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Exploration of Phase Diagram, Structural and Dynamic Behavior of [HMG][FSI] Mixtures with NaFSI across an Extended Composition Range.

Abstract : Hexamethylguanidinium bis(fluorosulfonyl)imide ([HMG][FSI]) has recently been shown to be a promising solid state organic ionic plastic crystal with potential application in advanced alkali metal batteries. This study provides a detailed exploration of the structural and dynamic behavior of [HMG][FSI] mixtures with the sodium salt NaFSI across the whole composition range from 0 to 100 mol%. All mixtures are solids at room temperature. A combination of differential scanning calorimetry (DSC), synchrotron X-ray diffraction (SXRD) and multinuclear solid state NMR spectroscopy is employed to identify a partial phase diagram. The 25 mol% NaFSI/75 mol% [HMG][FSI] composition presents as the eutectic composition with the eutectic transition temperature at 44 ° C. Both DSC and SXRD strongly support the formation of a new compound near 50 mol% NaFSI. Interestingly, the 53 mol% NaFSI [HMG][FSI] composition was consistently found to display features of a pure compound whereas the 50 mol% materials always showed a second phase. Many of the compositions examined showed unusual metastable behaviour. Moreover, the ion dynamics as determined by NMR, indicate that the Na(+) and FSI(-) anions are signifcantly more mobile than the HMG cation in the liquid state (including the metastable state) for these materials.
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https://hal-u-picardie.archives-ouvertes.fr/hal-03716513
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Soumis le : jeudi 7 juillet 2022 - 15:08:26
Dernière modification le : vendredi 5 août 2022 - 14:44:08

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Karolina Biernacka, Faezeh Makhlooghiazad, Ivan Popov, Haijin Zhu, Jean-Noël Chotard, et al.. Exploration of Phase Diagram, Structural and Dynamic Behavior of [HMG][FSI] Mixtures with NaFSI across an Extended Composition Range.. Physical chemistry chemical physics : PCCP, 2022, ⟨10.1039/d2cp01910h⟩. ⟨hal-03716513⟩

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