Spectroscopic studies of triflate ion association in polymer gel electrolytes and their constituents

Johnston, Sean F.; Ward, I. M.; Cruickshank, J.; Davies, G. R.

doi:10.1016/s0167-2738(96)00381-5

Cited by 41 publications

(24 citation statements)

References 13 publications

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“…Two characteristic regions can be easily distinguished. The initial low-concentration region (I) in which a decrease in conductivity is observed has been ascribed to ion pair formation [12]. The subsequent linear region (II), showing an increase in conductivity beyond the minimum, could be a result of triple ion formation or redissociation effect [12].…”

Section: Ac Conductivity Studiesmentioning

confidence: 99%

Structural and electrical properties of pure and H2SO4 doped (PVA)0.7(NaI)0.3 solid polymer electrolyte

Badr

Sheha

Bayomi

et al. 2009

Ionics

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Solid polymer electrolytes (SPE) based on poly-(vinyl alcohol) (PVA) 0.7 and sodium iodide (NaI) 0.3 complexed with sulfuric acid (SA) at different concentrations were prepared using solution casting technique. The structural properties of these electrolyte films were examined by X-ray diffraction (XRD) studies. The XRD data revealed that sulfuric acid disrupt the semi-crystalline nature of (PVA) 0.7 (NaI) 0.3 and convert it into an amorphous phase. The proton conductivity and impedance of the electrolyte were studied with changing sulfuric acid concentration from 0 to 5.1 mol/liter (M). The highest conductivity of (PVA) 0.7 (NaI) 0.3 matrix at room temperature was 10 −5 S cm −1 and this increased to 10 −3 S cm −1 with doping by 5.1 M sulfuric acid. The electrical conductivity (σ) and dielectric permittivity (ε′) of the solid polymer electrolyte in frequency range (500 Hz-1 MHz) and temperature range (300-400) K were carried out. The electrolyte with the highest electrical conductivity was used in the fabrication of a sodium battery with the configuration Na/SPE/MnO 2 . The fabricated cells give open circuit voltage of 3.34 V and have an internal resistance of 4.5 kΩ.

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Section: Ac Conductivity Studiesmentioning

confidence: 99%

Structural and electrical properties of pure and H2SO4 doped (PVA)0.7(NaI)0.3 solid polymer electrolyte

Badr

Sheha

Bayomi

et al. 2009

Ionics

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“…Three characteristic regions can be easily distinguished. The initial low concentration region (I) in which a decrease in conductivity is observed has been ascribed to ion pair formation [5]. The subsequent linear region (II) showing an increase in conductivity beyond the minimum(at about 25 mol%), could be a result of triple ion formation or a redissociation effect [5].…”

Section: Concentration Dependence Of Ionic Conductivitymentioning

confidence: 99%

“…The initial low concentration region (I) in which a decrease in conductivity is observed has been ascribed to ion pair formation [5]. The subsequent linear region (II) showing an increase in conductivity beyond the minimum(at about 25 mol%), could be a result of triple ion formation or a redissociation effect [5]. The final high salt concentration region (III) in which a decrease in conductivity is observed may be due to a rapid increase in viscosity [6] or the formation of higher-order ion aggregates.…”

Section: Concentration Dependence Of Ionic Conductivitymentioning

confidence: 99%

Vibrational and impedance spectroscopic analysis of poly(vinyl alcohol)-based solid polymer electrolytes

Hema

Selvasekerapandian

Hirankumar

2007

Ionics

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Solid polymer electrolytes based on poly(vinyl alcohol) (PVA) doped with NH 4 Br have been prepared by the solution-casting method. The complex formation between the polymer and the salt has been confirmed by Fourier transform infrared spectroscopy. The highest conductivity at 303 K has been found to be of the order of 10 −4 Scm −1 for 25 mol% NH 4 Br-doped PVA system. The ionic transference number of polymer electrolyte has been estimated by Wagner's polarization method, and the results reveal that the conducting species are predominantly ions.

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“…The vibrational spectrum of trifl ate in dipolar aprotic solvents (DAS) was previously studied using Raman and IR absorption spectroscopy [1][2][3][4]. The structure of polymeric electrolytes containing LiCF 3 SO 3 was studied by Raman and IR-Fourier spectroscopy [5][6][7][8][9].It was found that the formation of Li + CF 3 3 SO − and triplets Li + CF 3 3 SO − Li + in DMF and acetonitrile (AN) caused a high-frequency shift in the Raman spectrum of the symmetric vibrational bands δ s (CF 3 ) (near 750-760 cm -1 ) and ν s (SO 3 ) (1030-1060 cm -1 ) of the anion relative to their positions in the spectrum of the free CF 3 3 SO − ion [3, 10]. An analogous high-frequency shift was observed for the ν s (SO 3 ) vibrational band in IR spectra of LiCF 3 SO 3 solutions in DAS of different dielectric permittivity (ε) and electron-donor capability [1,2].…”

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mentioning

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Calculation of Vibrational Spectra for Coordinated Trifluoromethanesulfonate Ion in Dipolar Aprotic Solvents

Mikhailov

2015

J Appl Spectrosc

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Vibrational spectra of solvated and coordinated trifl uoromethanesulfonate ion in dipolar aprotic solvents were studied by the Hartree-Fock method in the framework of a continuous polarizable dielectric model. The best agreement between experimental and calculated vibrational spectra was achieved taking into account non-specifi c solvation of free and coordinated anions. The microstructures of the trifl uoromethanesulfonate ion with the lithium cation in a contact ion pair and triplet in acetonitrile were determined.Keywords: trifl uoromethanesulfonate ion, aprotic solvent, vibrational spectrum, Hartree-Fock approximation.Introduction. Knowledge of the nature of ionic association, which is studied effectively using vibrational spectroscopy, is necessary in order to use non-aqueous electrolyte solutions containing the trifl uoromethanesulfonate ion (CF 3 3 SO − ) (trifl ate) to develop novel chemical current sources with active-metal anodes. The vibrational spectrum of trifl ate in dipolar aprotic solvents (DAS) was previously studied using Raman and IR absorption spectroscopy [1][2][3][4]. The structure of polymeric electrolytes containing LiCF 3 SO 3 was studied by Raman and IR-Fourier spectroscopy [5][6][7][8][9].It was found that the formation of Li + CF 3 3 SO − and triplets Li + CF 3 3 SO − Li + in DMF and acetonitrile (AN) caused a high-frequency shift in the Raman spectrum of the symmetric vibrational bands δ s (CF 3 ) (near 750-760 cm -1 ) and ν s (SO 3 ) (1030-1060 cm -1 ) of the anion relative to their positions in the spectrum of the free CF 3 3 SO − ion [3, 10]. An analogous high-frequency shift was observed for the ν s (SO 3 ) vibrational band in IR spectra of LiCF 3 SO 3 solutions in DAS of different dielectric permittivity (ε) and electron-donor capability [1,2]. It was concluded [1-10] that solvated anions, contact ion pairs (CIP), and positively or negatively charged triplets could exist in DAS.The goal of the present work was to study the microstructure and vibrational spectra of model complexes of trifl ate with Li + in DAS.Calculations. The optimum geometry was calculated and the vibrational spectrum was interpreted using the Hartree-Fock method neglecting (RHF) and partially considering (MP2) electron correlation in basis set 6-31+G(d) using the Gaussian 03 program suite [11]. Non-specifi c solvation between dissolved compounds and DAS molecules was accounted for in terms of the polarizable continuum model (PCM) [12,13]. The geometry was fully optimized taking into account the symmetry of the model complexes. Stationary points during geometry optimization were located by monitoring whether all calculated vibrational frequencies were real.Results and Discussion. Free (not interacting with a cation) trifl ate ion has C 3v symmetry and 18 normal vibrations with the symmetry representations 5A 1 + A 2 + 6E [14]. The A 1 and E vibrations are active in both the IR and Raman spectrum. The A 2 vibration is active only in the IR spectrum and is related to rotations of the SO 3 and CF 3 groups around t...

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Spectroscopic studies of triflate ion association in polymer gel electrolytes and their constituents

Cited by 41 publications

References 13 publications

Structural and electrical properties of pure and H2SO4 doped (PVA)0.7(NaI)0.3 solid polymer electrolyte

Structural and electrical properties of pure and H2SO4 doped (PVA)0.7(NaI)0.3 solid polymer electrolyte

Vibrational and impedance spectroscopic analysis of poly(vinyl alcohol)-based solid polymer electrolytes

Calculation of Vibrational Spectra for Coordinated Trifluoromethanesulfonate Ion in Dipolar Aprotic Solvents

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