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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.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Proton Conducting Sulfonated Poly(Ionic Liquid) Block Copolymers

Herein, we report the synthesis of proton-conducting sulfonated poly(ionic liquid) block copolymers (S-PILBCPs) containing one block with sulfonic acid (sulfonated styrene, SS) and the other with an IL moiety (vinylbenzylmethylimidazolium bis(trifluoromethylsulfonyl)imide, VBMIm-TFSI) using reversible addition–fragmentation chain-transfer (RAFT) polymerization and post-polymerization modifications (i.e., functionalization, anion exchange reactions, and sulfonation). The S-PILBCPs uniquely conjoin the SS block with mobile protons (H + ) and the PIL block with mobile anions (TFSI – ), where multiple highly desired properties, including high proton conductivity (from the SS block), and high IL-philicity and oxygen solubility (from the PIL block) can exist compartmentally within a microphase separated morphology (evidenced by differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS)). High ion conductivity of 79.7 mS/cm at a PIL block composition of 21.6 mol % was observed at 80 °C and 90% relative humidity (RH) (comparable to the benchmark Nafion ionomer). This work successfully demonstrates the design of S-PILBCPs as a new material platform and showcases its promise as an ionomer for proton exchange membrane fuel cells (PEMFCs) as they simultaneously and compartmentally combine proton conductivity and oxygen solubility. Furthermore, these benefits have recently been leveraged to achieve substantial improvement in oxygen reduction reaction (ORR) activity and subsequently fuel cell performance.

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

Screening Ionic Liquids Based on Ionic Volume and Electrostatic Potential Analyses

Ionic liquids are known to have tunable solvation properties, based on the pairing of different anions and cations, but the compositional landscape is vast and challenging to navigate efficiently. Some computational screening protocols are available, but they can be either time-consuming or difficult to implement. Herein, we perform a detailed investigation of the fundamental role of electrostatic interactions in these systems. We effectively develop a bridge between the previous volume-based approach (VBA) with a quantum structure–property relationship (QSPR) approach to create fast, simple screening guidelines. We propose a new parameter that is applicable to both monovalent and multivalent ions, the ionic polarity index (IPI), which is defined as the ratio of the average electrostatic surface potential ($\bar{V}$) of the ion to the net charge of the ion (q). The IPI correlation has been tested on a diverse dataset of 121 ions and reliable predictions can be obtained within a homologous series of ionic liquid compounds.

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

Ion transport in polymerized lyotropic liquid crystals containing ionic liquid

In this work, we investigate the effect of morphology and segmental dynamics on ion transport in polymerized lyotropic liquid crystals (polyLLCs) containing 1-butyl-3-methylimidazolium tetrafluoroborate as ionic liquid (IL). We demonstrate that two important factors, which affect ion conduction in polyLLCs, are grain size and chain density at the interface. The polyLLC with large grain size (70 nm) shows significant reduction in ion conductivity (one order of magnitude) compared to its homopolymer/IL mixture. However, the polyLLC with small grain size (20 nm) has little difference in ion conductivity compared to its homopolymer/IL mixture. It is observed that decreasing the chain density enhances the interaction of IL with polymer chains and consequently slows the relaxation of polymer chains. Finally, in addition, comparing the dynamics of polymer chains in mixtures of homopolymer/IL and templated LLC mesophases shows that the confinement in LLC structure prolongs the relaxation of polymer chains.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Mechanisms of Ion Transport in Block Copolymeric Polymerized Ionic Liquids

We present the results of a multiscale simulation framework investigating the ion transport mechanisms in multicomponent polymerized ionic liquids. Three different classes of polymeric ionic liquid systems, namely, random copolymers, lamellae forming block copolymers, and homopolymers, are constructed at the coarse-grained scale, and their atomistic counterparts are derived by using a reverse mapping method. Using such a framework, we investigate the influence of morphology on ion transport properties of such polymerized ionic liquids. Here, our results for ion mobilities are in qualitative agreement with experimental observations. Further analysis of random copolymer and block copolymer systems reveal that the reduced ion mobilities in such systems arise from the influence of architecture and morphology on ion coordination and intramolecular hopping events.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Partial breaking of the Coulombic ordering of ionic liquids confined in carbon nanopores

Ionic liquids are composed of equal quantities of positive and negative ions. In the bulk, electrical neutrality occurs in these liquids due to Coulombic ordering, in which ion shells of alternating charge form around a central ion. Their structure under confinement is far less well understood. This hinders the widespread application of ionic liquids in technological applications. Here we use scattering experiments to resolve the structure of a widely used ionic liquid (EMI–TFSI) when it is confined inside nanoporous carbons. We show that Coulombic ordering reduces when the pores can accommodate only a single layer of ions. Instead, equally charged ion pairs are formed due to the induction of an electric potential of opposite sign in the carbon pore walls. This non-Coulombic ordering is further enhanced in the presence of an applied external electric potential. Furthermore, this finding opens the door for the design of better materials for electrochemical applications.

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DOE OSTI2017

Synthesis and characterization of low viscosity hexafluoroacetylacetonate-based hydrophobic magnetic ionic liquids

Magnetic ionic liquids (MILs) are distinguished from traditional ionic liquids (ILs) by the incorporation of a paramagnetic component within their chemical structure. Hydrophobic MILs are novel solvents that can be used in many applications, including liquid–liquid extraction (LLE) and catalysis. Low viscosity and low water solubility are essential features that determine their feasibility in LLE. Here, we synthesized extremely hydrophobic MILs by using transition and rare earth metal hexafluoroacetylacetonate chelated anions paired with the trihexyl(tetradecyl)phosphonium ([P 66614 + ]) cation. Hydrophobic MILs exhibiting water solubilities less than 0.01% (v/v) were synthesized in a rapid two-step procedure. Furthermore, the viscosities of the MILs are among some of the lowest ever reported for hydrophobic MILs (276.5–927.9 centipoise (cP) at 23.7 °C) dramatically improving the ease of handling these liquids. For the first time, the magnetic properties of MILs possessing hexafluoroacetylacetonate chelated metal anions synthesized in this study are reported using a superconducting quantum interference device (SQUID) magnetometer. We also achieved an effective magnetic moments (μ eff ) as high as 9.7 and 7.7 Bohr magnetons (μ B ) by incorporating high spin dysprosium and gadolinium ions, respectively, into the anion component of the MIL. The low viscosity, high hydrophobicity, and large magnetic susceptibility of these MILs make them highly attractive and promising solvents for separations and purification, liquid electrochromic materials, catalytic studies, as well as microfluidic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Synergistic Effects of Mixing Sulfone and Ionic Liquid as Safe Electrolytes for Lithium Sulfur Batteries

Here we report a strategy of mixing both the ionic liquid and sulfone with synergistic effects of reducing viscosity, increasing ionic conductivity, reducing the polysulfide dissolution, and improving the safety. The mixtures of the ionic liquids and sulfones also show distinctly different physicochemical properties, including the thermal properties and crystallization behavior. Using these electrolytes, lithium sulfur batteries assembled with lithium and mesoporous carbon composites show a reversible specific capacity of 1265 mAh g-1 (second cycle) by using 40% 1.0 M LiTFSI in MPPY∙TFSI with 60% 1.0 M LiTFSI in MIPS in the first cycle. This capacity is slightly lower than what was obtained in the pure 1.0 M LiTFSI in the sulfone electrolytes; however, it exhibits an excellent cycling stability and remains as high as 655 mAh g-1 even after 50 cycles. Our strategy provides a method to alleviate the polysulfide dissolution and redox shuttle phenomenon, with an improved ionic conductivity at the same time.

electrochemistry↗
DOE OSTI2021

Solubility Behavior of CO 2 in Ionic Liquids Based on Ionic Polarity Index Analyses

Ionic liquids (ILs) can serve as effective CO 2 solvents with an appropriate selection of different anions and cations. However, due to the large library of potential IL compositions, rapid screening methods are needed for characterizing and ranking the expected properties. We have recently proposed the ionic polarity index (IPI) parameter, effectively connecting volume-based approaches and electrostatic potential analyses, providing a single metric that can potentially be used to rapidly screen for desirable IL properties. In this work, the corresponding anion and cation IPIs are used to generate correlations with respect to the CO 2 volumetric solubility in ILs. The relationships are generally applicable to groups of ILs within a homologous ion series, and this can be particularly valuable for pre-screening different ion pairings for maximizing gas solvation performance.

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

Tandem dissolution of UO 3 in amide-based acidic ionic liquid and in situ electrodeposition of UO 2 with regeneration of the ionic liquid: a closed cycle

A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO 3 to UO 2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid N,N-dimethylacetimidium bis(trifluoromethanesulfonimide) in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonimide) serving as the diluent. Bulk electrolysis performed at 1.0 V vs. Ag reference yields a dark brown-black uranium deposit (UO 2 ) on the cathode. Anodic oxidation of water in the presence of dimethylacetamide regenerates the acidic ionic liquid. We have demonstrated the individual steps in the cycle together with a sequential dissolution, electroreduction, and regeneration cycle.

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

Synthesis and properties of polymerized ionic liquids

Polymerization of ionic liquids results in the formation of ionic polymers, which are called poly (ionic liquid)s or polymerized ionic liquids (PIL). This is a brand new form of ionicity in polymer chains with a broad range of applications, though ionic polymers have a long history with the sub-families of polyelectrolytes and ionomers. Although mobility of ions in ionic liquids has named them as the promising candidates for various applications, their applicability is limited in many practical systems because of not having the advantages of neither liquids nor solids, suffering from both leakage issue and high viscosity. PILs perfectly fit with the practical requirements while having almost all features of ionic liquids. This review summarizes some potential applications of PILs. The architecture of PILs can be easily re-designed by both the polymer backbone and outer ion. Not only by post-polymerization but also by in situ ion exchange, the chemical and mechanical properties of PILs can be tuned. Lastly, owing to the high chemical activity and flexible architecture, PILs are the promising candidates for sensors and actuators, electroactive binders, solid and gel electrolytes, non-blocking matrix of nanocomposites, etc.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Nanocrystals in Molten Salts and Ionic Liquids: Experimental Observation of Ionic Correlations Extending beyond the Debye Length

The nature of the interface between the solute and the solvent in a colloidal solution has attracted attention for a long time. For example, the surface of colloidal nanocrystals (NCs) is specially created to impart colloidal stability in a variety of polar and nonpolar solvents. This work focuses on a special type of colloids where the solvent is a molten inorganic salt or organic ionic liquid. The stability of such colloids is difficult to rationalize because solvents with high density of mobile charges efficiently screen the electrostatic double-layer repulsion, and purely ionic molten salts represent an extreme case where the Debye length is only similar to 1 angstrom. We introduce a detailed investigation of NC dispersions in molten salts and ionic liquids using small-angle X-ray scattering (SAXS), atomic pair distribution function (PDF) analysis and molecular dynamics (MD) simulations. Our SAXS analysis confirms that a wide variety of NCs (Pt, CdSe/CdS, InP, InAs, ZrO 2 ) can be uniformly dispersed in molten salts like AlCl 3 /NaCl/KCl (AlCl 3 /AlCl 4 - ) and NaSCN/KSCN and in ionic liquids like 1-butyl-3-methylimidazolium halides (BMIM + X - , where X = Cl, Br, I). By using a combination of PDF analysis and molecular modeling, we demonstrate that the NC surface induces a solvent restructuring with electrostatic correlations extending an order of magnitude beyond the Debye screening length. These strong oscillatory ion-ion correlations, which are not accounted by the traditional mechanisms of steric and electrostatic stabilization of colloids, offer additional insight into solvent-solute interactions and enable apparently "impossible" colloidal stabilization in highly ionized media.

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