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Nanocomposites of Cellulose and Conducting Polymer for Electrical Energy Storage
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The world’s increased energy storage demand, as well as the environmental concerns related to the combustion of fossil fuels, has triggered a transition to intermittent renewable energy sources as well as to electrical and hybrid vehicles. Current day rechargeable batteries are, due to the invention and development of lithium ion batteries, technologically well positioned to answer to some of these demands. Conventional batteries, however, utilize inorganic materials of limited supply that require large amounts of energy during refining and processing. The materials also add a significant cost to the final product, making the rechargeable batteries less attractive for large scale applications. During the last decade, significant efforts have been made to find suitable organic matter based electrode materials that can replace the inorganic materials. One class of organic materials that can be used for electrical energy storage, or be included as components in organic matter based energy storage systems, is conducting polymers.

The aim of this thesis was to investigate the possibilities and limitations of using the conducting polymer polypyrrole in energy storage applications. The polymer was synthesized onto cellulose extracted from the Cladophora sp. algae, and the result was a flexible composite material. Symmetrical energy storage devices constructed with the composite material were shown to exhibit a pseudocapacitive behavior. The resistance in the cells was investigated and was found to scale linearly with the separator thickness. Cells could be cycled for 4,000 cycles without significant capacitance loss and cells that were overcharged to 1.8 V cell potential, were found to be protected by a resistive potential drop. Devices were constructed as proof-of-concept and were used to power a remote control and a digital thermometer.

The self-discharge in polypyrrole was studied extensively. It was found that oxygen was responsible for the oxidation of the reduced electrode, while the positive electrode self-discharged due to a faradaic reaction. Through spectroscopy and the temperature dependence of the self-discharge, it was suggested that the self-discharge of oxidized polypyrrole is linked to the degradation at high potentials, commonly referred to as overoxidation.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2014. , 60 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1125
Keyword [en]
Polypyrrole, Nanocomposites, Energy storage, Conducting polymers, Cellulose
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
URN: urn:nbn:se:uu:diva-218815ISBN: 978-91-554-8883-3 (print)OAI: oai:DiVA.org:uu-218815DiVA: diva2:697449
Public defence
2014-04-04, Å4001, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:30 (English)
Opponent
Supervisors
Available from: 2014-03-13 Created: 2014-02-18 Last updated: 2014-04-29
List of papers
1. Cycling stability and self-protective properties of a paper-based polypyrrole energy storage device
Open this publication in new window or tab >>Cycling stability and self-protective properties of a paper-based polypyrrole energy storage device
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2011 (English)In: Electrochemistry communications, ISSN 1388-2481, E-ISSN 1873-1902, Vol. 13, no 8, 869-871 p.Article in journal (Refereed) Published
Abstract [en]

A composite consisting of polypyrrole and cellulose from the Cladophora sp. green algae is shown to exhibit excellent cycling stability when used as the electrodes in an aqueous symmetric supercapacitor device. The capacitance of the device, which was 32.4 F g− 1, only decreased by 0.7% during 4000 galvanostatic cycles employing a current of 10 mA and potential cut-off limits of 0 and 0.8 V. No change in the electrode material's morphology could be seen when comparing cycled and pristine materials with scanning electron microscopy. Furthermore, no significant loss in capacitance was observed even when charging the device to 1.8 V. Measurements of the electrode potentials versus a common reference show that this effect was due to a device intrinsic self-protective mechanism which prevented degradation of the polypyrrole.

Keyword
Conducting polymer, Polypyrrole, Cycling stability, Composite, Cellulose
National Category
Natural Sciences Inorganic Chemistry Engineering and Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials; Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-156540 (URN)10.1016/j.elecom.2011.05.024 (DOI)000294582300032 ()
Available from: 2011-08-01 Created: 2011-08-01 Last updated: 2017-12-08Bibliographically approved
2. Influence of the cellulose substrate on the electrochemical properties of paper-based polypyrrole electrode materials
Open this publication in new window or tab >>Influence of the cellulose substrate on the electrochemical properties of paper-based polypyrrole electrode materials
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2012 (English)In: Journal of Materials Science, ISSN 0022-2461, E-ISSN 1573-4803, Vol. 47, no 13, 5317-5325 p.Article in journal (Refereed) Published
Abstract [en]

The influence of the cellulose substrate on the electrochemical performance of supercapacitor electrode materials made of polypyrrole (PPy) and cellulose is investigated. Composites were synthesized by chemical polymerization of pyrrole on dispersed fibers of cellulose from Cladophora algae and dispersed wood cellulose-based commercial filter papers, respectively, as well as on Cladophora cellulose and filter paper sheets. The resulting composites, which were characterized using scanning electron microscopy, cyclic voltammetry, and elemental analysis, were found to exhibit specific charge capacities proportional to the PPy content of the composites. The highest specific capacity (i.e., 171 C/g composite or 274 C/g PPy) was obtained for composites made from dispersed Cladophora cellulose fibers. The higher specific capacities for the Cladophora cellulose composites can be explained by the fact that the Cladophora cellulose fibers were significantly thinner than the wood cellulose fibers. While the PPy was mainly situated on the surface of the Cladophora cellulose fibers, a significant part of the PPy was found to be present within the wood fibers of the filter paper-based composites. The latter can be ascribed to a higher accessibility of the aqueous pyrrole solution to the wood-based fibers as compared to the highly crystalline algae based cellulose fibers. The present results clearly show that the choice of the cellulose substrate is important when designing electrode materials for inexpensive, flexible and environmentally friendly paper-based energy storage devices.

National Category
Composite Science and Engineering
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-174034 (URN)10.1007/s10853-012-6418-y (DOI)000302698400028 ()
Available from: 2012-05-10 Created: 2012-05-10 Last updated: 2017-12-07
3. Self-discharge in an electric energy storage device based on polypyrrole-cellulose composite electrodes
Open this publication in new window or tab >>Self-discharge in an electric energy storage device based on polypyrrole-cellulose composite electrodes
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(English)Manuscript (preprint) (Other academic)
National Category
Nano Technology
Identifiers
urn:nbn:se:uu:diva-218814 (URN)
Available from: 2014-02-18 Created: 2014-02-18 Last updated: 2014-12-15
4. Temperature dependence of the self-discharge in polypyrrole-cellulose composite electrodes
Open this publication in new window or tab >>Temperature dependence of the self-discharge in polypyrrole-cellulose composite electrodes
(English)Manuscript (preprint) (Other academic)
National Category
Nano Technology
Identifiers
urn:nbn:se:uu:diva-218813 (URN)
Available from: 2014-02-18 Created: 2014-02-18 Last updated: 2014-12-15
5. The influence of electrode and separator thickness on the cell resistance of symmetric cellulose–polypyrrole-based electric energy storage devices
Open this publication in new window or tab >>The influence of electrode and separator thickness on the cell resistance of symmetric cellulose–polypyrrole-based electric energy storage devices
2014 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 272, 468-475 p.Article in journal (Refereed) Published
Abstract [en]

The influence of the cell design of symmetric polypyrrole and cellulose-based electric energy storage devices on the cell resistance was investigated using chronopotentiometric and ac impedance measurements with different separator and electrode thicknesses. The cell resistance was found to be dominated by the electrolyte and current collector resistances while the contribution from the composite electrode material was negligible. Due to the electrolyte within the porous electrodes thin separators could be used in combination with thick composite electrodes without loss of performance. The paper separator contributed with a resistance of similar to 1.5 Omega mm(-1) in a 1.0 M NaNO3 electrolyte and the tortuosity value for the separator was about 2.5. The contribution from the graphite foil current collectors was about similar to 0.4-1.1 Omega and this contribution could not be reduced by using platinum foil current collectors due to larger contact resistances. The introduction of chopped carbon fibres into the electrode material or the application of pressure across the cells, however, decreased the charge transfer resistance significantly. As the present results demonstrate that cells with higher charge storage capacities but with the same cell resistance can be obtained by increasing the electrode thickness, the development of paper based energy storage devices is facilitated.

National Category
Nano Technology
Identifiers
urn:nbn:se:uu:diva-218812 (URN)10.1016/j.jpowsour.2014.08.041 (DOI)000344208700058 ()
Available from: 2014-02-18 Created: 2014-02-18 Last updated: 2017-12-06Bibliographically approved

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