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Sodium bis(oxalato)borate (NaBOB) in trimethyl phosphate: a fire-extinguishing, fluorine-free, and low-cost electrolyte for fullcell 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: 0000-0001-8148-8615
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.ORCID iD: 0000-0002-2736-9145
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2020 (English)In: ACS Applied Energy Materials, E-ISSN 2574-0962, Vol. 3, no 5, p. 4974-4982Article in journal (Refereed) Published
Abstract [en]

Sodium-ion batteries based on all-naturally abundant elements, in which no cobalt, nickel, copper, and fluorine is used, can lead to a major breakthrough in making batteries more sustainable. Safety aspects-in particular, flammability of electrolytes-in the state-of-the-art battery technology is another important concern, especially for applications in which large numbers of cells are employed. Nonflammable battery electrolytes studied so far are based on highly fluorinated compounds or high salt concentrations, which suffer from high cost and toxicity. We here propose an electrolyte based on a single solvent and low-cost and fluorine-free salt at a lower range of "standard" concentrations. Our results show-for the first time-that sodium bis(oxalato)borate (NaBOB) is soluble in the nonflammable solvent trimethyl phosphate (TMP). This finding enables a nonflammable electrolyte with high ionic conductivity and promising electrochemical performance in full-cell sodium-ion batteries. An electrolyte of 0.5 M NaBOB in TMP provides an ionic conductivity of 5 mS cm(-1) at room temperature, which is comparable to the commonly used electrolytes based on sodium hexafluorophosphate (NaPF6) and organic carbonate solvents. The proposed electrolyte shows a Coulombic efficiency of above 80% in the first cycle, which increased to about 97% from the second cycle in sodium-ion battery full-cells consisting of a hard carbon anode and a Prussian white cathode. This work opens up opportunities to design safe electrolytes which can further be optimized with electrolyte additives such as vinylene carbonate for industrial applications.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2020. Vol. 3, no 5, p. 4974-4982
Keywords [en]
electrolyte salt, non-flammable, fire-retardant, hardcarbon, full-cell, Na-ion battery, TMP, NaBOB
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-409478DOI: 10.1021/acsaem.0c00522ISI: 000537656400100OAI: oai:DiVA.org:uu-409478DiVA, id: diva2:1425578
Funder
ÅForsk (Ångpanneföreningen's Foundation for Research and Development), 19-705Swedish Foundation for Strategic Research Available from: 2020-04-21 Created: 2020-04-21 Last updated: 2024-06-25Bibliographically approved
In thesis
1. Realization of Sodium-ion Batteries: From Electrode to Electrolyte Materials
Open this publication in new window or tab >>Realization of Sodium-ion Batteries: From Electrode to Electrolyte Materials
2020 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Batteries are among the most important technologies required to enable the world to move beyond fossil fuels towards a more efficient and environmentally friendly society based on electricity from renewable sources. Unfortunately, the rapidly increasing number and size of batteries that the world needs in order to perform this paradigm shift is putting enormous strain on the supply of traditional raw materials for batteries, such as lithium and cobalt. Batteries built using only earth abundant elements could guarantee that the supply of energy storage will be available to everyone at reasonable prices. Sodium-ion batteries are among the most popular candidates to achieve battery systems that can provide performance close to or on par with lithium-ion batteries at a lower cost and environmental impact. Although the sodium-ion and lithium-ion batteries share many properties, there is a lot of research required before sodium-ion batteries can compete with the highly optimised lithium-ion batteries. This work explores the stability of the solid electrolyte interphase (SEI) formed on the anode in sodium-ion batteries through means of electrochemical measurements and x-ray photoelectron spectroscopy (XPS) analysis. The fundamental properties in regards to solubility and electrochemical stability of the surface layer on model anodes as well as on anode materials like hard carbon and tin-phosphide is discussed. The synthesis and electrochemical performance of Prussian white comprising of all earth abundant elements for use as a low-cost and high-performance cathode material is demonstrated. The work also includes several investigations of alternative solvents and salts for electrolytes that have been analysed in conjunction with sodium-ion cells based on hard carbon and Prussian white. The electrolytes studied possess a wide spectrum of different opportunities such as high ionic conductivity, non-flammability, fluorine-free composition and improved low and high-temperature performance.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2020. p. 78
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1941
Keywords
Sodium-ion batteries, electrolytes, Prussian white
National Category
Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-409502 (URN)978-91-513-0958-3 (ISBN)
Public defence
2020-06-12, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:00 (English)
Opponent
Supervisors
Available from: 2020-05-18 Created: 2020-04-22 Last updated: 2020-06-17
2. 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)
Opponent
Supervisors
Available from: 2024-08-13 Created: 2024-06-25 Last updated: 2024-08-13

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Mogensen, RonnieColbin, SimonMenon, Ashok SreekumarBjörklund, ErikYounesi, Reza

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