Ionic liquids (ILs) are salts that are liquid close to room temperature. Their possible applications are numerous, e.g., as solvents for green chemistry, in various electrochemical devices, and even for such “exotic” purposes as spinning-liquid mirrors for lunar telescopes. Here we concentrate on their use for new advancements in energy-storage and -conversion devices: Batteries, supercapacitors or fuel cells using ILs as electrolytes could be important building blocks for the sustainable energy supply of tomorrow. Interestingly, ILs show glassy freezing and the universal, but until now only poorly understood dynamic properties of glassy matter, dominate many of their physical properties. We show that the conductivity of ILs, an essential figure of merit for any electrochemical application, depends in a systematic way not only on their glass temperature but also on the so-called fragility, characterizing the non-canonical super-Arrhenius temperature dependence of their ionic mobility.
The electronic structures and band gaps of MFU‐4‐type metal‐organic frameworks can be systematically engineered leading to a family of isostructural microporous solids. Electrical properties of the microcrystalline samples are investigated by temperature‐dependent broad‐band dielectric and optical spectroscopy, which are corroborated by full band structure calculations performed for framework and cluster model compounds at multiple levels of density functional theory. The combined results glean a detailed picture of relative shifts and dispersion of molecular orbitals when going from zero‐dimensional clusters to three‐dimensional periodic solids, thus allowing to develop guidelines for tailoring the electronic properties of this class of semiconducting microporous solids via a versatile building block approach. Thus, engineering of the band gap in MFU‐4 type compounds can be achieved by adjusting the degree of conjugation of the organic ligand or by choosing an appropriate metal whose partially occupied d‐orbitals generate bands below the LUMO energy of the ligand which, for example, is accomplished by octahedral Co(II) ions in Co‐MFU‐4.
Most ionic liquids contain at least one rather complex ion species exhibiting a dipolar moment. In the present work, we provide a thorough evaluation of broadband dielectric spectra of 12 ionic liquids taking into account the often neglected reorientational dynamics of these ions. We confirm that this dynamics leads to a clear relaxational signature in the spectra, a fact that so far only was considered in few previous works. The obtained reorientational relaxation times are well consistent with earlier inelastic light-scattering and high-frequency dielectric investigations. Evaluating our dielectric spectra in terms of reorientational motions reveals a close coupling of the ion-rotation dynamics to the ionic charge transport in a broad temperature range from the low-viscosity liquid above room temperature deep into the high-viscosity supercooled state close to T g . This coupling does not seem to be mediated by the viscosity but probably is of more direct nature, pointing to a revolving-door mechanism as also considered for plastic-crystalline ionic conductors. Our results show that the reorientational motion of the dipolar ions plays a significant and so far widely overlooked role for the ionic charge transport in ionic liquids.
3D printers constitute a fast-growing worldwide market. These printers are often employed in research and development fields related to engineering or architecture, especially for structural components or rapid prototyping. Recently, there is enormous progress in available materials for enhanced printing systems that allow additive manufacturing of complex functional products, like batteries or electronics. The polymer polylactic acid (PLA) plays an important role in fused filament fabrication, a technique used for commercially available low-budget 3D printers. This printing technology is an economical tool for the development of functional components or cases for electronics, for example, for lab purposes. Here we investigate if the material properties of “as-printed” PLA, which was fabricated by a commercially available 3D printer, are suitable to be used in electrical measurement setups or even as a functional material itself in electronic devices. For this reason, we conduct differential scanning calorimetry measurements and a thorough temperature and frequency-dependent analysis of its dielectric properties. These results are compared to partially crystalline and completely amorphous PLA, indicating that the dielectric properties of “as-printed” PLA are similar to the latter. Finally, we demonstrate that the conductivity of PLA can be enhanced by mixing it with the ionic liquid “trihexyl tetradecyl phosphonium decanoate.” This provides a route to tailor PLA for complex functional products produced by an economical fused filament fabrication.
In the present work, we employ broadband dielectric spectroscopy to study the molecular dynamics of the prototypical glass former glycerol confined in two microporous zeolitic imidazolate frameworks (ZIF-8 and ZIF-11) with well-defined pore diameters of 1.16 and 1.46 nm, respectively.The spectra reveal information on the modified relaxation of the confined supercooled liquid, whose temperature dependence exhibits clear deviations from the typical super-Arrhenius temperature dependence of the bulk material, depending on temperature and pore size. This allows assigning well-defined cooperativity length scales of molecular motion to certain temperatures above the glass transition. We relate these and previous results on glycerol confined in other host systems to the temperature-dependent length scale deduced from nonlinear dielectric measurements. The combined experimental data can be consistently described by a critical divergence of this correlation length as expected within theoretical approaches assuming that the glass transition is due to an underlying phase transition.
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