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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Ionic liquid electrolyte for lithium-ion batteries

The ionic liquids disclosed herein are salts comprising a nitrogen or phosphorus such as a quaternary ammonium ion, a quaternary phosphonium ion, or an N-alkylated nitrogen heterocycle, and which include at least one functional substituent, e.g., a fluoro, cyano, carbonate ester, an alkenyl group, or an alkynyl group bonded to a carbon atom the cation. In a preferred embodiment, the cation is represented by the structure of Formula (I) as described herein.

Zhang, Zhengcheng↗
DOE OSTI2022

Influence of the Anions on the Interaction Energy between Water and Ionic Liquids

It is essential to understand the interaction energy between water and ionic liquids (ILs) in search of ILs for dehumidification applications. In this paper, the intermolecular interaction energy between water and 1-ethyl-3-methylimidazolium ([EMIM])-based ILs was investigated. The vapor-liquid equilibrium data were first measured for solutions of [EMIM][BF 4 ], [EMIM][N(CN) 2 ], [EMIM][CF 3 SO 3 ], and [EMIM][CH 3 SO 3 ] with water molar fractions of 8–95 % at temperatures of 303–343 K. The IL-IL and water-IL intermolecular interaction energies were determined by using the correlated non-random two-liquid model. The results revealed that fluorine atoms in anions reduce the attraction energy between IL and water, and thus, decrease the water affinity.

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

Molecular dynamics based study on the effects of cation size on the local structure and diffusion in polymerized ionic liquids

We have used coarse-grained molecular dynamics simulations to understand the effect of cation size on ion diffusion in polymerized ionic liquids at temperatures well above the glass transition temperature of the polymers. We investigated dependencies of the diffusion constant on the cation radius and static dielectric constant and interpreted these results in terms of underlying structural changes, and decoupling phenomenon. We have found non-monotonic effects of the cation radius on the diffusion constant, with a maximum at an intermediate radius resulting from two different size dependent effects. Changes in the radial distribution functions characterizing spatial distribution of cations with respect to anions result in a monotonic increase in the coordination number. This yields an increase in the effective interaction energy as a function of cation radius, which can explain the decrease in the diffusion constant. This increase is counteracted at small cation radii by a corresponding increase in decoupling of cation and anion dynamics. In addition, the diffusion constant is found to increase on increasing the static dielectric constant for all radii of the cations. These results highlight the significant role of decoupling in designing polymerized ionic liquids with an enhanced diffusion constant of cations.

Gillespie, Colin [ORNL] (ORCID:0000000320287080)↗
DOE OSTI2023

The role of ionic liquids in resolving the interfacial chemistry for (quasi-) solid-state batteries

Interfacial issues impede the advancement of current solid state battery technology; thus, interface engineering approaches are necessary to enable solid-state configuration. The advantage of solid-state cells stems from their low flammability and high electrochemical stability. Ionic liquids are viscous and nonflammable compounds that possess the requisite physical properties while optimizing the interface between solid electrodes and solid electrolytes, accelerating interfacial ion transport and enabling the fabrication of engineered interphases via the supply of robust chemical building blocks. In conclusion, this review summarizes the roles of ionic liquids in solid-state batteries focusing on the interface, with insights into their functionality as well as highlighting their applicability in the next generation battery systems.

25 ENERGY STORAGE↗
DOE OSTI2021

Distinguishing interfacial double layer and oxide-based capacitance on gold and pre-oxidized Fe-Cr in 1-ethyl-3-methylimidazolium methanesulfonate room temperature ionic liquid aqueous mixture

The frequency-dependent impedance of a metal/oxide/room temperature ionic liquid (RTIL) interface was separated into oxide layer (C ox ) and double layer (C dl ) capacitances using electrochemical impedance spectroscopy (EIS). A pre-formed oxide of known initial thickness on Fe-20 at.% Cr was investigated in 1-ethyl-3-methylimidazolium methanesulfonate ([Emim][MeSO 3 ]) RTIL + aqueous mixtures. The oxide thickness was calculated from C ox using the complex capacitance representation and the power-law model. The result was additionally verified by cross-sectional analysis using transmission electron microscopy. The C dl calculated from the constant-phase element (CPE) was distinguishable from C ox for Fe-20Cr, which enables monitoring of the interfaces of structural metals with oxide layers in RTILs containing water.

Constant-phase element↗
DOE OSTI2021

Insight into the Solid Electrolyte Interphase Formation in Bis(fluorosulfonyl)Imide Based Ionic Liquid Electrolytes

The formation of the solid electrolyte interphase (SEI) in an ionic liquid electrolyte of 0.5 m lithium bis(fluorosulfonyl)imide (LiFSI) in 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide at high cell voltages (1.7–1.9 V) is investigated in ordered mesoporous carbon (OMC) based Li metal cells using an operando small-angle neutron scattering (SANS) technique coupled with electrochemical impedance spectroscopy and ex situ X-ray photoelectron spectroscopy (XPS). It is demonstrated that discharging the OMC Li metal cells to ≈2 V and holding the cell voltage constant induces a rapid current increase with time, confirming extensive reduction and SEI formation. XPS analysis reveals that LiF is formed at open cell voltage (OCV), which is attributed to the carbenes generated at the lithium negative electrode because of its reaction with EMIm cation diffusing to and initiating the reaction with FSI - anions at the carbon positive electrode. It is confirmed that the chemical reaction at OCV and electrochemical reduction at high cell voltage of the FSI - anion plays a protective role against EMIm cation co-intercalation into the carbon positive electrode during the initial discharge. Operando SANS studies also suggest that slight differences occur in the surface composition and reaction mechanism as a function of cell voltage.

1-ethyl-3- methylimidazolium bis(fluorosulfonyl)im↗
DOE OSTI2026

Molecular-Level Insights into the Influence of Ionic Liquids on the Structure and Dynamics of Neutral and Charged Polyimides

We use all-atom molecular dynamics simulations to investigate how increasing ionic functionalization influences polyimide (PI) behavior in ionic liquid (IL) solvation environments. Here, we examine three polymer systems with varying charge densities: a neutral polyimide [N−PI] containing imidazole rings and progressively introduce charge through quaternization to create singly [C−PI] + and doubly charged [C−2PI] 2+ variants across a wide range of IL concentration (0−90 wt %). Through comprehensive structural, mechanical, and electrostatic analyses, we reveal that polymer charge density plays a central role in shaping IL organization and interaction with the polymer matrix. At low IL content, charged systems exhibit strong electrostatic complexation, leading to chain compaction, localized ESP environments, and elevated dielectric constants. As IL concentration increases, the effect of the different polymer charge states becomes less significant. Notably, an intermediate composition regime at approximately 50 wt % IL is associated with changes in IL-rich domain connectivity and overall system behavior across all three PI systems.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Transformational Nano-confined Ionic Liquid Membrane for Greater than or Equal to 97 Percent Carbon Dioxide Capture from Natural Gas Combined Cycle Flue Gas

A transformational process based on nano-confined ionic liquid (NCIL) membranes was developed for capturing ≥97% CO 2 from natural gas combined cycle (NCCC) flue gas. The NCIL membranes were prepared by loading amino acid ionic liquid into a framework composed of single-walled carbon nanotube mesh filled with graphene oxide quantum dots. The membranes exhibited CO 2 permeance as high as 2,000 GPU with a CO 2 /N2 selectivity of 2,300 for a typical NGCC flue gas composition. When H 2 O vapor sweep was applied in the permeate side, 96.6% CO2 dry-basis purity and 97.6% CO 2 capture rate were achieved for a simulated NGCC flue gas with single stage. In the process design, a highly H 2 O-selective membrane would be needed to recover majority of the H 2 O vapor, and the recovered H 2 O vapor could be recycled to the permeate side of the NCIL membrane. Sulfonated poly(ether ether ketone) membranes were successfully developed for this purpose. These membranes exhibited H 2 O permeance great than 11,000 GPU and H 2 O/CO 2 selectivity greater than 1,000 at 70ºC for a feed mixture consisting of 14.5 vol% H2O and balanced CO 2 . A standalone membrane model using MATLAB platform was developed for process simulation. The model was validated with experimental data. Techno-economic analysis based on the testing data collected during the current program suggests this transformational membrane process can achieve 97% CO 2 capture efficiency with a cost of $47.8/tonne of CO 2 , which is a 21% reduction versus DOE’s reference case B31B.97.

03 NATURAL GAS↗
DOE OSTI2026

Rational Design of Weakly‐Solvating Molecules for Salt‐In‐Pre‐Ionic‐Liquid Electrolytes for Li Metal Batteries

Lithium metal batteries (LMBs) promise step‐changes in energy densities but suffer from poor cycle life due to unstable electrolyte‐lithium interfaces. Conventional carbonate electrolytes exhibit excessive lithium‐ion solvation and low oxidative stability, leading to rapid capacity loss. Herein, we report a rationally designed weakly‐solvating cyclic sulfonamide, 1‐trifluoromethanesulfonyl)amide pyrrolidine (TFMSPyr), which integrates an electron‐withdrawing trifluoromethanesulfonyl functional group at pyrrolidinic‐N. TFMSPyr acts as a pre‐ionic‐liquid solvent that forms intrinsically localized, anion‐dominated solvation, coupling molecular architecture, solvation topology, and transport dynamics. As a result, LiFSI based salt‐in‐pre‐ionic‐liquid (SIPIL) electrolytes exhibit high lithium‐ion transference number, oxidative stability > 5 V versus Li/Li + and anion‐derived solid electrolyte interphases (SEI). Li||Cu cells with SIPIL deliver a first cycle Coulombic efficiency (CE) of ≈ 99% with average CE of 99.2% for 100 cycles, and lithium half‐cells with lithium iron phosphate (LFP) cathode exhibit 82% capacity retention after 400 cycles with CE of 99.98%. In anode‐free full cells, 95% of initial capacity is retained after 63 cycles with an average CE of 99.5%. These results demonstrate that molecular engineering of solvents offers a powerful pathway to stabilize lithium metal interfaces and enable practical Anodeless LMBs.

25 ENERGY STORAGE↗
DOE OSTI2026

In situ molecular imaging of ion clusters reveals the acid gas capture capacity and mechanism of water-lean ionic liquids

Water-lean solvents are a promising technology for capturing acid gases like carbon dioxide (CO 2 ). In situ liquid time-of-flight secondary ionization mass spectroscopy (ToF-SIMS) is used to study a representative solvent N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (2-EEMPA) with different CO 2 loadings to reveal the complex solvent structure upon CO 2 capture. Characteristic peaks of 2-EEMPA, such as m/z – 215 C 11 H 23 N 2 O 2 – (deprotonated 2-EEMPA) and m/z + 217 C 11 H 25 N 2 O 2 + (protonated 2-EEMPA), are detected due to acid gas uptake. Also, solvent molecules and carboxylate ion pairs, such as m/z – 259 C 12 H 23 N 2 O 4 – [(deprotonated 2-EEMPA∙∙∙CO 2 )] and m/z + 261 C 12 H 25 N 2 O 4 + (protonated 2-EEMPA∙∙∙CO 2 ), are observed. Interestingly, more than one CO 2 molecule can be captured per each solvent molecule as evidenced in SIMS mass spectra, for example, m/z – 321 C 13 H 25 N 2 O 7 – [(deprotonated 2-EEMPA)∙∙∙2CO 2 ∙∙∙H 2 O], m/z + 305 C 13 H 25 N 2 O 4 + [(protonated 2-EEMPA)∙∙∙2CO 2 ], m/z – 389 C 17 H 29 N 2 O 8 – [(deprotonated 2-EEMPA)∙∙∙3CO 2 ∙∙∙3CH 2 ], and m/z + 373 C 16 H 25 N 2 O 8 + [(protonated 2-EEMPA)∙∙∙3CO 2 ∙∙∙2C]. However, the monomer of 2-EEMPA and CO 2 seems to be most prevalent. Furthermore, solvent clusters are detected in loaded solvents, for instance m/z + 433 C 22 H 49 N 4 O 4 + [(2-EEMPA)2∙∙∙H] and m/z + 646 [(2-EEMPA) 3 -2H], while capturing CO 2 at different amounts. Relative abundance of cluster ions provides a semi-qualitative venue to assess the free energies of gas capture energetics, indicating the relative stability trend within the same solvent system, previously impossible. These observed ion clusters are verified with molecular modeling, where dimer, trimer, and cluster ions are validated for their presence either due to weak molecular interactions or hydrogen bonds. In situ molecular imaging of ionic liquids and molecular modeling reveals that the acid gas capture mechanism by ionic liquids includes both physical adsorption and chemical bonding with multiple reaction pathways, engaging cluster formation and alteration of solvent structures.

Acid gas capture↗
DOE OSTI2020

Synthesis of imidazolium-mediated Poly(benzoxazole) Ionene and composites with ionic liquids as advanced gas separation membranes

We report thermally rearranged (TR) polymers and ionic polymers are two material classes which have been employed in leading gas separation membranes. This work introduces a novel approach of combining the benzoxazole functionality associated with TR polymers with tailorable cationic groups, yielding a new type of imidazolium-mediated poly(benzoxazole) ionene polymer, “Im-PBO-Ionene” with the aim of enhanced CO 2 separation performance. The structural changes exhibited from the Coulombic interactions between the ionene backbone and the “free” ionic liquid (IL) resulted in enhanced gas separation performance, shown in fundamental characterizations, observed through increased diffusivities and more notably, retained high selectivities and 3x or 5x respective increases in CO 2 permeability upon the addition of 1 or 2 equivalents of IL per polymer repeat unit. These new high-performance ionenes demonstrate the versatility of ionene design and potential of the ionene + IL material platform for gas separation membranes with versatile incorporation of sophisticated functional and structural features.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Small angle X-ray studies of short-range order in non-stoichiometric pseudoprotic ionic liquids: the influence of chemical structure

Mixtures of organic acids and amines have been studied extensively owing to their unusual physicochemical properties and applications as solvents for extraction. In equimolar ratios they represent pseudoprotic ionic liquids, and in other, “nonstoichiometric” ratios they display a range of odd physicochemical behaviors. We report the results of small-angle X-ray scattering studies of a series of such systems with a range of chemical structures chosen to explore the link between molecular geometry and the character of the emergent nanoscale local liquid structure. We find that while the details vary, structure can emerge even when the hydrogen-bonding character of the components is changed significantly, and the character of their hydrocarbon substituents is altered. The consistent emergence of local order in the face of varying chemical structures indicates that the process is robust. Furthermore, this implies that the emergence of such structure may in fact be far more common in liquid mixtures than is currently recognized, and a great many structures may be suitable for the synthesis of pseudoprotic ionic liquids.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Fast and Non-Destructive Determination of Water Content in Ionic Liquids at Varying Temperatures by Raman Spectroscopy and Multivariate Regression Analysis

Imidazolium acetate ionic liquids (ILs) have been utilized as promising solvents in many applications that involve varying water content and temperature. These experimental variables affect the anion-cation intermolecular interactions, which in turn influence the performance of the ILs in these applications. Here, this paper shows Raman spectroscopy can be used as an operando method to measure water content in IL solvents when simultaneous temperature changes may occur. The Raman spectra of 1-alkyl-3-methylimidazolium acetate ILs (alkyl chain length n = 2, 4, 6, 8) with varying water content (from 0.028 to 0.899 water mole fraction) and temperature (from 78.1 K to 423.1 K) were measured. Increasing the water content or decreasing the temperature of the tested ILs weakens the anion-cation intermolecular interactions. The water content of these ILs can be quantified even in conditions when the temperature is changing using Raman spectroscopy combined with multivariate regression analysis, including principal component regression (PCR), partial-least-squares regression (PLSR), and artificial neural networks (ANNs). The ANN model combined with partial-least-squares (PLS) achieves the highest prediction accuracy of water content in ILs at varying temperatures (RMSECV = 0.017, R 2 CV = 99.1%, RMSEP = 0.019, R 2 P = 98.8%, RPD = 8.93). Raman spectroscopy provides a potential fast non-destructive operando method to monitor the water content of ILs even in applications when the temperature may be simultaneously altered; this information can lead to the optimized use of these ILs in many applications.

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

Application of Ionic Liquids for the Recycling and Recovery of Technologically Critical and Valuable Metals

Population growth has led to an increased demand for raw minerals and energy resources; however, their supply cannot easily be provided in the same proportions. Modern technologies contain materials that are becoming more finely intermixed because of the broadening palette of elements used, and this outcome creates certain limitations for recycling. The recovery and separation of individual elements, critical materials and valuable metals from complex systems requires complex energy-consuming solutions with many hazardous chemicals used. Significant pressure is brought to bear on the improvement of separation and recycling approaches by the need to balance sustainability, efficiency, and environmental impacts. Due to the increase in environmental consciousness in chemical research and industry, the challenge for a sustainable environment calls for clean procedures that avoid the use of harmful organic solvents. Ionic liquids, also known as molten salts and future solvents, are endowed with unique features that have already had a promising impact on cutting-edge science and technologies. This review aims to address the current challenges associated with the energy-efficient design, recovery, recycling, and separation of valuable metals employing ionic liquids.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Electric-Field-Induced Assembly of an Ionic Liquid–Water Interphase Enables Efficient Heavy Metal Electrosorption

Controlling ion desolvation, transport, and charge transfer at the electrode-electrolyte interface (EEI) is critical to enabling the rational design of efficient and selective separation of targeted heavy metals and decontamination of industrial waste water. One challenge is to sufficiently resolve and interrogate the intermediate transformation steps between solvated metal cations and bare cations for electroreduction at the EEI and establish pathways to modulate these steps to achieve efficient energy transfer for targeted reactive separations. Herein, we obtained a predictive understanding of the effect of adding a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium chloride (EMIMCl), to an aqueous electrolyte on modulating the desolvation and electrosorption of Pb 2+ cations using a combination of experimental and theoretical techniques. Here, we reveal formation of a compact interphase layer consisting of EMIMCl-Pb complex clusters under an applied electric field using operando electrochemical Raman spectroscopy, atomic force microscopy, and electrochemical impedance spectroscopy measurements combined with classical molecular dynamics simulations. The application of a larger negative potential is shown to result in formation of a well oriented layer with the positive imidazolium ring of the EMIMCl lying on the electrode and the long hydrophobic alkyl chain extending into the bulk electrolyte. This oriented layer is demonstrated to facilitate desolvation of incoming solvated Pb 2+ cations and decrease the charge transfer resistance for Pb electrodeposition, which has important implications for selective removal of Pb from contaminated mixtures. Overall, our studies open up new opportunities to modulate ion desolvation using hydrophobic ionic liquids in aqueous electrolytes for efficient heavy metal separation.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Active species in chloroaluminate ionic liquids catalyzing low-temperature polyolefin deconstruction

Abstract Chloroaluminate ionic liquids selectively transform (waste) polyolefins into gasoline-range alkanes through tandem cracking-alkylation at temperatures below 100 °C. Further improvement of this process necessitates a deep understanding of the nature of the catalytically active species and the correlated performance in the catalyzing critical reactions for the tandem polyolefin deconstruction with isoalkanes at low temperatures. Here, we address this requirement by determining the nuclearity of the chloroaluminate ions and their interactions with reaction intermediates, combining in situ 27 Al magic-angle spinning nuclear magnetic resonance spectroscopy, in situ Raman spectroscopy, Al K-edge X-ray absorption near edge structure spectroscopy, and catalytic activity measurement. Cracking and alkylation are facilitated by carbenium ions initiated by AlCl 3 - tert -butyl chloride (TBC) adducts, which are formed by the dissociation of Al 2 Cl 7 − in the presence of TBC. The carbenium ions activate the alkane polymer strands and advance the alkylation cycle through multiple hydride transfer reactions. In situ 1 H NMR and operando infrared spectroscopy demonstrate that the cracking and alkylation processes occur synchronously; alkenes formed during cracking are rapidly incorporated into the carbenium ion-mediated alkylation cycle. The conclusions are further supported by ab initio molecular dynamics simulations coupled with an enhanced sampling method, and model experiments using n-hexadecane as a feed.

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

Electrodeposition of Aluminum in the 1-Ethyl-3-Methylimidazolium Tetrachloroaluminate Ionic Liquid

The electrodeposition of Al was investigated in an ionic liquid (IL), with 1-ethyl-3-methylimidazolium tetrachloroaluminate ([EMIm]AlCl4) as the electrolyte with AlCl3 precursor. The [EMIm]AlCl4 electrolyte exhibited a wide and stable electrochemical window from 3.2 to 2.3 V on a glassy carbon electrode when temperature was increased from 30 °C to 110 °C. The addition of AlCl3 into [EMIm]AlCl4 generated significant well-developed nucleation growth loops, and new coupled reduction and oxidation peaks in cyclic voltammograms corresponding to the Al deposition and dissolution, respectively. A calculation model was proposed predicting compositions of anions in AlCl3/[EMIm]AlCl4 system, and [Al2Cl7]− was found to be the active species for Al deposition. In AlCl3/[EMIm]AlCl4 (1:5), the reduction rate constants were 1.18 × 10−5 cm s−1 and 3.37 × 10−4 cm s−1 at 30 °C and 110 °C, respectively. Scanning electron microscope (SEM), energy dispersive spectroscope (EDS), and X-ray diffraction (XRD) microscope results showed that the metallic Al film had been successfully deposited on glassy carbon electrodes through constant-potential cathodic reductions. The [EMIm]AlCl4 was a promising electrolyte directly used for Al deposition.

Shi, Meng↗