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Towards safer electrolytes: comparing the air stability and electrochemical properties of NaPF6, NaTFSI and Na[B(hfip)4]·DME for sodium-ion batteries

Darren Ould, James Courtney Orcid Logo, David J. Morgan Orcid Logo, Daniel Curtis Orcid Logo, Marcin Orzech Orcid Logo, Sajad Kiani Orcid Logo, Brent de Boode, Clare P. Grey Orcid Logo, Dominic S. Wright Orcid Logo, Serena Margadonna Orcid Logo

EES Batteries

Swansea University Authors: Darren Ould, James Courtney Orcid Logo, Daniel Curtis Orcid Logo, Marcin Orzech Orcid Logo, Sajad Kiani Orcid Logo, Serena Margadonna Orcid Logo

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DOI (Published version): 10.1039/d6eb00011h

Abstract

Sodium-ion batteries (SIBs) are a promising post lithium-ion battery (LIB) technology, which offer advantages in improved sustainability. This work investigates using NaTFSI [TFSI = bis(trifluoromethylsulfonyl)imide] and Na[B(hfip)4]·DME [hfip = OCH(CF3)2 (OiPrF), DME = 1,2-dimethoxyethane] as alter...

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Published in: EES Batteries
ISSN: 3033-4071
Published: Royal Society of Chemistry (RSC) 2026
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URI: https://cronfa.swan.ac.uk/Record/cronfa71325
Abstract: Sodium-ion batteries (SIBs) are a promising post lithium-ion battery (LIB) technology, which offer advantages in improved sustainability. This work investigates using NaTFSI [TFSI = bis(trifluoromethylsulfonyl)imide] and Na[B(hfip)4]·DME [hfip = OCH(CF3)2 (OiPrF), DME = 1,2-dimethoxyethane] as alternative electrolyte salts to the current benchmark standard NaPF6 and compares their air stability, electrochemical properties and performance in sodium-ion coin cells. Multinuclear NMR spectroscopic experiments found that NaPF6 and NaTFSI were stable to atmospheric air after one month, whereas Na[B(hfip)4]·DME showed signs of degradation. The air stability of NaPF6 was compared to LiPF6, where the latter underwent complete decomposition after 24 hours. Electrochemical investigations in 1 M solutions of ethylene carbonate: diethyl carbonate (EC:DEC) solvent revealed 1 M NaPF6 has the highest bulk conductivity. Cyclic voltammetry experiments showed 1 M NaPF6 and 1 M Na[B(hfip)4]·DME are compatible with aluminium foils up to 4.2 V vs. Na/Na+, whereas 1 M NaTFSI underwent aluminium corrosion. Corrosion could be supressed by either limiting cut-off voltage or by the addition of 2 wt% NaPF6 as an additive, both applicable mitigation strategies. Stable long-term cycling at 1C rate in cells using a Prussian white cathode and hard carbon anode occured with both 1 M NaPF6 and 1 M NaTFSI electrolytes. Thus, 1 M NaTFSI is a viable alternative to 1 M NaPF6 in SIBs with a Prussian white cathode, offering a potentially safer electrolyte choice by limiting HF generation on account of the strong C–F bonds in NaTFSI.
College: Faculty of Science and Engineering
Funders: Faraday Institution (SPR_100064)