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Importance of First Cycle Conditions on the Electrochemical Performance of Hard Carbon and Prussian White Based Sodium-Ion Batteries Using Fire Resistant, Fluorine-Free Electrolyte
Altris AB, Kungsgatan 70b, S-75318 Uppsala, Sweden..
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.
Altris AB, Kungsgatan 70b, S-75318 Uppsala, Sweden..
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.ORCID iD: 0009-0006-6676-7513
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2024 (English)In: Batteries & Supercaps, E-ISSN 2566-6223, Vol. 7, no 2Article in journal (Refereed) Published
Abstract [en]

Electrolytes based on sodium bis(oxolato)borate (NaBOB) in organophosphates (trimethyl phosphate and triethyl phosphate (TEP)) have shown promise in sodium-ion batteries when compared to conventional electrolytes in that they are fire resistant, fluorine-free and are of lower toxicity. However, these electrolytes tend to exhibit low initial Coulombic efficiency and high overpotentials. We have here demonstrated that NaBOB in TEP can be used in cells with near-commercial capacity loadings. Furthermore, we have shown that formation cycle conditions have a significant positive effect on the cell performance in these higher mass loading cells, and that modification of the formation cycle conditions can be used to increase the capacity retention, lower the overpotentials, and as such increase the rate capability. The viability of optimized formation protocols was also demonstrated in scaled up prototype cells. Formation cycling: In this article we present a solution to the poor cyclability of non-flammable sodium bis(oxolato)borate (NaBOB) in triethyl phosphate (TEP) electrolyte. By developing a formation cycle specific to this NaBOB in TEP electrolyte, we are able to cycle a 4.5 Ah full cell with high mass loading electrodes to beyond 900 cycles before reaching 80 % state of health.image

Place, publisher, year, edition, pages
John Wiley & Sons, 2024. Vol. 7, no 2
Keywords [en]
formation cycling, non-flammable electrolyte, sodium ion battery, Prussian white, hard carbon
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-528414DOI: 10.1002/batt.202300533ISI: 001123295600001OAI: oai:DiVA.org:uu-528414DiVA, id: diva2:1861474
Funder
Swedish Energy AgencyEU, Horizon 2020Available from: 2024-05-28 Created: 2024-05-28 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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Buckel, AlexanderColbin, SimonYounesi, Reza

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