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Physicochemical characterizations of novel dicyanamide-based ionic liquids applied as electrolytes for supercapacitors.

ABSTRACT: Novel ionic liquids (ILs), containing a dicyanamide anion (DCA^-), are synthesized and applied as suitable electrolytes for electrochemical double layer capacitors (EDLCs). The prepared ILs are either composed of triethyl-propargylammonium (N_222pr ⁺) or triethyl-butylammonium (N₂₂₂₄ ⁺) cations paired with the DCA^- anion. The structure of the cation influences its electrostatic interaction with the DCA^- anion and highly impacts the physical and electrochemical properties of the as-prepared ILs. The geometry and the length of the alkyl chain of the propargyl group in N_222pr ⁺ enhance the ionic conductivity of N_222pr-DCA (11.68 mS cm^-1) when compared to N₂₂₂₄-DCA (5.26 mS cm^-1) at 298 K. It is demonstrated that the Vogel-Tammann-Fulcher model governs the variations of the transport properties investigated over the temperature range of 298-353 K. A maximum potential window of 3.29 V is obtained when N_222pr-DCA is used as electrolyte in a graphene based symmetric EDLC system. Cyclic voltammetry and galvanostatic measurements confirm that both electrolytes exhibit an ideal capacitive behavior. The highest specific energy of 55 W h kg^-1 is exhibited in the presence of N₂₂₂₄-DCA at a current density of 2.5 A g^-1.

SUBMITTER: Zarrougui R

PROVIDER: S-EPMC9085644 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature

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Physicochemical characterizations of novel dicyanamide-based ionic liquids applied as electrolytes for supercapacitors.

Zarrougui Ramzi R Hachicha Rahma R Rjab Refka R Messaoudi Sabri S Ghodbane Ouassim O

RSC advances 20180801 54

Novel ionic liquids (ILs), containing a dicyanamide anion (DCA-), are synthesized and applied as suitable electrolytes for electrochemical double layer capacitors (EDLCs). The prepared ILs are either composed of triethyl-propargylammonium (N222pr +) or triethyl-butylammonium (N2224 +) cations paired with the DCA- anion. The structure of the cation influences its electrostatic interaction with the DCA- anion and highly i ...[more]

PMID: 35548773

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Project description:The dynamics of probe molecules is commonly used to investigate the structural dynamics of room-temperature ionic liquids; however, the extent to which this dynamics reflects the dynamics of the ionic liquids or is probe specific has remained debated. Here, we explore to what extent the vibrational and rotational dynamics of the dicyanamide anion, a common ionic liquid anion, correlates with the structural relaxation of ionic liquids. We use polarization-resolved, ultrafast infrared spectroscopy to probe the temperature- and probe-concentration-dependent dynamics of samples with small amounts of 1-ethyl-3-methylimidazolium ([emim]+) dicyanamide ([DCA]-) dissolved in four [emim]+-based ionic liquids with tetrafluoroborate ([BF4]-), bis(trifluoromethylsulfonyl)imide ([NTf2]-), ethylsufate ([EtSO4]-), and triflate ([OTf]-) as anions. The transient spectra after broad-band excitation at 2000-2300 cm-1, resonant with the symmetric and antisymmetric C≡N stretching vibrations, initially contain oscillatory signatures due to the vibrational coherence between both modes. Vibrational population relaxation occurs on two distinct time scales, ∼6-7 and ∼15-20 ps. The vibrational dynamics is rather insensitive to the details of the ionic liquid anion and temperature, except for the slow vibrational relaxation component. The decay of the excitation anisotropy, a measure of the rotational dynamics of [DCA]-, markedly depends on temperature, and the obtained decay time exhibits an activation energy of ∼15-21 kJ/mol. Remarkably, neither the rotation time nor the activation energy can be simply explained by the variation of the macroscopic viscosity. Hence, our results suggest that the dynamics of dicyanamide is only in part representative of the ionic liquid structural dynamics. Rather, the dynamics of the probe anion seems to be determined by the specific interaction of [DCA]- with the ionic liquid's ions for the class of [emim]+-based ionic liquids studied here.

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Physicochemical characterizations of novel dicyanamide-based ionic liquids applied as electrolytes for supercapacitors.

Publications

Physicochemical characterizations of novel dicyanamide-based ionic liquids applied as electrolytes for supercapacitors.

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