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Sulfonated Cellulose Membranes for Energy Storage Applications
Linköping University, Department of Science and Technology, Laboratory of Organic Electronics. Linköping University, Faculty of Science & Engineering.
2023 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In the ongoing efforts to reduce the dependency of mankind on fossil fuels for the supply of energy, renewable energy sources such as solar cells and wind turbines are employed to an increasing extent. Transitioning a large portion of electrical grids to intermittent power sources come with several problems that need to be taken into account and handled, such as ensuring supply at peak power demand and considering frequency regulation and other issues related to the stability of the grid. One possible way to increase the amount of intermittent energy sources while maintaining a stable grid and power supply is to use large scale energy storage systems to store energy that can then be used as needed.

One of the most promising energy storage systems for this purpose is the redox flow battery, an electrochemical energy storage system in which the power output and total energy storage capacity are decoupled, the former relating to the area of the electrochemical cell and the latter to the amount of electrolyte. This decoupling is a great advantage since large electrolyte tanks can be used to store huge amounts of energy in a stationary manner.

Redox flow batteries and other devices such as fuel cells and certain types of batteries are dependent on a selective membrane for their function. The membrane needs to efficiently transport certain species while blocking others, and the function of the membrane is often greatly influencing the performance of the devices that employ them. Current state-of-the-art ion selective membranes are often produced from PFSA-based materials, which are problematic in terms of sustainability and cost. Finding ways to replace such membranes with equally functional components produced from bio-based materials would be a large step forward in terms of improving the sustainability and cost-efficiency of large scale electrochemical energy storage.

In this work, functionalized cellulose nanofibrils are used as starting material to produce novel bio-based selective membranes aimed to be employed in electrochemical energy storage systems, in particular redox flow batteries. The possibility to precisely tune the properties of membranes via the degree of modification of the starting material is investigated, as well as some strategies to further improve the performance of membranes via additives and post-fabrication modifications.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2023. , p. 49
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 2277
Keywords [en]
Nanocellulose, Membranes, Ionic transport, Redox flow batteries
National Category
Energy Engineering
Identifiers
URN: urn:nbn:se:liu:diva-191941DOI: 10.3384/9789179295929ISBN: 9789179295912 (print)ISBN: 9789179295929 (electronic)OAI: oai:DiVA.org:liu-191941DiVA, id: diva2:1739570
Public defence
2023-03-24, K1, Kåkenhus, Campus Norrköping, Norrköping, 10:00 (English)
Opponent
Supervisors
Available from: 2023-02-27 Created: 2023-02-27 Last updated: 2023-12-06Bibliographically approved
List of papers
1. Sulfonated Cellulose Membranes Improve the Stability of Aqueous Organic Redox Flow Batteries
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2022 (English)In: Advanced Energy and Sustainability Research, ISSN 2699-9412, Vol. 3, no 9, article id 2200016Article in journal (Refereed) Published
Abstract [en]

The drawbacks of current state-of-the-art selective membranes, such as poor barrier properties, high cost, and poor recyclability, limit the large-scale deployment of electrochemical energy devices such as redox flow batteries (RFBs) and fuel cells. In recent years, cellulosic nanomaterials have been proposed as a low-cost and green raw material for such membranes, but their performance in RFBs and fuel cells is typically poorer than that of the sulfonated fluoropolymer ionomer membranes such as Nafion. Herein, sulfonated cellulose nanofibrils densely cross-linked to form a compact sulfonated cellulose membrane with limited swelling and good stability in water are used. The membranes possess low porosity and excellent ionic transport properties. A model aqueous organic redox flow battery (AORFB) with alizarin red S as negolyte and tiron as posolyte is assembled with the sulfonated cellulose membrane. The performance of the nanocellulose-based battery is superior in terms of cyclability in comparison to that displayed by the battery assembled with commercially available Nafion 115 due to the mitigation of crossover of the redox-active components. This finding paves the way to new green organic materials for fully sustainable AORFB solutions.

Place, publisher, year, edition, pages
Wiley, 2022
Keywords
aqueous organic redox flow batteries; crossover; ion-selective membranes; nanocellulose
National Category
Other Chemical Engineering
Identifiers
urn:nbn:se:liu:diva-187403 (URN)10.1002/aesr.202200016 (DOI)000823291000001 ()
Note

Funding Agencies|VINNOVA (Digital Cellulose Center); BillerudKorsnas; Knut and Alice Wallenberg foundation [KAW 2019.0604, KAW 2021.0195]; Swedish Energy Agency [52023-1]; Vetenskapradet [2016-05990]

Available from: 2022-08-22 Created: 2022-08-22 Last updated: 2023-12-06Bibliographically approved
2. Sulfonated Cellulose Membranes: Physicochemical Properties and Ionic Transport versus Degree of Sulfonation
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2022 (English)In: Advanced Sustainable Systems, ISSN 2366-7486, Vol. 6, no 11, article id 2200275Article in journal (Refereed) Published
Abstract [en]

The next generation of green ion selective membranes is foreseen to be based on cellulosic nanomaterials with controllable properties. The introduction of ionic groups into the cellulose structure via chemical modification is one strategy to obtain desired functionalities. In this work, bleached softwood fibers are oxidatively sulfonated and thereafter homogenized to liberate the cellulose nanofibrils (CNFs) from the fiber walls. The liberated CNFs are subsequently used to prepare and characterize novel cellulose membranes. It is found that the degree of sulfonation collectively affects several important properties of the membranes via the density of fixed charged groups on the surfaces of the CNFs, in particular the membrane morphology, water uptake and swelling, and correspondingly the ionic transport. Both ionic conductivity and cation transport increase with the increased level of sulfonation of the starting material. Thus, it is shown that the chemical modification of the CNFs can be used as a tool for precise and rational design of green ion selective membranes that can replace expensive conventional fluorinated ionomer membranes.

Place, publisher, year, edition, pages
Wiley-V C H Verlag GMBH, 2022
Keywords
crosslinked sulfonated nanocelluloses; ionic transport; pore sizes; selective membranes; water uptake
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:liu:diva-188444 (URN)10.1002/adsu.202200275 (DOI)000846651200001 ()
Note

Funding Agencies|VINNOVA (Digital Cellulose Center); BillerudKorsnas; Knut and Alice Wallenberg foundation [KAW 2019.0604, KAW 2021.0195]; Vetenskapradet [2016-05990]; Wallenberg Wood Science Center; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University [2009-00971]

Available from: 2022-09-14 Created: 2022-09-14 Last updated: 2023-12-06Bibliographically approved

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