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Biohybrid Polymer Electrodes for Renewable Energy Storage
Linköping University, Department of Physics, Chemistry and Biology, Biomolecular and Organic Electronics. Linköping University, Faculty of Science & Engineering.
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Daily and seasonally fluctuating energy supply and demand requires adequate energy storage solutions. In recent years electrochemical supercapacitors have attracted considerable attention due to their ability to both store and deliver electrical energy efficiently. Our efforts are focused on developing and optimizing sustainable organic electrode materials for supercapacitors based on renewable bioorganic materials, offering a cheap, environmentally friendly and scalable alternative to store energy. In particular, we are using the second most abundant biopolymer in nature, lignin (Lig), which is an insulating material. However, when used in combination with electroactive and conducting polymers such as polypyrrole (PPy) and poly(3,4-ethylenedioxythiophene) (PEDOT), the biohybrid electrodes PPy/Lig and PEDOT/Lig display significantly enhanced energy storage performance as compared to the pristine conducting polymers without the lignin. Redox cyclic voltammetry and galvanostatic charge/discharge measurements indicate that the enhanced performance is due to the additional pseudocapacitance generated by the quinone moieties in lignin. Moreover, a conjugated redoxpolymer poly(aminoanthraquinone) PAAQ, with intrinsic quinone functions and excellentstability, has been combined with lignin and PEDOT resulting in a trihybrid bioelectrode. PEDOT compensates the low conductivity of PAAQ and provides electrical pathways to the quinone groups. The electrochemically generated quinones undergo a two electron, two protonredox process within the biohybrid electrodes as revealed by FTIR spectroelectrochemistry.These remarkable features reveal the exciting potential of a full organic energy storage device with long cycle life. Therefore, supercapacitor devices were designed in symmetric or asymmetric two electrode configuration. The best electrochemical performance was achieved by the asymmetric supercapacitor based on PEDOT+Lignin/PAAQ as the positive electrode and PEDOT/PAAQ as the negative electrode. This device exhibits superior electrochemical performance and outstanding stability after 10000 charge/discharge cycles due to the synergistic effect of the two electrodes. Finally, we have characterized the response of this supercapacitor device when charged with the intermittent power supply from an organic photovoltaic module. We have designed charging/discharging conditions such that reserve power was available in the storage device at all times. This work has resulted in an inexpensive fully organic system witht he dual function of energy conversion and storage.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2017. , 64 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1834
National Category
Energy Systems Renewable Bioenergy Research Energy Engineering Materials Chemistry
Identifiers
URN: urn:nbn:se:liu:diva-136156ISBN: 9789176855737 (print)OAI: oai:DiVA.org:liu-136156DiVA: diva2:1086093
Public defence
2017-04-27, Plank, Fysikhuset, Campus Valla, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2017-03-31 Created: 2017-03-31 Last updated: 2017-03-31Bibliographically approved
List of papers
1. Biopolymer hybrid electrodes for scalable electricity storage
Open this publication in new window or tab >>Biopolymer hybrid electrodes for scalable electricity storage
2016 (English)In: Materials Horizons, ISSN 2051-6347, E-ISSN 2051-6355, Vol. 3, no 3, 174-185 p.Article, review/survey (Refereed) Published
Abstract [en]

Powering the future, while maintaining a cleaner environment and a strong socioeconomic growth, is going to be one of the biggest challenges faced by mankind in the 21st century. The first step in overcoming the challenge for a sustainable future is to use energy more efficiently so that the demand for fossil fuels can be reduced drastically. The second step is a transition from the use of fossil fuels to renewable energy sources. In this sense, organic electrode materials are becoming increasingly attractive compared to inorganic electrode materials which have reached a plateau regarding performance and have severe drawbacks in terms of cost, safety and environmental friendliness. Using organic composites based on conducting polymers, such as polypyrrole, and abundant, cheap and naturally occurring biopolymers rich in quinones, such as lignin, has recently emerged as an interesting alternative. These materials, which exhibit electronic and ionic conductivity, provide challenging opportunities in the development of new charge storage materials. This review presents an overview of recent developments in organic biopolymer composite electrodes as renewable electroactive materials towards sustainable, cheap and scalable energy storage devices.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2016
National Category
Other Environmental Engineering
Identifiers
urn:nbn:se:liu:diva-128741 (URN)10.1039/c5mh00261c (DOI)000375296600002 ()
Note

Funding Agencies|Knut and Alice Wallenberg Foundation; Wallenberg Scholar grant

Available from: 2016-05-31 Created: 2016-05-30 Last updated: 2017-03-31
2. Spectroelectrochemical investigation of redox states in a polypyrrole/lignin composite electrode material
Open this publication in new window or tab >>Spectroelectrochemical investigation of redox states in a polypyrrole/lignin composite electrode material
Show others...
2015 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, Vol. 3, no 24, 12927-12937 p.Article in journal (Refereed) Published
Abstract [en]

We report spectroelectrochemical studies to investigate the charge storage mechanism of composite polypyrrole/lignin electrodes. Renewable bioorganic electrode materials were produced by electropolymerization of pyrrole in the presence of a water-soluble lignin derivative acting as a dopant. The resulting composite exhibited enhanced charge storage abilities due to a lignin-based faradaic process, which was expressed after repeated electrochemical redox of the material. The in situ FTIR spectroelectrochemistry results show the formation of quinone groups, and reversible oxidation-reduction of these groups during charge-discharge experiments in the electrode materials. The most significant IR bands include carbonyl absorption near 1705 cm(-1), which is attributed to the creation of quinone moieties during oxidation, and absorption at 1045 cm(-1) which is due to hydroquinone moieties.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2015
National Category
Materials Chemistry
Identifiers
urn:nbn:se:liu:diva-120069 (URN)10.1039/c5ta00788g (DOI)000356022800044 ()
Note

Funding Agencies|Knut and Alice Wallenberg foundation; Marie Curie network Renaissance; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]

Available from: 2015-07-06 Created: 2015-07-06 Last updated: 2017-03-31
3. High performance PEDOT/lignin biopolymer composites for electrochemical supercapacitors
Open this publication in new window or tab >>High performance PEDOT/lignin biopolymer composites for electrochemical supercapacitors
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2016 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, Vol. 4, no 5, 1838-1847 p.Article in journal (Refereed) Published
Abstract [en]

Developing sustainable organic electrode materials for energy storage applications is an urgent task. We present a promising candidate based on the use of lignin, the second most abundant biopolymer in nature. This polymer is combined with a conducting polymer, where lignin as a polyanion can behave both as a dopant and surfactant. The synthesis of PEDOT/Lig biocomposites by both oxidative chemical and electrochemical polymerization of EDOT in the presence of lignin sulfonate is presented. The characterization of PEDOT/Lig was performed by UV-Vis-NIR spectroscopy, FTIR infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, cyclic voltammetry and galvanostatic charge-discharge. PEDOT doped with lignin doubles the specific capacitance (170.4 F g(-1)) compared to reference PEDOT electrodes (80.4 F g(-1)). The enhanced energy storage performance is a consequence of the additional pseudocapacitance generated by the quinone moieties in lignin, which give rise to faradaic reactions. Furthermore PEDOT/Lig is a highly stable biocomposite, retaining about 83% of its electroactivity after 1000 charge/discharge cycles. These results illustrate that the redox doping strategy is a facile and straightforward approach to improve the electroactive performance of PEDOT.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2016
National Category
Biological Sciences
Identifiers
urn:nbn:se:liu:diva-125323 (URN)10.1039/c5ta10096h (DOI)000368839200035 ()
Note

Funding Agencies|Power Papers project from the Knut and Alice Wallenberg foundation; Wallenberg Scholar grant from the Knut and Alice Wallenberg foundation; Marie Curie network Renaissance (NA); European Research Council by Starting Grant Innovative Polymers for Energy Storage (iPes) [306250]; Basque Government

Available from: 2016-02-23 Created: 2016-02-19 Last updated: 2017-03-31

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