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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
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: 2018-11-26
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
Strietzel, C., Emanuelsson, R., Strömme, M. & Sjödin, M. (2018). Flexible All Organic Batteries Based on Conducting Redox Polymers. In: MRS (Ed.), MRS Fall meeting 2018: Flexible/Wearable Energy Storage I. Paper presented at MRS Fall meeting 2018. Boston November. Boston, Article ID BM08.11.02.
Open this publication in new window or tab >>Flexible All Organic Batteries Based on Conducting Redox Polymers
2018 (English)In: MRS Fall meeting 2018: Flexible/Wearable Energy Storage I / [ed] MRS, Boston, 2018, article id BM08.11.02Conference paper, Published paper (Refereed)
Abstract [en]

Batteries consisting of naturally occurring organic materials can be envisioned as sustainable alternatives to conventional metal-based batteries, thus

avoiding the negative environmental impact associated with the production and recycling of the latter. In this way the negative environmental impact of the

constantly increasing demand for secondary batteries can be decreased. Apart from being fully organic, such batteries also open up for flexible battery

designs as they can be produced in a roll-to-roll process and they are anticipated to be viable in a broad range of applications as energy supplies in

innovative flexible electronics designs. In the current work, fully organic batteries are realized utilizing conducting redox polymers (CRPs) as electrode

materials. CRPs combine the high charge storage capacity of a redox active pendant group (PG) with the conduction properties of a conducting polymer

(CP) backbone, both to reduce the need for addition of conductive carbon black and increasing the stability of the PG redox conversion in a battery setup.

The first results from a fully organic, aqueous battery based on CRP electrode material are presented. Challenges and possibilities of this type of battery in flexible battery designs are discussed.

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-366559 (URN)
Conference
MRS Fall meeting 2018. Boston November
Available from: 2018-11-21 Created: 2018-11-21 Last updated: 2018-11-26
Banerjee, A., Araujo, R. B., Sjödin, M. & Ahuja, R. (2018). Identifying the tuning key of disproportionation redox reaction in terephthalate: A Li-based anode for sustainable organic batteries. Nano Energy, 47, 301-308
Open this publication in new window or tab >>Identifying the tuning key of disproportionation redox reaction in terephthalate: A Li-based anode for sustainable organic batteries
2018 (English)In: Nano Energy, ISSN 2211-2855, E-ISSN 2211-3282, Vol. 47, p. 301-308Article in journal (Refereed) Published
Abstract [en]

The ever-increasing consumption of energy storage devices has pushed the scientific community to realize strategies toward organic electrodes with superior properties. This is owed to advantages such as economic viability and eco-friendliness. In this context, the family of conjugated dicarboxylates has emerged as an interesting candidate for the application as negative electrodes in advanced Li-ion batteries due to the revealed thermal stability, rate capability, high capacity and high cyclability. This work aims to rationalize the effects of small molecular modifications on the electrochemical properties of the terephthalate anode by means of first principles calculations. The crystal structure prediction of the investigated host compounds dilithium terephthalate (Li2TP) and diethyl terephthalate (Et2Li0TP) together with their crystal modification upon battery cycling enable us to calculate the potential profile of these materials. Distinct underlying mechanisms of the redox reactions were obtained where Li2TP comes with a disproportionation reaction while Et2Li0TP displays sequential redox reactions. This effect proved to be strongly correlated to the Li coordination number evolution upon the Li insertion into the host structures. Finally, the calculations of sublimation enthalpy inferred that polymerization techniques could easily be employed in Et2Li0TP as compared to Li2TP. Similar results are observed with methyl, propyl, and vinyl capped groups. That could be a strategy to enhance the properties of this compound placing it into the gallery of the new anode materials for state of art Li-batteries.

Keywords
Li-ion organic battery, Lithium terephthalate, Disproportionation, Redox potential
National Category
Physical Chemistry Materials Chemistry Engineering and Technology
Identifiers
urn:nbn:se:uu:diva-354095 (URN)10.1016/j.nanoen.2018.02.038 (DOI)000430057000031 ()
Funder
Swedish Research Council, 2016-06014
Available from: 2018-06-19 Created: 2018-06-19 Last updated: 2018-07-04Bibliographically approved
Sterby, M., Emanuelsson, R., Strömme, M. & Sjödin, M. (2018). In Situ Methods for Understanding Charge Transport in a Conducting Redox Polymer. In: MRS (Ed.), Materials Research Society. Fall meeting 2018. Boston: Excitons, Electrons and Ions in Organic Materials. Paper presented at MRS Fall meeting. Boston 2018. Boston, Article ID EP05.01.07.
Open this publication in new window or tab >>In Situ Methods for Understanding Charge Transport in a Conducting Redox Polymer
2018 (English)In: Materials Research Society. Fall meeting 2018. Boston: Excitons, Electrons and Ions in Organic Materials / [ed] MRS, Boston, 2018, article id EP05.01.07Conference paper, Published paper (Refereed)
Abstract [en]

Organic materials can be used to ensure sustainable electrical energy storage, but since organic molecules are generally insulating conducting additives are commonly used to ensure electrical conductivity throughout the material. A different approach is to use conducting redox polymers (CRPs). CRPs consist of a redox active pendant group, used for its high capacity, attached to a conducting polymer backbone. The CRP presented here is aimed to be used as the positive electrode in a water-based organic battery. In this work we employ 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 respiration and in photosynthesis. The aim of the study is to understand the charge transport properties of the CRP. The CRP studied is characterized by various in-situ electrochemical methods including conductance, Quartz Crystal Microbalance (QCM), UV-vis and Electron Paramagnetic Resonance (EPR). Based on the results the electron and ion transport during electrochemical redox conversion will 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.

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-366558 (URN)
Conference
MRS Fall meeting. Boston 2018
Available from: 2018-11-21 Created: 2018-11-21 Last updated: 2018-11-26
Karlsson, C., Strietzel, C., Huang, H., Sjödin, M. & Jannasch, P. (2018). Nonstoichiometric Triazolium Protic Ionic Liquids for All-Organic Batteries. ACS Applied Energy Materials
Open this publication in new window or tab >>Nonstoichiometric Triazolium Protic Ionic Liquids for All-Organic Batteries
Show others...
2018 (English)In: ACS Applied Energy Materials, ISSN 2574-0962Article in journal (Refereed) Published
Abstract [en]

Nonstoichiometric protic ionic liquids (NSPILs) are efficient electrolytes for protic electrochemical devices such as the all-organic proton battery, which has been suggested as a sustainable approach to energy storage. NSPILs contain a mixture of proton donors and acceptors and are ideal for this purpose due to their high proton conductivity, high electrochemical stability, low cost, and ease of synthesis. However, the electrolyte proton activity must be controlled carefully in these devices since it greatly influences the kinetics and energetics of the electrode redox reactions and, hence, also impacts battery device performance. In this study, specific NSPILs were designed and evaluated as electrolytes for the all-organic proton battery. The NSPILs were based on either 1,2,4-triazole or 1-methyl-1,2,4-triazole partially protonated with bis(trifluoromethylsulfonyl)imide (TFSI) to produce a range of NSPILs with different degrees of protonation. Both types of NSPIL investigated here exhibited a maximum conductivity of 1.2 S/cm (at 120 and 70 °C, respectively), and the eutectic composition of 1-methyl-1,2,4-triazolium TFSI also had high conductivity at 25 °C (24.9 mS/cm), superior to, e.g., imidazolium TFSI NSPILs. Pulsed field gradient NMR in conjunction with electrochemical impedance spectroscopy showed that the conductivity originated mainly from vehicle diffusion and proton hopping. Quinone functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) electrodes exhibited reversible, fast, and stable redox conversion in these electrolytes, and a model is suggested to determine proton activities of NSPILs based on the quinone formal potential. An all-organic proton battery cell was assembled to demonstrate the usefulness of these electrolytes in devices. Fast and complete redox conversion with a cell potential of 0.45 V was demonstrated, even up to scan rates corresponding to 140 C. Compared to the pyridine based electrolytes used for the all-organic proton battery up until now, the present electrolytes display several advantages including lower melting point, lower toxicity, and compatibility with plastic materials.

Place, publisher, year, edition, pages
American Chemical Society, 2018
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-364966 (URN)10.1021/acsaem.8b01389 (DOI)
Funder
SweGRIDS - Swedish Centre for Smart Grids and Energy Storage
Available from: 2018-11-07 Created: 2018-11-07 Last updated: 2018-11-07
Wang, H., Emanuelsson, R., Strömme, M. & Sjödin, M. (2018). Quinone redox potential tunning and characterization of quinone-PEDOT as a lithium cathode. In: : . Paper presented at 2018  Electronic Processes in Organic Materials Gordon Research Conference.
Open this publication in new window or tab >>Quinone redox potential tunning and characterization of quinone-PEDOT as a lithium cathode
2018 (English)Conference paper, Poster (with or without abstract) (Other academic)
National Category
Nano Technology
Identifiers
urn:nbn:se:uu:diva-368269 (URN)
Conference
2018  Electronic Processes in Organic Materials Gordon Research Conference
Available from: 2018-12-03 Created: 2018-12-03 Last updated: 2018-12-06
Åkerlund, L., Emanuelsson, R., Strömme, M. & Sjödin, M. (2018). The proton trap – a new route to high potential organic energy storage. In: : . Paper presented at Gordon Research Conference: Electronic Processes in Organic Materials.
Open this publication in new window or tab >>The proton trap – a new route to high potential organic energy storage
2018 (English)Conference paper, Poster (with or without abstract) (Refereed)
Abstract [en]

Floods, droughts and unpredictable weather could be the new normal state and reality for millions of people in a near future, unless we drastically decrease our greenhouse gas emissions so that the temperature increase can be kept below 2°C, as was agreed upon at the climate meeting in Paris 2015. To tackle environmental issues, material innovations will most certainly be essential for many of the technical solutions needed. One of the major challenges we are facing is how to deal with the massive energy demand following the average lifestyle of today in a way that is both reliable and sustainable. Renewable energy sources have a varying output over time and cannot by themselves meet these requirements; hence ways to store the energy is crucial. Our work is aimed at finding and developing new organic materials for energy storage that can contribute to a better alternative than the batteries that are on the market today. Many aspects of the resource exploitation for making a lithium ion battery are far from sustainable and, with the increasing number of electronic devices for numerous applications, we need new options. One way to make organic energy storage is to combine a conducting polymer backbone with a redox active pendant group, as to combine the features of conductivity and insolubility brought by the polymer backbone with the capacity of the pendant group. For this combination to be applicable the two parts must match in their respective activity windows. Additionally, one also needs to have a matching electrolyte system, in which the energy storage material is cycling reversibly at a reasonable scan rate and where no degradation occurs, to get a fully viable system for practical applications.

In this work[1] we have developed new copolymers for organic energy storage containing something we call the proton trap. The proton trap system enables reversible cycling of hydroquinones, which, in comparison to their lithiated analogues, can provide a higher energy density originating in the higher redox potential. The proton trap system is based on incorporating a proton acceptor into the compound, which enables reversible proton transfer during redox-cycling. Thanks to the proton trap system, the redox processes of hydroquinone compounds can be utilized in many different electrolytes, without the use of coordinating salts (e.g. Li-salts) or protic solvents (as in aqueous electrolytes).

With a cathode based on the pure proton trap material (no additives) and Li-foil as the anode, functioning batteries were assembled and characterized. After the publication of this study, the problems connected to the linker unit have been targeted and new results continue to take us small steps forward in the work targeting renewable organic batteries for a future of sustainable energy storage. When also finding a functioning and sustainable anode material we can enable fully organic based battery systems, enabling a closed loop of renewable energy production and storage, which is something we need in order to keep the climate changes under control.

[1] Åkerlund, L., Emanuelsson, R., Renault, S., Huang, H., Brandell, D., Strømme, M., Sjödin M. (2017). The proton trap Technology—Toward high potential quinone‐based organic energy storage. Advanced Energy Materials, 7(20), 1700259.

Keywords
Organic energy storage, Proton trap, Conducting redox polymers, Hydroquinones
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-359834 (URN)
Conference
Gordon Research Conference: Electronic Processes in Organic Materials
Funder
SweGRIDS - Swedish Centre for Smart Grids and Energy Storage, 125809601
Available from: 2018-09-06 Created: 2018-09-06 Last updated: 2018-09-06
Emanuelsson, R., Sterby, M., Strømme, M. & Sjödin, M. (2017). An All-Organic Proton Battery. Journal of the American Chemical Society, 139(13), 4828-4834
Open this publication in new window or tab >>An All-Organic Proton Battery
2017 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 139, no 13, p. 4828-4834Article in journal (Refereed) Published
Abstract [en]

Rechargeable batteries that use organic matter as. the capacity-carrying material have previously been considered a technology for the future. Earlier batteries in which both the anode and cathode consisted of organic material required significant amounts of conductive additives and were often based on metal-ion electrolytes containing Li+ or Na+. However, we have used conducting poly(3,4-ethylenedioxythiophene) (PEDOT), functionalized with anthraquinone (PEDQT-AQ) or, benzonquinone (PEDOT-BQ) pendant groups as the negative and positive electrode materials, respectively, to make an all-organic proton battery devoid of metals. The electrolyte consists of a proton donor and acceptor slurry containing substituted pyridinium triflates and the corresponding pyridine base. This slurry allows the 2e(-)/2H(+) quinone/hydroquinone redox reactions while suppressing proton reduction in the battery cell. By using strong (acidic) proton donors, the formal potential of the quinone redox reactions is tuned into the potential region in which the PEDOT backbone is conductive, thus eliminating the need for conducting additives. In this all-organic proton battery cell, PEDOT-AQ and PEDOT-BQ deliver 103 and 120 mAh g(-1), which correspond to 78% and 75%, respectively, of the theoretical specific capacity of the materials at an average cell potential of 0.5 V. We show that PEDOT-BQ determines the cycling stability of the device while PEDOT-AQ provides excellent reversibility for at least 1000 cycles. This proof-of-concept shows the feasibility of assembling all organic proton batteries which require no conductive additives and also reveals where the challenges and opportunities lie on the path to producing plastic batteries.

Keywords
rechargeable lithium batteries, li-ion batteries, electrode materials, energy-storage, cathode, anode, salt, electrochemistry, derivatives, polymer
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-319048 (URN)10.1021/jacs.7b00159 (DOI)000398764000036 ()28293954 (PubMedID)
Funder
Swedish Foundation for Strategic Research Swedish Research CouncilCarl Tryggers foundation Swedish Energy AgencyEU, Horizon 2020, H2020/2014-2020 644631
Available from: 2017-03-30 Created: 2017-03-30 Last updated: 2017-05-16Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0003-4126-4347

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