society of Electrochemistry, Lausanne, Switzerland. Huang, X., Yang, Li., Strømme, M., Sjödin M., Gogoll, A. (2014) Novel n- type thiophene-based terephthalate redox polymer for energy storage. 248th American Chemical Society National Meeting, San Francisco, USA. Huang, X., Yang, Li., Strømme, M., Sjödin M., Gogoll, A. (2014) Low potential Thiophene-based Terephthalate Redox Polymer for Energy Storage. Gordon Research Conference: Electronic Processes in Organic Materials, Lucca, Italy. Contents 1. General introduction ................................................................................. 17 2. Aims of the thesis...................................................................................... 18 3. Electrical Energy Storage ......................................................................... 19 3.1 Organic Energy Storage ..................................................................... 21 3.2 Polymers as active electrode materials ............................................... 23 3.2.1 Organic Conducting Polymers .................................................... 24 3.2.2 Organic Redox Polymers ............................................................ 28 3.2.3 Conducting Redox Polymers ...................................................... 29 4. Monomer Design and Synthetic Strategies for Low Potential Conducting Redox Polymers ........................................................................ 30 4.1 Potential match ................................................................................... 30 4.2 Synthetic Tools ................................................................................... 32 4.2.1 Formation of carbon-heteroatom bonds ...................................... 33 4.2.2 Carbon-carbon bond formation ................................................... 37 4.2.3 Synthetic route design ................................................................. 44 4.3 Effect of the linker and computational tools ...................................... 47 4.3.1 DFT calculation .........................................................................
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