Abstract

Na+-conducting, binary electrolytic mixtures, based on 1-ethyl-3-methyl-imidazolium, trimethyl-butyl-ammonium, and N-alkyl-N-methyl-piperidinium ionic liquid (IL) families, were designed and investigated. The anions were selected among the per(fluoroalkylsulfonyl)imide families. Sodium bis(trifluoromethylsulfonyl)imide, NaTFSI, was selected as the salt. The NaTFSI-IL electrolytes, addressed to safer sodium battery systems, were studied and compared in terms of ionic conductivity and thermal stability as a function of the temperature, the nature of the anion and the cation aliphatic side chain length. Room temperature conductivities of interest for sodium batteries, i.e., largely overcoming 10−4 or 10−3 S cm−1, are displayed. Similar conduction values are exhibited by the EMI-based samples even below −10 °C, making these electrolyte mixtures potentially appealing also for low temperature applications. The NaTFSI-IL electrolytes, with the exception of the FSI-ones, are found to be thermally stable up to 275 °C, depending on the nature of the cation and/or anion, thus extending their applicability above 100 °C and remarkably increasing the reliability and safety of the final device, especially in the case of prolonged overheating.

Highlights

  • The sodium-ion battery technology is a promising alternative to the currently market-dominating lithium-ion one due to the much larger availability, the lower cost and the similar redox potential (2.71 V vs. H+/H2) of Na with respect to Li [1,2]

  • Ionic liquids (ILs), salts molten at room temperature or below, are appealing substitutes as safer electrolytic solvents for replacing the organic ones [4]

  • The investigated ionic liquid electrolytes have exhibited a purity level above 99.5 wt.%; in particular, the content of lithium, halide and moisture is below 2 ppm

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Summary

Introduction

The sodium-ion battery technology is a promising alternative to the currently market-dominating lithium-ion one due to the much larger availability, the lower cost and the similar redox potential (2.71 V vs. H+/H2) of Na with respect to Li [1,2]. To the lithium ones, the sodium-ion devices use electrolytes based on hazardous and volatile organic solvents, representing severe safety issues especially in case of upscaled systems and electric/thermal abuse [3]. In this scenario, ionic liquids (ILs), salts molten at room temperature or below, are appealing substitutes as safer (due to their exceptional flame retarding properties, negligible vapor pressure, thermal robustness) electrolytic solvents for replacing the organic ones [4]. The physicochemical investigations were restricted to a very limited number of IL cations (mainly pyrrolidinium) and anions (mainly, bis(trifluoromethylsulfonyl)imide) and, only few ionic liquid types were studied until now for being addressed to sodium devices.

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