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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Theory-Enabled High-Throughput Screening of Ion Dissociation Explains Conductivity Enhancements in Diluted Ionic Liquid Mixtures

The growing demand for room-temperature ionic liquids (RTILs) for energy applications necessitates the development of an efficient screening platform. Here, in this study, we successfully developed a fully automated high-throughput RTIL screening platform specifically designed for assessing ionic conductivity. By utilizing the 96 wells of a microtiter plate as individual electrolysis cells, we measured the ionic conductivity of 22 different RTILs, encompassing various combinations of cations and anions, and benchmarked the values with existing literature. We also employed the screening platform to investigate the conductivities of RTIL mixtures with a nonaqueous solvent, ethylene glycol (EG). Specific combinations of RTILs with EG result in approximately 200% enhancement in the conductivity values compared to the pure RTILs. To understand the underlying mechanisms responsible for this enhancement, we developed a theoretical framework for ionic conductivity that considers factors such as the degree of dissociation, viscous forces, and molal volume of the RTIL-EG mixtures. The optimized electrolyte mixture was then employed in the migration-assisted moisture gradient (MAMG) CO 2 capture process to study the effects of improved ionic conductivity on the energy efficiency of the process. Notably, the enhanced conductivity of the RTIL-EG mixture led to a nearly 50% reduction in energy consumption for capturing CO 2 . These outcomes highlight the effectiveness of our strategy in screening RTILs and improving existing processes. Moreover, this fully automated high-throughput setup, combined with the developed theoretical framework, provides a comprehensive platform for screening and studying RTIL mixtures with different solvents, enabling their application in various fields.

25 ENERGY STORAGE↗
DOE OSTI2024

Ionic Thermoelectric Generators in Vertical and Planar Topologies Based on Fluorinated Polymer Hybrid Materials with Ionic Liquids

Abstract Ionic thermoelectrics (TEs), in which voltage generation is based on ion migration, are suitable for applications based on their low cost, high flexibility, high ionic conductivity, and wide range of Seebeck coefficients. This work reports on the development of ionic TE materials based on the poly(vinylidene fluoride‐trifluoroethylene), Poly(VDF‐co‐TrFE), as host polymer blended with different contents of the ionic liquid, IL, 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMIM][TFSI]. The morphology, physico‐chemical, thermal, mechanical, and electrical properties of the samples are evaluated together with the TE response. It is demonstrated that the IL acts as a nucleating agent for polymer crystallization. The mechanical properties and ionic conductivity values are dependent on the IL content. A high room temperature ionic conductivity of 0.008 S cm −1 is obtained for the sample with 60 wt% of [EMIM][TFSI] IL. The TE properties depend on both IL content and device topology‐vertical or planar‐the largest generated voltage range being obtained for the planar topology and the sample with 10 wt% of IL content, characterized by a Seebeck coefficient of 1.2 mV K −1 . Based on the obtained maximum power density of 4.9 µW m −2 , these materials are suitable for a new generation of TE devices.

Pereira, Nelson↗
DOE OSTI2021

Membrane-Based Air Dehumidification Using Organic Ionic Liquid Desiccant

Membrane Ionic Liquid Desiccant Air Dehumidification (MILDAD) is a promising alternative to conventional dehumidification systems that employ mechanical compressors and refrigerant-based cooling with evaporator and condensing coils. However, its application has been limited due to high manufacturing and installation cost, durability issues, concerns with corrosion due to leakage and salt carry over into the downstream air and onto surfaces. This paper reviews substantial progress made with new systems based on combining advanced ionic membranes that are pressure resistant, thin walled with high water permeability, and non-porous with synthetic organic, non-crystalline ionic liquid desiccants. Alternative design configurations are discussed comparing cross flow shell-and-tube membrane contactors employing ionic membrane tubes through which ionic liquid desiccant air flows. Performance data for MILDAD prototypes is provided. Dehumidification of the incoming supply airstream and regeneration into exhausted building air is demonstrated. The latent effectiveness of the MILDAD system will be discussed along with some future steps to improve performance of the system.

ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION↗
DOE OSTI2023

Factors that influence the activity of biomass-degrading enzymes in the presence of ionic liquids—a review

Ionic liquids (ILs) are seen as a more sustainable alternative to volatile organic solvents that are accelerating innovations in many industries such as energy storage, separations, and bioprocessing. The ability to effectively deconstruct lignocellulosic biomass is a significant hurdle in the biorefining/bioprocessing industry and presents limitations towards the commercial production of bioproducts (such as biofuels, biomaterials, etc. ). Certain ILs have been shown to promote effective lignin removal, cellulose recovery, and sugar yields from various biomass feedstocks such as corn stover, wheat straw, sugarcane bagasse, sorghum, switchgrass, miscanthus, poplar, pine, eucalyptus, and certain mixtures of municipal solid waste. However, these improvements are often counteracted by the limited biocompatibility of ILs, which results in an IL-induced reduction in enzyme activity and stability—an important downstream step in the conversion of biomass to biofuels/bioproducts. As a result, significant efforts have been made to discover and engineer compatible enzyme-IL systems and to improve our understanding on the effect that these ILs have on these systems. This review seeks to examine the impact of ionic liquids on enzymes involved in lignocellulosic biomass deconstruction, with a specific focus on their relevance in the context of pretreatment. Beyond presenting an overview of the ionic liquid pretreatment landscape, we outline the main factors that influence enzyme activity and stability in the presence of ILs This data is consolidated and analyzed to apply this body of knowledge towards new innovations that could lead to improvements in the processing of biomass to biofuels and bioproducts.

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

Non-Isochronal Behavior of Charge Transport at Liquid–Liquid and Liquid–Glass Transition in Aprotic Ionic Liquids

A reversible, first-order transition separating two liquid phases of a single-component material is a fascinating yet poorly understood phenomenon. Here, we investigate the liquid–liquid transition (LLT) ability of two tetraalkylphosphonium ionic liquids (ILs), [P 666,14 ]Cl and [P 666,14 ][1,2,4-triazolide], using differential scanning calorimetry and dielectric spectroscopy. The latter technique also allowed us to study the LLT at elevated pressure. We found that cooling below 205 K transforms [P 666,14 ]Cl and [P 666,14 ][Trz] from one liquid state (liquid 1) to another (the self-assembled liquid 2), while the latter facilitates the charge transport decoupled from structural dynamics. In contrast to temperature, pressure was found to play an essential role in the self-organization of a liquid 2 phase, resulting in different time scales of charge transport for rapidly and slowly compressed samples. Furthermore, τ σ (P LL ) was found to be much shorter than τ σ (T LL , P=atm), which constitutes the first example of non-isochronal behavior of charge transport at LLT. In turn, dielectric studies through the liquid–glass transition revealed the non-monotonic behavior of τ σ at elevated pressure for [P 666,14 ]Cl, while for [P 666,14 ][Trz] τ σ (P g ) was almost constant. These results highlight the diversity of liquid–liquid transition features within the class of phosphonium ionic liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Membrane-Based Air Dehumidification Using Organic Ionic Liquid Desiccant

Membrane Ionic Liquid Desiccant Air Dehumidification (MILDAD) is a promising alternative to conventional dehumidification systems that employ mechanical compressors and refrigerant-based cooling with evaporator and condensing coils. However, its application has been limited due to high manufacturing and installation cost, durability issues, concerns with corrosion due to leakage and salt carry over into the downstream air and onto surfaces. This paper reviews substantial progress made with new systems based on combining advanced ionic membranes that are pressure resistant, thin walled with high water permeability, and non-porous with synthetic organic, non-crystalline ionic liquid desiccants. Alternative design configurations are discussed comparing cross flow shell-and-tube membrane contactors employing ionic membrane tubes through which ionic liquid desiccant air flows. Performance data for MILDAD prototypes is provided. Dehumidification of the incoming supply airstream and regeneration into exhausted building air is demonstrated. The latent effectiveness of the MILDAD system will be discussed along with some future steps to improve performance of the system.

Bahar, Bamdad↗
DOE OSTI2021

Solvent-Cast Solid Electrolyte Membranes Based on a Charged Rigid-Rod Polymer and Ionic Liquids

Solid-state electrolytes are attractive for use in electrochemical devices because they remove the need for a flammable liquid electrolyte while contributing to the structural integrity of the device. We have recently developed a class of solid electrolytes, termed molecular ionic composites (MICs), composed of ionic liquids (ILs) and a rigid-rod polyelectrolyte, poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) (PBDT). MIC materials, originally obtained through an ion-exchange process between IL and PBDT aqueous solution, possess an unprecedented combination of high ionic conductivity, high thermal stability, low flammability and widely tunable tensile storage moduli. Here we present a facile solvent casting method for preparing MIC membranes. These membranes are uniform, flexible, and tough, with tunable composition and thickness (≥ 40 μm). Unlike the previous ion-exchange method, which only allowed incorporation of hydrophilic ILs, we can now incorporate hydrophobic ILs to prepare MIC membranes for, e.g. battery electrolytes. A sodium (Na) metal symmetric cell constructed with a PBDT-Pyr 14 TFSI membrane as the solid electrolyte shows long-term stable cycling (> 500 h.) at 60 °C. Furthermore, the ability to prepare MICs using both hydrophilic and hydrophobic ILs initiates a wider range of MIC materials and broadens the array of applications accessible by MIC membranes.

25 ENERGY STORAGE↗
DOE OSTI2021

How Do Ionic Liquids “Fold” Ionenes? Computational and Experimental Analysis of Imidazolium Polymers Based on Ether and Alkyl Chain Variations Dissolved in an Ionic Liquid

Molecular dynamics (MD) simulations and complementary experiments are used here to understand the inter- and intramolecular structure and conformational properties of ionenes (i.e., cationic polymers formed from condensation reactions) dissolved in an ionic liquid (IL), 1-ethyl-3-methylimidazolium bistriflimide [C 2 mim + ][Tf 2 N - ]. The simulated structural properties are benchmarked against experimental analyses of these same polymers, mainly using dynamic light scattering (DLS) experiments. Four different imidazolium ionenes are considered, corresponding to variations in the chemistry and structure of the repeat units including: (1) poly (decylimidazolium) (PD 10 ); (2) poly (tetraethyleneglycolimidazolium) (PE 10 ); (3) alternating copolymer (P(ED) 5 ); and (4) a block copolymer (PE 5 D 5 ). Detailed computational analyses of the polymer structure and conformational properties were performed, including the radius of gyration, end-to-end distance, torsional distributions, and site-site and spatial distribution functions. Overall, there is a competition between intramolecular associations between the imidazolium groups and the ether sites in the polymers versus the intermolecular interactions of the polymer imidazolium groups with the surrounding anion molecules. The polymer with only ether linkages (PE 10 ) results in the most intramolecular interactions, leading to significant coiling behavior and chain contraction. These strong interactions reduce chain flexibility, but they also result in much more linear chain configurations and alignment of the imidazolium groups. The polymer structure is strongly affected as the concentration of alkyl groups is increased, and we find that the polymer architecture (alternating versus block copolymer) also has an important influence. Furthermore, these detailed observations are important for understanding the connection between the molecular design of imidazolium polymers and their emergent structural properties, which could lead to unique opportunities for creating polymer composites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Machine learning-enabled discovery of ionic liquid–solvent electrolytes exhibiting high ionic conductivity

Ionic liquids (ILs), which are a class of materials with versatile nature and growing popularity, are facing impediments toward widespread usage as electrolytes due to various factors such as low ionic conductivity, high viscosity, high market price etc. One of the ways these limitations can be addressed is by mixing ILs with a molecular solvent. In a combinatorial sense, there exists an immense number of specific IL–solvent combinations. An exhaustive experimental or even simulation-based investigation of the chemical space spanned by such combinations can be extremely time-consuming, expensive, and nearly impossible. An alternative approach is to employ machine learning-based models developed from available databases. Although there exists prior literature that integrates machine learning to investigate mixtures of specific solvents with ILs, these models lack generalization necessitating development of a large number of ML models to handle various solvents. To remedy this shortcoming, as a part of designing green electrolytes with high ionic conductivity that can have potential applications in next-generation batteries and solar cells, this work aims to develop a unified machine learning model to predict ionic conductivity of any IL–solvent mixture system. In this regard, three models, namely, Random Forest, extreme gradient boosting (XGBoost), and artificial neural network (ANN) were formulated using the NIST ILThermo database. The dataset contained 549 unique ionic liquids from 16 cation families and 81 unique solvents, representing a total of 23 712 datapoints. SHAPLEY additive explanation (SHAP) method was used to assess the impact of various features on model prediction and their significance was compared with literature to gain physical insight about the model behavior. Finally, using the developed models, approximately 2.5 million IL–solvent mixtures at five different compositions were screened at room temperature. The high-throughput screening yielded nearly 19 000 IL–solvent mixtures for which ionic conductivity was found to exceed the ionic conductivity of conventional Li-ion battery electrolyte.

25 ENERGY STORAGE↗
DOE OSTI2023

Machine learning predictions of diffusion in bulk and confined ionic liquids using simple descriptors

Ionic liquids have many intriguing properties and widespread applications such as separations and energy storage. However, ionic liquids are complex fluids and predicting their behavior is difficult, particularly in confined environments. We introduce fast and computationally efficient machine learning (ML) models that can predict diffusion coefficients and ionic conductivity of bulk and nanoconfined ionic liquids over a wide temperature range (350–500 K). The ML models are trained on molecular dynamics simulation data for 29 unique ionic liquids as bulk fluids and confined in graphite slit pores. This model is based on simple physical descriptors of the cations and anions such as molecular weight and surface area. Here, we also demonstrate that accurate results can be obtained using only descriptors derived from SMILES (simplified molecular-input line-entry system) codes for the ions with minimal computational effort. This offers a fast and efficient method for estimating diffusion and conductivity of nanoconfined ionic liquids at various temperatures without the need for expensive molecular dynamics simulations.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Synthesis, antibiotic structure–activity relationships, and cellulose dissolution studies of new room-temperature ionic liquids derived from lignin

Ionic liquids (ILs) are promising pretreatment solvents for lignocellulosic biomass, but are largely prepared from petroleum precursors. Benzaldehydes from depolymerized lignin, such as vanillin, syringaldehyde, and 4-methoxy benzaldehyde, represent renewable feedstocks for the synthesis of ionic liquids. We herein report syntheses of novel lignin-derived ionic liquids, with extended N -alkyl chains, and examine their melting points, cellulose dissolution capacities, and toxicity profiles against Daphnia magna and E. coli strain 1A1. The latter organism has been engineered to produce isoprenol, a drop-in biofuel and precursor for commodity chemicals. The new N,N -diethyl and N,N -dipropyl methyl benzylammonium ILs were liquids at room temperature, showing 75–100 °C decreased melting points as compared to their N,N,N -trimethyl benzylammonium analog. Extension of N -alkyl chains also increased antibacterial activity threefold, while ionic liquids prepared from vanillin showed 2- to 4-fold lower toxicity as compared to those prepared from syringaldehyde and 4-methoxybenzaldehyde. The trend of antibacterial activity for anions of lignin-derived ILs was found to be methanesulfonate < acetate < hydroxide. Microcrystalline cellulose dissolution, from 2 to 4 wt% after 20 min at 100 °C, was observed in all new ILs using light microscopy and IR spectroscopy. Ionic liquids prepared from H-, S- and G-lignin oxidation products provided differential cytotoxic activity against E. coli and D. magna , suggesting these compounds could be tailored for application specificity within a biorefinery.

09 BIOMASS FUELS↗
DOE OSTI2021

Diffusion coefficient and nucleation density studies on electrochemical deposition of aluminum from chloroaluminate ionic liquid electrolytes

In this study, aluminum was electrodeposited from ionic liquids comprising a melt of alkyl imidazolium chlorides and aluminum chloride (AlCl 3 ). The ionic liquids utilized in this study were 1-ethyl-3-methyl-imidazolium chloride (EMIC)-AlCl 3 , 1-butyl-3-methylimidazolium chloride (BMIC)-AlCl 3 , and 1-hexyl-3-methyl-imidazolium chloride (HMIC)-AlCl 3 at the AlCl 3 mole fraction of 0.667 (molar ratio of 1:2). The electrochemical behavior of chloroaluminate species in the three ionic liquids was investigated by cyclic voltammetry (CV) and chronoamperometry (CA) techniques at different temperatures. The cyclic voltammograms indicated that the reduction of Al 2 Cl 7 – species to metallic aluminum followed a diffusion-controlled phenomenon. Moreover, even at a less negative applied potential, the higher current density was obtained for EMIC-AlCl 3 ionic liquid. That indicates that EMIC-AlCl 3 favors less energy consumption during the electrodeposition. The chronoamperometric analysis revealed that the onset of aluminum deposition from such ionic liquids proceeds via a three-dimensional instantaneous nucleation process. The concentrations of Al 2 Cl 7 – ions in the ionic liquids were calculated based on the thermodynamic data, which were 2520, 2271, and 2035 mol m –3 for EMIC-AlCl 3 , BMIC-AlCl 3 , and HMIC-AlCl 3 , respectively. The diffusion coefficient (D) values of Al 2 Cl 7 – species in such ionic liquids were also calculated at various temperatures. The D values determined from the CA technique at 363 K are 2.16 × 10 –11 , 1.03 × 10 –11 , and 0.87 × 10 –11 m 2 s –1 for EMIC-AlCl 3 , BMICAlCl 3 , and HMIC-AlCl 3 , respectively. In addition, the D value increased as temperature increased and decreased as the hydrocarbon group in the ionic liquid increased. As a result, the calculated grain sizes of nucleation range from 2 to 4 μm for these ionic liquids and are in good agreement with experimental data obtained from SEM micrographs.

42 ENGINEERING↗
DOE OSTI2026

Isopentane Disproportionation in Lewis Acidic Chloroaluminate Ionic Liquid

Lewis acidic chloroaluminate ionic liquid diluted in dichloromethane catalyzes the disproportionation of alkanes, such as isopentane, via carbenium ions in a reaction readily initiated by carbenium ion precursors such as tert-butyl chloride (TBC). The carbenium ion-AlCl 4 – ion-pairs stabilized by the ionic liquid-dichloromethane solution are the key intermediates in two distinctive kinetic regimes, i.e., a transient regime (0–5 min) and a steady-state regime (after 5 min). The transient regime constitutes the majority of isopentane conversion and is governed by the initial carbenium ion concentration. In the steady-state regime, disproportionation occurs at a considerably lower rate, affected by the carbenium ion concentration, the concentration of the ionic liquid, and the reaction temperature. The formation of alkenes observed in the 1 H NMR spectra of the reacting substrates, along with the DFT calculations, suggests that deprotonation of carbenium ion-pairs reduces their concentration, decreasing, in turn, the reaction rate. Kinetic modeling indicates that the transient regime is significantly controlled by the hydride transfer (k HT ) and the deprotonation rate constants (k DP ), while the steady-state regime is additionally influenced by the alkene protonation rate constant (k –DP ). The overall activation energy of the reaction at the steady state, expressed as E a,steady-state regime = E a,HT – E a,DP + E a,–DP , was 54 kJ/mol. The reaction mechanism and the kinetics highlight the potential of Lewis acid-catalyzed conversions of hydrocarbons under remarkably mild conditions.

Deprotonation↗
DOE OSTI2022

Temperature-Dependent Constrained Diffusion of Micro-Confined Alkylimidazolium Chloride Ionic Liquids

Alkylimidazolium chloride ionic liquids (ILs) have many uses in a variety of separation systems, including micro-confined separation systems. To understand the separation mechanism in these systems, the diffusion properties of analytes in ILs under relevant operating conditions, including micro-confinement dimension and temperature, should be known. For example, separation efficiencies for various IL-based microextraction techniques are dependent on the sample volume and temperature. Temperature-dependent (20–100 °C) fluorescence recovery after photobleaching (FRAP) was utilized to determine the diffusion properties of a zwitterionic, hydrophilic dye, ATTO 647, in alkylimidazolium chloride ILs in micro-confined geometries. These micro-confined geometries were generated by sandwiching the IL between glass substrates that were separated by ~1 to 100 μm. From the measured temperature-dependent FRAP data, we note alkyl chain length-, thickness-, and temperature-dependent diffusion coefficients, with values ranging from 0.021 to 46 μm 2 /s. Deviations from Brownian diffusion are observed at lower temperatures and increasingly less so at elevated temperatures; the differences are attributed to alterations in intermolecular interactions that reduce temperature-dependent nanoscale structural heterogeneities. Furthermore, the temperature- and thickness-dependent data provide a useful foundation for efficient design of micro-confined IL separation systems.

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

High-throughput measurements of CO 2 permeance and solubility in ionic liquid reveal a synergistic role of ionic interactions and void fractions

The factors that govern CO 2 solubility in ionic liquids (ILs) are of great interest for the development of new materials for CO 2 capture and utilization. The cationic functional group (i.e., imidazolium, pyrrolidinium, pyridinium, etc.), alkyl chain length of cation, degree of fluorination of anion, anion size, and the void fraction in IL are known to influence CO 2 solubility. However, a comprehensive explanation of how these factors collectively affect CO 2 solubility has not been developed yet. This knowledge gap is largely attributed to the lack of CO 2 solubility data for IL structures other than imidazolium based ILs. We report here an automated high-throughput (HT) setup for the measurement of CO 2 solubility in room-temperature ILs (RTILs) combining six different anions and nine different cations for a total of 19 different specific ranges of RTILs. The HT setup first dispenses up to 200 µL of RTILs in a 96-well microtiter plate and then utilizes a robotic arm to measure cyclic voltammogram (CV) in each well using maneuverable Ag electrodes. The Cottrell analysis of the CO 2 reduction CV peak provides a direct measurement of CO 2 permeance in RTILs, which yields Henry’s constant from the estimated diffusion coefficient of CO 2 . Henry’s constants thus obtained are in very good agreement with those reported earlier. The measured CO 2 permeance and Henry’s constant of all RTILs seem to follow a first-order dependence on void fraction and a second-order dependence on electrostatic interaction between anion and cation of IL, with some synergistic dependence on the product of a void fraction and electrostatic interaction, making them two important descriptors for the design of novel ILs.

CO2 Solubility↗