Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “ionic liquid”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Polarizability effects on the structure and dynamics of ionic liquids

Polarization effects on the structure and dynamics of ionic liquids are investigated using molecular dynamics simulations. Four different ionic liquids were simulated, formed by the anions Cl{sup −} and PF{sub 6}{sup −}, treated as single fixed charge sites, and the 1-n-alkyl-3-methylimidazolium cations (1-ethyl and 1-butyl-), which are polarizable. The partial charge fluctuation of the cations is provided by the electronegativity equalization model (EEM) and a complete parameter set for the cations electronegativity (χ) and hardness (J) is presented. Results obtained from a non-polarizable model for the cations are also reported for comparison. Relative to the fixed charged model, the equilibrium structure of the first solvation shell around the imidazolium cations shows that inclusion of EEM polarization forces brings cations closer to each other and that anions are preferentially distributed above and below the plane of the imidazolium ring. The polarizable model yields faster translational and reorientational dynamics than the fixed charges model in the rotational-diffusion regime. In this sense, the polarizable model dynamics is in better agreement with the experimental data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Ionic Liquids for Direct Air Capture of CO 2 using Electric‐Field‐Mediated Moisture Gradient Process (Final Technical Report)

The final report provides executive summary, a list of publications, and information on training graduate students and postdoctoral researchers. We carried out computational and experimental research on understanding molecular-level mechanism of how CO 2 is absorbed in a solution containing ethylene glycol as the solvent and KOH as the salt in the presence of ionic liquids and under the influence of electric field. In doing so, we developed an automated high-throughput method which allowed us to measure the solubility of CO 2 in a large number of ionic liquids, considerably speeding up the CO 2 solubility measurement. We also demonstrated how varying the concentration of ionic liquids in ethylene glycol can result in a maximum in ionic conductivity. Reaction of CO 2 and subsequent release results in a 50% reduction when the process is operated at an ionic liquid-ethylene glycol concentration yielding maximum ionic conductivity amongst all the ionic liquid-ethylene glycol combinations studied as a part of this research. We utilized machine learning models to identify unique ionic liquid-solvent combinations with ionic conductivity much higher than that measured for ionic liquid-ethylene glycol combinations. We demonstrated that the rate of CO 2 reaction with KOH in ethylene glycol can be optimized with the type of ionic liquid and its concentration. Overall, the research led to publication of 10 peer-reviewed research articles and several presentations at national conferences. We are also in the process of developing additional manuscripts based on the research carried out as a part of this project. Two graduate students and two postdoctoral researchers were supported on the funding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Immobilization of Candida antarctic Lipase B on Functionalized Ionic Liquid Modified MWNTs

Multiwalled carbon nanotubes (MWNTs) were modified by imidazole-based ionic liquids with different alkyl groups. The modified support samples were characterized by scanning transmission electron microscopy, Raman spectra, thermogravimetric analyses, and X-ray photoelectron spectroscopy. The samples were used to immobilize Candida antarctic lipase (CALB) and the influence of alkyl chain length of ionic liquids on enzymatic properties was investigated by the hydrolysis reaction of triacetin. The results revealed that functionalized ionic liquids modification did not destroy the structure of MWNTs. Compared with the immobilized CALB on MWNTs, the immobilized CALB on novel carriers all exhibited higher activity, thermal stability, and reusability. Especially, the activity of MWNTs-IL (8C)-CALB improved 15.23-folds than MWNTs-CALB, meanwhile, after incubation at 70 °C for 20 min, residual enzyme activity of MWNTs-IL (8C)-CALB was 46% of the initial activity, while MWNTs-CALB already lost all activity. Besides, MWNTs-IL (8C)-CALB retained 64.5% of its initial activity after 4 cycles, while MWNTs-CALB retained only 2.12%. .

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Diffusivity and Structure of Room Temperature Ionic Liquid in Various Organic Solvents

Room-temperature ionic liquids (RTILs) hold promise for applications in electric double layer capacitors (EDLCs), owing to a much wider potential window, lower vapor pressure, and better thermal and chemical stabilities compared to conventional aqueous and organic electrolytes. However, because the low diffusivity of ions in neat RTILs negates the EDLCs’ advantage of high power density, the ionic liquids are often used in mixture with organic solvents. In this study, we measured the diffusivity of cations and anions in RTIL, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) ([BMIM + ][TFSI – ]), mixed with 10 organic solvents, by using the pulsed-field gradient NMR method. The ion diffusivity was found to follow that of neat solvents and in most studied solvents showed an excellent agreement with the predicted values reported in the recent molecular dynamics (MD) study [Thompson, M. W.; J. Phys. Chem. B 2019, 123, 1340-1347]. In two solvents consisting of long-chain molecules, however, the MD simulations predictions slightly underestimated the ionic diffusivities. The degree of ion dissociation was also estimated for each solvent by comparing the ionic conductivity with the molar conductivity derived from the diffusion measurements. The degree of ion dissociation and the hydrodynamic radius of ions suggest that the ions are coordinated by ~1 solvent molecule. Finally, the scarcity of solvent–ion interactions explains the fact that the diffusivity of ions in the mixture significantly depends on the viscosity of the solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Structure and lifetimes in ionic liquids and their mixtures

With the aid of molecular dynamics simulations, we study the structure and dynamics of different ionic liquid systems, with focus on hydrogen bond, ion pair and ion cage formation. To do so, we report here radial distribution functions, their number integrals, and various time–correlation functions, from which we extract well-defined lifetimes by means of the reactive flux formalism. We explore the influence of polarizable force fields vs. non-polarizable ones with downscaled charges (±0.8) for the example of 1-butyl-3-methylimidazolium bromide. Furthermore, we use 1-butyl-3-methylimidazolium trifluoromethanesulfonate to investigate the impact of temperature and mixing with water as well as with the chloride ionic liquid. Smaller coordination numbers, larger distances, and tremendously accelerated dynamics are observed when the polarizable force field is applied. The same trends are found with increasing temperature. Adding water decreases the ion–ion coordination numbers whereas the water–ion and water–water coordination is enhanced. A domain analysis reveals that the nonpolar parts of the ions are dispersed and when more water is added the water clusters increase in size. The dynamics accelerate in general upon addition of water. In the ionic liquid mixture, the coordination number around the cation changes between the two anions, but the number integrals of the cation around the anions remain constant and the dynamics slow down with increasing content of the chloride ionic liquid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Molecular simulation study of dynamical properties of room temperature ionic liquids with carbon pieces

Room temperature ionic liquids (RTILs) with dispersed carbon pieces exhibit distinctive physiochemical properties. In order to explore the molecular mechanism, RTILs/carbon pieces mixture we investigated it by molecular dynamics (MD) simulation in this work. Rigid and flexible carbon pieces in the form of graphene with different thicknesses and carbon nanotubes in different sizes were dispersed in a representative RTIL 1-butyl-3-methyl-imidazolium dicyanamide ([Bmim][DCA]). Our study demonstrated that the diffusion coefficients of RTILs in the presence of flexible carbons are similar to those of bulk RTILs at varying temperatures, which is in contrast to the decreased diffusion of RTILs in the presence of rigid carbons. In addition, interfacial ion number density at rigid carbon surfaces was higher than that at flexible ones, which is correlated with the accessible external surface area of carbon pieces. The life time of cation-anion pair in the presence of carbon pieces also exhibited a dependence on carbon flexibility. RTILs with dispersed rigid carbon pieces showed longer ion pair life time than those with flexible ones, in consistence with the observation in diffusion coefficients. Furthermore, this work highlights the necessity of including the carbon flexibility when performing MD simulation of RTILs in the presence of dispersed carbon pieces in order to obtain the reliable dynamical and interfacial structural properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

High-Throughput Screening and Accurate Prediction of Ionic Liquid Viscosities Using Interpretable Machine Learning

Ionic liquids (ILs) are a novel group of green solvents with great promise for various industrial applications, including carbon capture and lignocellulosic biomass deconstruction. However, the use of ILs at the industrial scale remains challenging due to their high viscosities at ambient temperatures. To develop ILs with lower viscosities, a systematic study of their quantitative structure–property relationship (QSPR) is desirable. Here, we developed four machine learning (ML) models to predict viscosity at various temperature and pressure ranges, trained over a wide range of ILs consisting of various cationic and anionic families. ML methods including two-factor polynomial regression (two-factor PR), support vector regression (SVR), feed-forward neural networks (FFNN), and categorical boosting (CATBoost) were developed based on features that have proven useful in previous ML studies: COSMO-RS (conductor-like screening model for real solvents)-derived surface screening charge densities (sigma profiles). FFNN and CATBoost were the most accurate in predicting IL viscosities with lower average absolute relative deviation and higher R2 values on the test set. Tanimoto similarity scores were calculated to characterize the chemical space and structural similarity of the investigated ions. Furthermore, SHapley Additive exPlanation (SHAP) analysis was employed to interpret the ML results. Temperature, the polar area of ILs, and the nonpolar regions of ions are key features that influence the viscosity predictions. Importantly, the IL viscosity prediction here is the most accurate reported to date.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Effects of dilution in ionic liquid supercapacitors

Room-temperature ionic liquids (RTILs) are synthetic electrolytes that have a large electrochemical stability window, making them attractive candidates for electric double-layer capacitor (EDLC) applications. Due to their high viscosities and low ionic conductivities, RTILs are often diluted with organic solvent for practical use. Here, we study the effects of dilution on the performance of RTIL EDLCs using a simple mean-field model. We find that dilution diminishes the unfavorable hysteresis that results from a spontaneous surface charge separation (SSCS). As a result, the RTIL concentration can be used to modulate the proximity to the SSCS transition, and maximize capacitance. The interplay between the concentration and the correlation strength gives rise to complex zero-potential phase behavior, including a tricritical point and a λ-line, very similar to the Blume–Capel dilute Ising model. Additionally, electrodes that are solvophilic aid in the prevention of SSCS by drawing solvent molecules to the electrode and displacing ions. Solvophilic electrodes give rise to a phase transition at finite potential where the surface charge rapidly increases with a small increase in potential, leading to a substantial increase in capacitance and energy storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Low Mach number fluctuating hydrodynamics model for ionic liquids

We present a new mesoscale model for ionic liquids based on a low Mach number fluctuating hydrodynamics formulation for multicomponent charged species. The low Mach number approach eliminates sound waves from the fully compressible equations leading to a computationally efficient incompressible formulation. The model uses a Gibbs free energy functional that includes enthalpy of mixing, interfacial energy, and electrostatic contributions. These lead to a new fourth-order term in the mass equations and a reversible stress in the momentum equations. We calibrate our model using parameters for [DMPI+][F6P-], an extensively-studied room temperature ionic liquid (RTIL), and numerically demonstrate the formation of mesoscopic structuring at equilibrium in two and three dimensions. In simulations with electrode boundaries the measured double layer capacitance decreases with voltage, in agreement with theoretical predictions and experimental measurements for RTILs. Finally, we present a shear electroosmosis example to demonstrate that the methodology can be used to model electrokinetic flows.

42 ENGINEERING↗
DOE OSTI2014

Physical Properties and CO2 Reaction Pathway of 1-Ethyl-3-Methylimidazolium Ionic Liquids with Aprotic Heterocyclic Anions

Ionic liquids (ILs) with aprotic heterocyclic anions (AHA) are attractive candidates for CO2 capture technologies. In this study, a series of AHA ILs with 1-ethyl-3-methylimidazolium ([emim](+)) cations were synthesized, and their physical properties (density, viscosity, and ionic conductivity) were measured. In addition, CO2 solubility in each IL was determined at room temperature using a volumetric method at pressures between 0 and 1 bar. The AHAs are basic anions that are capable of reacting stoichiometrically with CO2 to form carbamate species. An interesting CO2 uptake isotherm behavior was observed, and this may be attributed to a parallel, equilibrium proton exchange process between the imidazolium cation and the basic AHA in the presence of CO2, followed by the formation of "transient" carbene species that react rapidly with CO2. The presence of the imidazolium-carboxylate species and carbamate anion species was verified using H-1 and C-13 NMR spectroscopy. While the reaction between CO2 and the proposed transient carbene resulted in cation-CO2 binding that is stronger than the anion-CO2 reaction, the reactions of the imidazolium AHA ILs were fully reversible upon regeneration at 80 degrees C with nitrogen purging. The presence of water decreased the CO2 uptake due to the inhibiting effect of the neutral species (protonated form of AHA) that is formed.

Seo, S↗
DOE OSTI2016

Comparing two tetraalkylammonium ionic liquids. II. Phase transitions

Phase transitions of the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N{sub 1114}][NTf{sub 2}], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N{sub 1444}][NTf{sub 2}], were investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD) measurements, and Raman spectroscopy. XRD and Raman spectra were obtained as a function of temperature at atmospheric pressure, and also under high pressure at room temperature using a diamond anvil cell (DAC). [N{sub 1444}][NTf{sub 2}] experiences glass transition at low temperature, whereas [N{sub 1114}][NTf{sub 2}] crystallizes or not depending on the cooling rate. Both the ionic liquids exhibit glass transition under high pressure. XRD and low-frequency Raman spectra provide a consistent physical picture of structural ordering-disordering accompanying the thermal events of crystallization, glass transition, cold crystallization, pre-melting, and melting. Raman spectra in the high-frequency range of some specific cation and anion normal modes reveal conformational changes of the molecular structures along phase transitions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Comparison of Hydrogels Prepared with Ionic-Liquid-Isolated vs Commercial Chitin and Cellulose

Physical and/or covalently linked (chemical) hydrogels were prepared from chitin and cellulose extracted with ionic liquid from shrimp shells and wood biomass, respectively, and compared with hydrogels prepared from commercially available biopolymers, practical grade chitin, and microcrystalline cellulose. The highly porous aerogels were formed by initial dissolution of the biopolymers in NaOH/urea aqueous systems using freeze/thaw cycles, followed by thermal treatment (with or without epichlorohydrin as a cross-linker) and supercritical CO 2 drying. The ionic-liquid-extracted cellulose pulp and chitin, as well as practical grade chitin could form both stable physical and chemical hydrogels, whereas biopolymers of lower apparent molecular weight such as microcrystalline cellulose required a covalent cross-linker for hydrogel formation and commercially available pure chitin was not suitable for the preparation of hydrogels of either type. Hydrogels prepared from the ionic-liquid- extracted biopolymers exhibited properties substantially different from those made from the commercially available biopolymers. As a result, loading of an active ingredient into the hydrogel and its subsequent release was demonstrated using indigo carmine and revealed that the release rate was controlled mainly by the biopolymer concentration of the gel network.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Effect of hydrophobic ionic liquids aqueous solubility on metal extraction from hydrochloric acid media: Mathematical modelling and trivalent thallium behavior

A mathematical model to explain cations’ solubility of both protic and aprotic ionic liquids in a wide range of hydrochloric acid solutions has been developed. The concept of this model is based on an assumption of the mineral acid extraction into the organic phase, formation of a salt there between an ionic liquid cation and chloride-anion due to ions recombination and partial salt back-extraction. The proposed approach allows estimating corresponding extraction constants. Comparison of calculated and experimentally measured solubility product constants shows that they are in good agreement. It has been determined also that the more the hydrophilicity of the ionic liquids’ cation the more hydrochloric acid is extracted. Furthermore, this model has been utilized to facilitate analysis of thallium transfer into hydrophobic ionic liquids providing insights into the mechanism of metal extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Liquid Structure of CO 2 –Reactive Aprotic Heterocyclic Anion Ionic Liquids from X-ray Scattering and Molecular Dynamics

A combination of X-ray scattering experiments and molecular dynamics simulations were conducted to investigate the structure of ionic liquids (ILs) which chemically bind CO 2 . The structure functions were measured and computed for four different ILs consisting of two different phosphonium cations, triethyloctylphosphonium ([P 2228 ] + ) and trihexyltetradecylphosphonium ([P 66614 ] + ), paired with two different aprotic heterocyclic anions which chemically react with CO 2 , 2-cyanopyrrolide, and 1,2,4-triazolide. Simulations were able to reproduce the experimental structure functions, and by deconstructing the simulated structure functions, further information on the liquid structure was obtained. All structure functions of the ILs studied had three primary features which have been seen before in other ILs: a prepeak near 0.3–0.4 Å–1 corresponding to polar/nonpolar domain alternation, a charge alternation peak near 0.8 Å–1, and a peak near 1.5 Å–1 due to interactions of adjacent molecules. The liquid structure functions were only mildly sensitive to the specific anion and whether or not they were reacted with CO 2 . Upon reacting with CO 2 , small changes were observed in the structure functions of the [P 2228 ] + ILs, whereas virtually no change was observed upon reacting with CO 2 in the corresponding [P 66614 ] + ILs. When the [P 2228 ] + cation was replaced with the [P 66614 ] + cation, there was a significant increase in the intensities of the prepeak and adjacency interaction peak. While many of the liquid structure functions are similar, the actual liquid structures differ as demonstrated by computed spatial distribution functions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Aqueous ionic liquid–mediated depolymerization of textile waste

Textile waste, dominated by polyester-cotton blends, largely evades recycling and ends up in landfills or incinerators. Here, we demonstrate an aqueous ionic liquid–mediated route for selective depolymerization of textile waste, including polyester and polycotton (polyester/cotton blend). Using aqueous cholinium lysinate ([Ch][Lys]), we depolymerized poly(ethylene terephthalate) (PET) textiles with over 95 % terephthalic acid (TPA) yields, comparable to virgin PET resin. Notably, colored fabrics showed no inhibitory effect from dyes. While protic ionic liquids such as ethanolammonium acetate showed limited efficiency, their precursor amine enabled near-complete PET conversion—ethanolamine promoted aminolysis with byproduct formation whereas butylamine achieved higher TPA recovery through combined hydrolysis and aminolysis. Importantly, polycotton blends achieved complete PET depolymerization with TPA yield above 85 % and preserved cotton. These results establish aqueous ionic liquids as efficient, selective agents for deconstructing polyester in blended textiles, offering flexible product and ionic liquid management pathways toward scalable and facile textile recycling.

Amines↗
DOE OSTI2021

Ion specific, thin film confinement effects on conductivity in polymerized ionic liquids.

Acrylate-based polymerized ionic liquids (PILs) with ammonium (Am) or imidazolium (Im) cations and tetrafluoroborate (BF4) or bis(trifluoromethanesulfonyl)imide (TFSI) anions were synthesized and spin coated onto gold interdigitated electrodes on silica to investigate nanoconfinement effects on ion transport. The film thickness ranged from 23 to 313 nm. A significant reduction of the in-plane conductivity was observed in some PIL thin films with thickness below 100 nm. Specifically, Am BF4 PIL showed the largest conductivity drop (ca. 50% difference between a 22 nm and a 261 nm film) while Im TFSI PIL showed almost no change under confinement. The difference in conductivity drop is discussed in terms of (i) differences in interfacial layer thickness by fitting a two-layer conductivity model and (ii) potential changes in glass transition temperature (T-g) under confinement, which were estimated using the Vogel-Fulcher-Tammann fits of bulk conductivities. Decreasing film thickness also caused the dielectric loss peaks to shift to lower frequency, indicating that the ion diffusion process slowed under confinement.

Zhao, Qiujie↗
DOE OSTI2018

Solvate Ionic Liquids at Electrified Interfaces

Solvate ionic liquids (SILs) are a promising electrolyte for Li-ion batteries; thus, their behavior at electrified interfaces is crucial for the operation of these batteries. We report molecular dynamics simulation results for a prototypical SIL of lithium triglyme bis(trifluoro-methanesulfonyl)imide ([Li(G3)][TFSI]) sandwiched between electrified surfaces. At negatively charged as well as neutral electrodes, the electrolyte largely maintains the characteristics of SILs, e.g., a majority of the interfacial Li + ions remains coordinated by the similar number of oxygen atoms on G3 ligands as the bulk Li + ions. The persistence of the complex ions is attributed to the 1:1 Li-G3 ratio in bulk SILs and the fact that G3 molecules readily adapt to the interfacial environment, e.g., by aligning themselves with the surface to ensure good solvation of the interfacial Li + ions. Nevertheless, the interfacial Li + ions also display changes of solvation from that in bulk SIL by deviating from the molecular plane formed by the oxygen atoms on G3 ligands as electrodes become more negatively charged. Using density functional theory along with natural bond orbital calculations, we examine the effects of such structural distortion on the properties of the complex cation. Both the frontier orbital energies of the complex cation and the donor-acceptor interactions between Li + ions and G3 ligands are found to be dependent on the deviation of Li + ions from the molecular plane of the G3 ligands, which suggest that the reduction of Li + ions should be facilitated by the structural distortion. These results bear important implications for the nanostructures and properties of SILs near electrified interfaces during actual operations of Li-ion batteries and serve to provide guidance toward the rational design of new SILs electrolytes.

25 ENERGY STORAGE↗