Conductances of some uni-univalent electrolytes in adiponitrile at 25.degree.

Sears, Paul G.; Caruso, Joseph A.; Popov, Alexander I.

doi:10.1021/j100863a020

Cited by 24 publications

(10 citation statements)

References 5 publications

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“…The density of the pure components and all mixtures was measured at atmospheric pressure from (293.15–363.15) K and the resulting data are presented in Tables – . Excellent agreement was found between density data of each pure component measured herein with those available in the literature: that is, <0.1% average deviation between experimental and literature values for [Pyrr 14 ][TFSI] − and ADN ,− and ca. 0.2% deviation for GLN − , and BTN. − The percentage deviations between experimental density values reported in this work for the neat components and those reported previously in the literature are shown in Figures S7 to S10.…”

Section: Resultssupporting

confidence: 82%

“…The viscosity of the pure IL (77.7 mPa·s at 298.15 K) has been measured many times previously, and the values reported here are in good agreement with values in the literature (ca. 0.2–2% deviation between experimental and literature values). ,,,,− The viscosity data of the pure dinitrile solvents, although less readily found in the literature, are considered in reasonable agreement with the available data, GLN ,, and ADN. ,,,, However, the measured viscosity of the pure BTN (0.8 mPa·s at 298.15 K) appears to be overestimated across the full temperature range when compared to reference values (0.55 mPa·s at 298.15 K). ,, While the absolute difference is small (ca. 0.25 mPa·s), the relative difference is over 30% at 298 K and most significant for the neat mononitrile solvent.…”

Section: Resultsmentioning

confidence: 54%

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Physical–Chemical Characterization of Binary Mixtures of 1-Butyl-1-methylpyrrolidinium Bis{(trifluoromethyl)sulfonyl}imide and Aliphatic Nitrile Solvents as Potential Electrolytes for Electrochemical Energy Storage Applications

et al. 2016

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In the scope of improving the energy and power densities of electrochemical double layer capacitors (EDLCs), the development of high performance electrolytes with enhanced operative voltages is imperative. The formulation of mixtures containing ionic liquids with organic molecular solvents is an important strategy in the pursuit of developing highly electrochemically stable and safe materials while retaining fast transport properties for high power applications. In this work, we report on the physical–chemical investigations into binary mixtures containing the ionic liquid 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide with one mononitrile solvent, butyronitrile, and two dinitrile solvents, glutaronitrile and adiponitrile, as potential electrolytes for EDLCs. The thermal, volumetric, and transport properties of the binary mixtures are investigated as functions of the electrolyte composition and temperature. Furthermore, the electrolyte composition which exhibits the highest conductivity for each of the binary mixtures was determined, and its electrochemical stability is reported using a glassy carbon macrodisk electrode.

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Section: Resultssupporting

confidence: 82%

Section: Resultsmentioning

confidence: 54%

Physical–Chemical Characterization of Binary Mixtures of 1-Butyl-1-methylpyrrolidinium Bis{(trifluoromethyl)sulfonyl}imide and Aliphatic Nitrile Solvents as Potential Electrolytes for Electrochemical Energy Storage Applications

et al. 2016

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Section: Methodsmentioning

confidence: 51%

“…The specific resistivity of the remaining quaternary ammoniums used in this study is expected to be close to the specific resistivity of NBu 4 I, as it was shown that the chain length of substituents (ethyl to hexyl) and the symmetry of quaternary ammonium salts changes the specific conductivity by less than 10%. [29][30][31] The IR drop across the working and reference electrodes at current densities of 1 to 5 mA/cm 2 is less than 1 mV in this study. (I R = J A (ρ L/A) = J ρ L = 5 mA cm −2 × 0.071 cm × 0.5 cm < 1 mV, where A is the area of the working electrode, L is the distance between the reference and working electrodes, ρ is the specific resistivity of the solution, and R is the solution resistance.…”

Section: Methodsmentioning

confidence: 59%

Electrochemical Stability of Quaternary Ammonium Cations: An Experimental and Computational Study

Mousavi

Kashefolgheta

Stein

et al. 2015

J. Electrochem. Soc.

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Quaternary ammonium ions, NR 4 + , are among the most electrochemically stable organic cations. Because of their wide electrochemical windows, they are frequently used in batteries and electrochemical capacitors. Improving the electrochemical stability and expanding the electrochemical windows of quaternary ammonium ion is highly desired. In this work, we investigated the electrochemical stability of quaternary ammonium ions and showed that the chain length, type (primary vs. secondary), size, and steric hindrance of the saturated alkyl substituents have only a very small effect (less than 150 mV) on their electrochemical stability toward reduction. To provide a molecular understanding of substituent effects on electrochemical stability, quantum calculations were performed employing density functional theory, and it was shown that the structure of saturated aliphatic alkyl substituents has only minimal effects on the electronic environment around the positive nitrogen center and the LUMO energy level of quaternary ammonium cations. Moreover, a linear correlation between the cathodic limit and the LUMO energy levels of the NR 4 + , N-butylpyridinium, and 1-ethyl-3-methylimidazolium ions was found, suggesting that electrochemical stabilities of new cations may be computationally predicted on the basis of LUMO energies of these systems. With the increasing global demand for energy, improving existing energy storage technologies is as critical as developing more efficient methods for energy production. For one important class of energy storage technologies, namely electrical energy storage, the energy density of a device is usually limited by the voltage window in which the device can function. Therefore, expanding the working voltage range of such devices is highly desired. The electrochemical decomposition of electrolytes, which are commonly used in energy storage devices such as electrochemical capacitors, often limits the useful voltage window 1 because these devices can function properly only within the electrochemical window of their electrolyte. Modifying the structure of electrolytes and improving their electrochemical stabilities has been the focus of numerous studies to date. [2][3][4][5][6][7][8][9][10][11][12][13][14][15] The electrochemical window of an electrolyte is the voltage range in which the electrolyte is chemically stable and does not get reduced or oxidized as a result of the applied potential. 16 The upper end of the electrochemical window is usually limited by the oxidation of the anion, and the lower end of the electrochemical window is determined by the reduction of the cation. 1 One of the most electrochemically stable classes of organic cations comprises the quaternary ammonium ions, NR 4 + . These are highly inert toward reduction, offer wide electrochemical windows, and are, therefore, frequently used in batteries and capacitors. 2,5,6,17 Much research has been devoted to improving the electrochemical stability of quaternary ammonium ions. 4,[9][10][11][12][13][14][15] Reduction of qua...

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“…The discrepancy between the ion-pair dissociation constants of tri (isoamyl) butylammonium tetraphenylborate and the tetrabutylammonium iodide is puzzling, especially in view of the fact that both electrolytes exhibit normal behavior in adiponitrile solutions. 20 It should be pointed out, however, that tetraalkylammonium halides show appreciable association even in solvents of high dielectric constant such as acetonitrile,21 where the ion-pair dissociation constant for tetramethylammonium iodide, for example, is 3.62 X 10~2.…”

Section: Resultsmentioning

confidence: 99%

Conductances and dissociation of some 5-substituted tetrazoles in 1,1,3,3-tetramethylguanidine at 25.degree.

Caruso¹,

Sears²,

Popov³

1967

J. Phys. Chem.

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Electrical conductances of tetrazole, nine 5-substituted tetrazoles, picric acid, tetrabutylammonium iodide, and tri (isoamyl) butylammonium tetraphenylborate were measured in 1,1,3,3-tetramethylguanidine (TMG) at 25°. Dissociation constants of these compounds were determined from the conductance data. The inductive effect of the substituent groups on the acid strength of the 5-substituted tetrazoles is illustrated by a reasonable linearity of the Taft plot. The dielectric constant of TMG was found to be 11.00 ± 0.02 at 25°.

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Conductances of some uni-univalent electrolytes in adiponitrile at 25.degree.

Cited by 24 publications

References 5 publications

Physical–Chemical Characterization of Binary Mixtures of 1-Butyl-1-methylpyrrolidinium Bis{(trifluoromethyl)sulfonyl}imide and Aliphatic Nitrile Solvents as Potential Electrolytes for Electrochemical Energy Storage Applications

Physical–Chemical Characterization of Binary Mixtures of 1-Butyl-1-methylpyrrolidinium Bis{(trifluoromethyl)sulfonyl}imide and Aliphatic Nitrile Solvents as Potential Electrolytes for Electrochemical Energy Storage Applications

Electrochemical Stability of Quaternary Ammonium Cations: An Experimental and Computational Study

Conductances and dissociation of some 5-substituted tetrazoles in 1,1,3,3-tetramethylguanidine at 25.degree.

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