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A Halogen‐Free and Flame‐Retardant Sodium Electrolyte Compatible with Hard Carbon Anodes
Uppsala University, Disciplinary Domain of Science and Technology, Faculty of Science and Technology. Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Faculty of Science and Technology. Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.ORCID iD: 0000-0002-5511-3841
Uppsala University, Disciplinary Domain of Science and Technology, Faculty of Science and Technology. Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.ORCID iD: 0000-0002-1442-6593
Department of Materials and Environmental Chemistry Arrhenius Laboratory Stockholm University Stockholm SE‐10691 Sweden.
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2021 (English)In: Advanced Materials Interfaces, ISSN 2196-7350, Vol. 8, no 23, article id 2101135Article in journal (Refereed) Published
Abstract [en]

For sodium-ion batteries, two pressing issues concerning electrolytes are flammability and compatibility with hard carbon anode materials. Non-flammable electrolytes that are sufficiently stable against hard carbon have—to the authors’ knowledge—previously only been obtained by either the use of high salt concentrations or additives. Herein, the authors present a simple, fluorine-free, and flame-retardant electrolyte which is compatible with hard carbon: 0.38 m sodium bis(oxalato)borate (NaBOB) in triethyl phosphate (TEP). A variety of techniques are employed to characterize the physical properties of the electrolyte, and to evaluate the electrochemical performance in full-cell sodium-ion batteries. The results reveal that the conductivity is sufficient for battery operation, no significant self-discharge occurs, and a satisfactory passivation is enabled by the electrolyte. In fact, a mean discharge capacity of 107 ± 4 mAh g−1 is achieved at the 1005th cycle, using Prussian white cathodes and hard carbon anodes. Hence, the studied electrolyte is a promising candidate for use in sodium-ion batteries.

Place, publisher, year, edition, pages
Wiley John Wiley & Sons, 2021. Vol. 8, no 23, article id 2101135
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-462863DOI: 10.1002/admi.202101135ISI: 000709853100001OAI: oai:DiVA.org:uu-462863DiVA, id: diva2:1624273
Funder
Swedish Research Council Formas, 2016-01257, 2018–05973ÅForsk (Ångpanneföreningen's Foundation for Research and Development), 20–675VinnovaSwedish National Infrastructure for Computing (SNIC)Available from: 2022-01-03 Created: 2022-01-03 Last updated: 2024-06-25Bibliographically approved
In thesis
1. Developing Electrolyte Solutions for Sodium-Ion Batteries: Challenging the Use of Hexafluorophosphate
Open this publication in new window or tab >>Developing Electrolyte Solutions for Sodium-Ion Batteries: Challenging the Use of Hexafluorophosphate
2024 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The ability to store energy will be critical for achieving a functioning electrified society largely based on renewable energy sources. Batteries are anticipated to be a vital part of the infrastructure required to facilitate this energy storage. Electrolyte solutions are an essential component of most batteries, including sodium-ion batteries, which are emerging as a potentially more sustainable alternative to lithium-ion batteries.

This thesis critically assesses the use of sodium hexafluorophosphate as an electrolyte in sodium-ion batteries. Although widely used in lithium-ion batteries, the suitability of hexafluorophosphate for sodium-ion batteries needs re-evaluation. In this thesis, properties meriting the use of sodium hexafluorophosphate are explored, including its solubility in different organic solvents, conductivity, ability to prevent anodic aluminium dissolution, and cycling performance in battery cells. Sodium bis(oxalato)borate is investigated as an example of a fluorine-free alternative that may better align with the goal of increasing the sustainability of contemporary batteries. The main drawback of sodium bis(oxalato)borate is its significantly lower solubility compared to sodium hexafluorophosphate. However, at the same concentration in a given solvent, both electrolytes exhibit similar conductivities, challenging the notion that hexafluorophosphate enhances conductivity through low ion association.

Both electrolytes also prevent anodic aluminium dissolution. However, the use of sodium hexafluorophosphate does not consistently ensure adequate passivation of the negative electrode, suggesting that solvents or additives are more central for this process in these systems. In contrast, sodium bis(oxalato)borate appear to significantly contribute to the passivation of the negative electrode, even when used as an additive. As a sole electrolyte, sodium bis(oxalato)borate enable promising cycling performance in both lab-scale cells and in cells close to commercial standards. This research indicates that sodium hexafluorophosphate can be replaced with a fluorine-free electrolyte without compromising battery performance. The findings highlight the potential for more sustainable sodium-ion batteries and represent a step towards reducing the environmental impact of an electrified society.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2024. p. 54
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 2417
National Category
Materials Chemistry
Research subject
Chemistry with specialization in Materials Chemistry; Chemistry with specialization in Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-533190 (URN)978-91-513-2169-1 (ISBN)
Public defence
2024-09-06, Lecture hall Heinz-Otto Kreiss, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
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Available from: 2024-08-13 Created: 2024-06-25 Last updated: 2024-08-13

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Colbin, SimonMogensen, RonnieBuckel, AlexanderNaylor, Andrew J.Kullgren, JollaYounesi, Reza

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