RESUMEN
In this work, a series of novel boronium-bis(trifluoromethylsulfonyl)imide [TFSI-] ionic liquids (IL) are introduced and investigated. The boronium cations were designed with specific structural motifs that delivered improved electrochemical and physical properties, as evaluated through cyclic voltammetry, broadband dielectric spectroscopy, densitometry, thermogravimetric analysis, and differential scanning calorimetry. Boronium cations, which were appended with N-alkylpyrrolidinium substituents, exhibited superior physicochemical properties, including high conductivity, low viscosity, and electrochemical windows surpassing 6 V. Remarkably, the boronium ionic liquid functionalized with both an ethyl-substituted pyrrolidinium and trimethylamine, [(1-e-pyrr)N111BH2][TFSI], exhibited a 6.3 V window, surpassing previously published boronium-, pyrrolidinium-, and imidazolium-based IL electrolytes. Favorable physical properties and straightforward tunability make boronium ionic liquids promising candidates to replace conventional organic electrolytes for electrochemical applications requiring high voltages.
RESUMEN
Ion dynamics and charge transport in 1-methyl-3-octylimidazolium ionic liquids with chloride, bromide, tetrafluoroborate, tricyanomethanide, hexafluorophosphate, triflate, tetrachloroaluminate, bis(trifluoromethylsulfonyl)imide, and heptachlorodialuminate anions are investigated by broadband dielectric spectroscopy, rheology, viscometry, and differential scanning calorimetry. A detailed analysis reveals an anion and temperature-dependent separation of characteristic molecular relaxation rates extracted from various representations of the dielectric spectra. The separation in rates extracted from the electric modulus and conductivity formalisms is interpreted as an experimental signature of significant heterogeneity in the local ion dynamics associated with the structural glass transition, viscosity, and dc ion conductivity. It is further found that the degree of dynamic heterogeneity correlates with the strengths of slow dielectric and mechanical relaxations previously attributed to the dynamics of mesoscale solvophobic aggregates. Increasing local dynamic heterogeneity correlates with an increase in the strength of the slow, aggregate dielectric relaxation and a decrease in the strength of the slow, aggregate mechanical relaxation. Accordingly, increasing local dynamic heterogeneity, brought about by change in temperature and/or cation/anion chemical structure, correlates with an increase in the static dielectric permittivities and a decrease in the contribution of aggregate dynamics to the zero-shear viscosities. The established correlation provides a new ability to distinguish between the influence of mesoscale aggregate shape/morphology versus local and mesoscale ion dynamics on the transport properties of ionic liquids.
RESUMEN
All-cellulose xerogel composites were fabricated using a facile, scalable three-step process-(1) partial ionic liquid dissolution, (2) non-solvent rinsing, and (3) drying. The xerogel composites are composed of two phases where the yarn center is non-porous highly crystalline cellulose I surrounded by mesoporous amorphous regenerated cellulose. The composite had high 149 m2 g-1 Brunauer-Emmett-Teller (BET) surface area with 11.7 nm average pore diameter. The porosity was calculated using density-based (Ïρ = 0.49) and volume-based (ÏV = 0.52) methods. The porosity evolution mechanism is attributed to non-solvent-induced polarity shifts, and these results are compared with non-porous morphologies produced by varying the choice in non-solvents. Although similar decrystallization behavior was measured for all samples, non-porous yarns had a smaller diameter and significantly reduced BET surface area (0.03 m2 g-1). The presented fabrication method offers controllable mesoporous phase formation along with freestanding structural capability towards the development of advanced functional cellulosic materials.
RESUMEN
Deep eutectic solvents (DESs) are an emerging class of non-aqueous solvents that are potentially scalable, easy to prepare and functionalize for many applications ranging from biomass processing to energy storage technologies. Predictive understanding of the fundamental correlations between local structure and macroscopic properties is needed to exploit the large design space and tunability of DESs for specific applications. Here, we employ a range of computational and experimental techniques that span length-scales from molecular to macroscopic and timescales from picoseconds to seconds to study the evolution of structure and dynamics in model DESs, namely Glyceline and Ethaline, starting from the parent compounds. We show that systematic addition of choline chloride leads to microscopic heterogeneities that alter the primary structural relaxation in glycerol and ethylene glycol and result in new dynamic modes that are strongly correlated to the macroscopic properties of the DES formed.
RESUMEN
Polymerized ionic liquids are a promising class of versatile solid-state electrolytes for applications ranging from electrochemical energy storage to flexible smart materials that remain limited by their relatively low ionic conductivities compared to conventional electrolytes. Here, we show that the in situ polymerization of the vinyl cationic monomer, 1-ethyl-3-vinylimidazolium with the bis(trifluoromethanesulfonyl)imide counteranion, under nanoconfinement within 7.5 ± 1.0 nm diameter nanopores results in a nearly 1000-fold enhancement in the ionic conductivity compared to the material polymerized in bulk. Using insights from broadband dielectric and Raman spectroscopic techniques, we attribute these results to the role of confinement on molecular conformations, ion coordination, and subsequently the ionic conductivity in the polymerized ionic liquid. These results contribute to the understanding of the dynamics of nanoconfined molecules and show that in situ polymerization under nanoscale geometric confinement is a promising path toward enhancing ion conductivity in polymer electrolytes.
RESUMEN
Broadband dielectric spectroscopy is employed to probe dynamics in low molecular weight poly(cis-1,4-isoprene) (PI) confined in unidirectional silica nanopores with mean pore diameter, D, of 6.5 nm. Three molecular weights of PI (3, 7 and 10 kg/mol) were chosen such that the ratio of D to the polymer radius of gyration, Rg, is varied from 3.4, 2.3 to 1.9, respectively. It is found that the mean segmental relaxation rate remains bulk-like but an additional process arises at lower frequencies with increasing molecular weight (decreasing D/Rg. In contrast, the mean relaxation rates of the end-to-end dipole vector corresponding to chain dynamics are found to be slightly slower than that in the bulk for the systems approaching D/Rg â¼ 2, but faster than the bulk for the polymer with the largest molecular weight. The analysis of the spectral shapes of the chain relaxation suggests that the resulting dynamics of the 10kg/mol PI confined at length-scales close to that of the Rg are due to non-ideal chain conformations under confinement decreasing the chain relaxation times. The understanding of these faster chain dynamics of polymers under extreme geometrical confinement is necessary in designing nanodevices that contain polymeric materials within substrates approaching the molecular scale.
RESUMEN
The impact of mesoscale organization on dynamics and ion transport in binary ionic liquid mixtures is investigated by broad-band dielectric spectroscopy, dynamic-mechanical spectroscopy, X-ray scattering, and molecular dynamics simulations. The mixtures are found to form distinct liquids with macroscopic properties that significantly deviate from weighted contributions of the neat components. For instance, it is shown that the mesoscale morphologies in ionic liquids can be tuned by mixing to enhance the static dielectric permittivity of the resulting liquid by as high as 100% relative to the neat ionic liquid components. This enhancement is attributed to the intricate role of interfacial dynamics associated with the changes in the mesoscopic aggregate morphologies in these systems. These results demonstrate the potential to design the physicochemical properties of ionic liquids through control of solvophobic aggregation.
RESUMEN
Broadband dielectric spectroscopy is employed to investigate the impact of supramolecular structure on charge transport and dynamics in hydrogen-bonded 2-ethyl-4-methylimidazole and 4-methylimidazole. Detailed analyses reveal (i) an inverse relationship between the average supramolecular chain length and proton conductivity and (ii) no direct correlation between the static dielectric permittivity and proton conductivity in imidazoles. These findings raise fundamental questions regarding the widespread notion that extended supramolecular hydrogen-bonded networks facilitate proton conduction in hydrogen bonding materials.
RESUMEN
The role of anions in charge transport and localized dipolar relaxations in tributyloctylphosphonium ionic liquids is investigated by broadband dielectric spectroscopy and rheology. The dielectric spectra are quantitatively described by a combination of the random barrier model which accounts for ion transport and empirical Havriliak-Negami functions to characterize dipolar relaxations. Two secondary relaxations are observed at temperatures below the calorimetric glass transition temperature, where the primary structural relaxation is essentially frozen at the relevant experimental time scales. The faster process has an anion independent activation energy of 30 kJ/mol and is attributed to libration motion of the phosphonium cation. The slower relaxation is similar to a process previously assigned to a Johari-Goldstein relaxation in imidazolium-based ionic liquids; however, the activation energy is significantly higher in the phosphonium systems. For the charge transport dominated regime, it is observed that variation of the anion results in differences in the dc ionic conductivity and characteristic charge transport rates by â¼2.5 decades. Upon scaling by the calorimetric glass transition temperature, both transport quantities are observed to coincide. From these results, a picture of glass transition assisted hopping emerges as the underlying microscopic mechanism of ion conduction, in agreement with recent results obtained for other classes of aprotic ionic liquids.
RESUMEN
Experimental evidence of the dynamics of mesoscopic structure in room-temperature ionic liquids-a feature expected to correlate with many physicochemical properties of these materials-remains limited. Here, we report the observation of slow, sub-α relaxations corresponding to dynamics of nanoscale hydrophobic aggregates in a systematic series of 1-alkyl-3-methylimidazolium-based ionic liquids from detailed analysis of dynamic-mechanical and broad-band dielectric spectra. The emergence of the sub-α relaxations correlates with increases in the zero-shear viscosity and static dielectric permittivity, constituting direct evidence of the influence of mesoscale aggregation on the physicochemical properties of ionic liquids.
RESUMEN
Continuous progress in energy storage and conversion technologies necessitates novel experimental approaches that can provide fundamental insights regarding the impact of reduced dimensions on the functional properties of materials. Here, we demonstrate a nondestructive experimental approach to probe nanoscale ion dynamics in ultrathin films of polymerized 1-vinyl-3-ethylimidazolium bis(trifluoromethylsulfonyl)imide over a broad frequency range spanning over 6 orders of magnitude by broadband dielectric spectroscopy. The approach involves using an electrode configuration with lithographically patterned silica nanostructures, which allow for an air gap between the confined ion conductor and one of the electrodes. We observe that the characteristic rate of ion dynamics significantly slows down with decreasing film thicknesses above the calorimetric glass transition of the bulk polymer. However, the mean rates remain bulk-like at lower temperatures. These results highlight the increasing influence of the polymer/substrate interactions with decreasing film thickness on ion dynamics.
RESUMEN
The impact of supramolecular hydrogen bonded networks on dynamics and charge transport in 2-ethyl-4-methylimidazole (2E4MIm), a model proton-conducting system, is investigated by broadband dielectric spectroscopy, depolarized dynamic light scattering, viscometry, and calorimetry. It is observed that the slow, Debye-like relaxation reflecting the supramolecular structure in neat 2E4MIm is eliminated upon the addition of minute amounts of levulinic acid. This is attributed to the dissociation of imidazole molecules and the breaking down of hydrogen-bonded chains, which leads to a 10-fold enhancement of ionic conductivity.
RESUMEN
Charge transport and structural dynamics in the 1:2 mol ratio mixture of lidocaine and decanoic acid (LID-DA), a model deep eutectic mixture (DEM), have been characterized over a wide temperature range using broad-band dielectric spectroscopy and depolarized dynamic light scattering. Additionally, Fourier transform infrared spectroscopy measurements were performed to assess the degree of proton transfer between the neutral parent molecules. From our detailed analysis of the dielectric spectra, we have determined that this carboxylic-acid-based DEM is approximately 25% ionic at room temperature. Furthermore, we have found that the characteristic diffusion rate of mobile charge carriers is practically identical to the rate of structural relaxation at all measured temperatures, indicating that fast proton transport does not occur in LID-DA. Our results demonstrate that while LID-DA exhibits the thermal characteristics of a DEM, its charge transport properties resemble those of a protic ionic liquid.