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An Attempt to Formulate Non-Carbonate Electrolytes for Sodium-Ion Batteries
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.ORCID iD: 0000-0003-2538-8104
2021 (English)In: Batteries & Supercaps, E-ISSN 2566-6223, Vol. 4, no 5, p. 791-814Article in journal (Refereed) Published
Abstract [en]

Non-aqueous carbonate solvents have been the main choice for the development of lithium-ion batteries, and similarly most research on sodium-ion batteries have been performed using carbonate-based solvents. However, the differences between sodium and lithium batteries – in term chemistry/electrochemistry properties as well as electrode materials used – open up opportunities to have a new look at solvents that have attracted little attention as electrolyte solvent. This work investigates properties of a wide range of different solvent classes in the context of sodium-ion battery electrolytes and compares them to the performance of propylene carbonate. The thirteen solvents studied here include one or several members of glymes, carbonates, lactones, esters, pyrrolidones, sulfones, and alkyl phosphates. Out of those, five outperforming solvents of γ-butyrolactone (GBL), γ-valerolactone (GVL), N-methyl-2-pyrrolidone (NMP), propylene carbonate (PC), and trimethyl phosphate (TMP) were further investigated using additives of ethylene sulfite (ES), vinylene carbonate (VC), fluoroethylene carbonate (FEC), prop-1-ene-1,3-sultone (PES), sulfolane (TMS), tris(trimethylsilyl) phosphite (TTSPI), and sodium bis(oxalato)borate (NaBOB). The solvents TMS and tetraethylene glycol dimethyl ether (TEGDME) were tested in 1 : 1 mixtures by volume with the co-solvents; NMP, dimethoxyethane (DME), and TMP. All electrolytes used NaPF6 as the salt. Primary evaluation relied on electrochemical cycling of full-cell sodium-ion batteries consisting of Prussian white cathodes and hard-carbon anodes. Galvanostatic cycling was performed using both two- and three-electrode cells, in addition, cyclic and linear sweep voltammetry was used to further evaluate the electrolyte formulations. Moreover, the resistance was measured on the anode and cathode, using Intermittent current interruption (ICI) technique.

Place, publisher, year, edition, pages
John Wiley & Sons, 2021. Vol. 4, no 5, p. 791-814
Keywords [en]
electrolytes, full-cell, hard carbon, Na-ion batteries, solvents
National Category
Inorganic Chemistry Materials Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-448183DOI: 10.1002/batt.202000252ISI: 000616169000001OAI: oai:DiVA.org:uu-448183DiVA, id: diva2:1578420
Funder
StandUpÅForsk (Ångpanneföreningen's Foundation for Research and Development), 20-675Available from: 2021-07-06 Created: 2021-07-06 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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Supervisors
Available from: 2024-08-13 Created: 2024-06-25 Last updated: 2024-08-13

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Mogensen, RonnieColbin, SimonYounesi, Reza

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