Startseite Naturwissenschaften How the cation size impacts on the relaxational and diffusional dynamics of supercooled butylammonium-based ionic liquids: DPEBA–TFSI versus BTMA–TFSI
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How the cation size impacts on the relaxational and diffusional dynamics of supercooled butylammonium-based ionic liquids: DPEBA–TFSI versus BTMA–TFSI

  • Philipp Münzner EMAIL logo , Catalin Gainaru und Roland Böhmer
Veröffentlicht/Copyright: 11. November 2021
Zeitschrift für Physikalische Chemie
Aus der Zeitschrift Zeitschrift für Physikalische Chemie Band 236 Heft 6-8

Abstract

Li-bis(trifluoromethylsulfonyl)imide based ionic liquids with either butyl-trimethylammonium or N,N-dimethyl-N-(2-(propionyloxy)-ethyl)butan-1-ammonium as the anion were studied using proton and fluorine relaxometry as well as using field-gradient diffusometry to gain separate access to cation and anion dynamics in these compounds. The transport parameters obtained for these ionic liquids are compared with the estimates based on the conductivity data from literature and from the present work. The impact of cation size on correlation effects, the latter parameterized in terms of various Haven ratios, is mapped out.

Keywords: field-gradient diffusometry; ionic liquids; nuclear magnetic resonance; spin-lattice relaxation
Corresponding author: Philipp Münzner, Fakultät Physik, Technische Universität Dortmund, 44221 Dortmund, Germany, E-mail:
Dedicated to Paul Heitjans on the occasion of his 75th birthday.

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: We thank the Deutsche Forschungsgemeinschaft for funding this work under project No. 396060266.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

Appendix: Radio-frequency electric impedance experiments on BTMA–TFSI

For BTMA–TFSI low-temperature electrical impedance data are obviously not available. Therefore, we carried out coaxial high-frequency reflectometry as well as low-frequency impedance measurements and present our results in Figure 6 in the modulus format. The complex electrical modulus is M* = M′ + iM" = 1/ε* = iωε 0/σ* where σ* designates the complex conductivity, ε* the complex dielectric constant, and ε 0 the permittivity of free space. From the maxima of M" conductivity relaxation times for the liquid and for the crystalline phase were determined and added to Figure 5. The σ 0 data obtained in this work are given in Table 1. For the liquid, the dc conductivities determined from the data are included in Figure 4 as well. From microwave experiments for BTMA–TFSI it was reported that σ 0 = 1.72 mS cm−1 at 25 °C [21].

Figure 6: The imaginary part of the electrical modulus M" spectra of BTMA–TFSI is shown. For 310–240 K the data are recorded upon cooling in steps of 10 K. After the sample had crystallized, a few additional modulus spectra were taken. As an example, here we show an M" spectrum acquired at 260 K. Clearly, as compared to the liquid, in the crystal a much slower conductivity response (lower peak frequency and larger peak amplitude) is observed.
Figure 6:

The imaginary part of the electrical modulus M" spectra of BTMA–TFSI is shown. For 310–240 K the data are recorded upon cooling in steps of 10 K. After the sample had crystallized, a few additional modulus spectra were taken. As an example, here we show an M" spectrum acquired at 260 K. Clearly, as compared to the liquid, in the crystal a much slower conductivity response (lower peak frequency and larger peak amplitude) is observed.

Table 1:

Compilation of the dc-conductivities measured in the present work. The first four entries correspond to the crystallized sample, the others refer to the liquid state.

T (K) 245 250 255 260 260 270 280 290 300
log10[σ 0/(S cm−1)] −11.7 −11.1 −10.3 −9.45 −3.84 −3.46 −3.15 −2.91 −2.69

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Received: 2021-10-15
Accepted: 2021-10-25
Published Online: 2021-11-11
Published in Print: 2022-06-27

© 2021 Walter de Gruyter GmbH, Berlin/Boston

Artikel in diesem Heft

  1. Frontmatter
  2. Preface
  3. Special issue on the occasion of the 75th birthday of Paul Heitjans
  4. Contribution to Special Issue dedicated to Paul Heitjans
  5. Unusual cation coordination in nanostructured mullites
  6. A novel high entropy spinel-type aluminate MAl2O4 (M = Zn, Mg, Cu, Co) and its lithiated oxyfluoride and oxychloride derivatives prepared by one-step mechanosynthesis
  7. Two new quaternary copper bismuth sulfide halides: CuBi2S3Cl and CuBi2S3Br as candidates for copper ion conductivity
  8. Sintering behavior and ionic conductivity of Li1.5Al0.5Ti1.5(PO4)3 synthesized with different precursors
  9. Status and progress of ion-implanted βNMR at TRIUMF
  10. How Li diffusion in spinel Li[Ni1/2Mn3/2]O4 is seen with μ ±SR
  11. Nuclear magnetic resonance (NMR) studies of sintering effects on the lithium ion dynamics in Li1.5Al0.5Ti1.5(PO4)3
  12. Anion reorientations and cation diffusion in a carbon-substituted sodium nido-borate Na-7,9-C2B9H12: 1H and 23Na NMR studies
  13. Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: I. A multinuclear solid state NMR study of the system Li6PS5-xSexI and of Li6AsS5I
  14. Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: II. Multinuclear solid state NMR of the systems Li6PS5−x Se x Cl and Li6PS5−x Se x Br
  15. Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T 1 3D 7Li NMR of superionic Li10GeP2S12
  16. How the cation size impacts on the relaxational and diffusional dynamics of supercooled butylammonium-based ionic liquids: DPEBA–TFSI versus BTMA–TFSI
  17. Solid-state NMR studies of non-ionic surfactants confined in mesoporous silica
  18. Inorganic-organic hybrid materials based on the intercalation of radical cations: 2-(4-N-methylpyridinium)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-N-oxide in fluoromica clay
  19. Lithium tracer diffusion in near stoichiometric LiNi0.5Mn1.5O4 cathode material for lithium-ion batteries
  20. On the CaF2-BaF2 interface
  21. The ionic conductivity of alkali aluminum germanium phosphate glasses – comparison of Plasma CAIT with two electrode DC measurements
  22. Thin-film chemical expansion of ceria based solid solutions: laser vibrometry study
  23. Predicting conductivities of alkali borophosphate glasses based on site energy distributions derived from network former unit concentrations
  24. Ionic transport in K2Ti6O13
  25. F anion transport in nanocrystalline SmF3 and in mechanosynthesized, vacancy-rich Sm1—x BaxF3—x
  26. An overview of thermotransport in fluorite-related ionic oxides
https://doi.org/10.1515/zpch-2021-3138
Schlagwörter für diesen Artikel
field-gradient diffusometry; ionic liquids; nuclear magnetic resonance; spin-lattice relaxation

Artikel in diesem Heft

  1. Frontmatter
  2. Preface
  3. Special issue on the occasion of the 75th birthday of Paul Heitjans
  4. Contribution to Special Issue dedicated to Paul Heitjans
  5. Unusual cation coordination in nanostructured mullites
  6. A novel high entropy spinel-type aluminate MAl2O4 (M = Zn, Mg, Cu, Co) and its lithiated oxyfluoride and oxychloride derivatives prepared by one-step mechanosynthesis
  7. Two new quaternary copper bismuth sulfide halides: CuBi2S3Cl and CuBi2S3Br as candidates for copper ion conductivity
  8. Sintering behavior and ionic conductivity of Li1.5Al0.5Ti1.5(PO4)3 synthesized with different precursors
  9. Status and progress of ion-implanted βNMR at TRIUMF
  10. How Li diffusion in spinel Li[Ni1/2Mn3/2]O4 is seen with μ ±SR
  11. Nuclear magnetic resonance (NMR) studies of sintering effects on the lithium ion dynamics in Li1.5Al0.5Ti1.5(PO4)3
  12. Anion reorientations and cation diffusion in a carbon-substituted sodium nido-borate Na-7,9-C2B9H12: 1H and 23Na NMR studies
  13. Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: I. A multinuclear solid state NMR study of the system Li6PS5-xSexI and of Li6AsS5I
  14. Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: II. Multinuclear solid state NMR of the systems Li6PS5−x Se x Cl and Li6PS5−x Se x Br
  15. Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T 1 3D 7Li NMR of superionic Li10GeP2S12
  16. How the cation size impacts on the relaxational and diffusional dynamics of supercooled butylammonium-based ionic liquids: DPEBA–TFSI versus BTMA–TFSI
  17. Solid-state NMR studies of non-ionic surfactants confined in mesoporous silica
  18. Inorganic-organic hybrid materials based on the intercalation of radical cations: 2-(4-N-methylpyridinium)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-N-oxide in fluoromica clay
  19. Lithium tracer diffusion in near stoichiometric LiNi0.5Mn1.5O4 cathode material for lithium-ion batteries
  20. On the CaF2-BaF2 interface
  21. The ionic conductivity of alkali aluminum germanium phosphate glasses – comparison of Plasma CAIT with two electrode DC measurements
  22. Thin-film chemical expansion of ceria based solid solutions: laser vibrometry study
  23. Predicting conductivities of alkali borophosphate glasses based on site energy distributions derived from network former unit concentrations
  24. Ionic transport in K2Ti6O13
  25. F anion transport in nanocrystalline SmF3 and in mechanosynthesized, vacancy-rich Sm1—x BaxF3—x
  26. An overview of thermotransport in fluorite-related ionic oxides
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