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New pyrrolidinium and piperidinium bis(trifluoromethanesulfonyl)imide (TFSI) ionic liquids (ILs) having allyl substituents were synthesized and characterized. All of them are liquid at room temperature and stable up to 300 o C. The pyrrolidinium-based ILs showed better conductivities and lower viscosities than the corresponding piperidinium-based ILs. Among them, 1-allyl-1-methylpyrrolidinium TFSI showed the lowest viscosity of 52 cP, the highest conductivity of 5.7 mS cm −1, and the most negative cathodic voltage window of −3.2 V (vs. Fc/Fc + ) on a platinum electrode, which are the improved results compared to the corresponding analogue having a saturated substituent, 1-methyl-1-propylpyrrolidinium TFSI.

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