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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Polycation ionic liquid tailored PEO-based solid polymer electrolytes for high temperature lithium metal batteries

Poly(ethylene oxide) (PEO)-based polymer electrolytes are promising candidates for solid-state electrolytes in safer, next generation lithium metal batteries. Despite their benefits however, PEO-based electrolyte exhibits highly crystalline ethylene oxide chains that provide poor ionic conductivity and, thus severely limit its practical application. Here, we report the use of hydroxypropyl trimethylammonium bis(trifluoromethane) sulfonimide chitosan salt (HACC-TFSI), which is an amorphous poly(ionic liquid) based biomass chitosan derivative, as a modifier for PEO-based solid polymer electrolytes (SPEs) to address these deficiencies. Hybrid SPEs with HACC-TFSI display enlarged amorphous regions with enhanced ionic conductivity. Interactions between quaternary ammonium cations and TFSI-anions in hybrid SPEs are also found to promote dissociation between Li + and TFSI - , which further increases ionic mobility. Moreover, the electrochemical stability, mechanical strength, and thermal stability of hybrid SPEs are collectively superior to blank SPEs without HACC-TFSI. LiFePO 4 /SPEs/Li full-cells assembled using 10wt% HACC-TFSI in PEO (10%HACC-TFSI/SPEs) electrolyte provide a capacity of 161.3 mAh g -1 and operate with excellent cycle performances at 0.2 C and 60 C. Finally, even when the temperature is increased to 150 C, LiFePO 4 /SPEs/Li cells with 10%HACC-TFSI/SPEs still display remarkable cycle performance with 73% capacity retention after 100 cycles at 1 C rate.

25 ENERGY STORAGE↗
NASA NTRSDate not supplied

Improvements in Ionic Liquid Technology for Carbon Dioxide Removal Applications

Carbon dioxide removal from cabin air continues to be of vital importance for future space missions. Current and proposed approaches have employed solid sorbents, hollow fiber membrane separators, and direct liquid sorbent contactors. Recent developments in ionic liquids have potential to improve performance in all three of these technologies. Efficient encapsulation of ionic liquids by polymeric shell can enable their use in a solid sorbent-like configuration without significant integration intervention to the current space technology. Poly(ionic liquid)-ionic liquid membranes have the potential to cross over the Robeson selectivity-permeability upper bound, and thereby outperform traditional membranes used in hollow fibers. Advances in ionic liquid chemistry enables performance improvements in liquid sorbent contactors owing to the tunable gravimetric CO2 capacity, reaction enthalpy and liquid viscosity. This paper will describe recent work in each of these areas.

Ionic Liquid,Carbon Dioxide,Air Revitalization↗
NASA NTRS2017

Ionic Polyimides: New High Performance Polymers for Additive Manufacturing

There is currently a very limited set of engineering polymers that have been demonstrated as viable for use in 3-D printing. Additive manufacturing of custom components will require a much larger array of polymers, especially those with physical, thermal, chemical, and mechanical properties that can be tailor-made. The development of ‘Ionic Polyimides’ offers a solution to this shortage by combining the well understood and widely accepted properties of conventional polyimides, with a new approach to polymer synthesis. Polyimides and polymeric ionic liquids (poly(ILs)) are at the forefront of advanced polymer materials, each with their own set of advantages and disadvantages. While it is clear that more types of polymer materials are needed for fused deposition modeling (FDM) additive manufacturing, there is a need to explore these classes of materials. The synthesis process developed by the Bara Research Group at the University of Alabama allows full control over polymer structure, nanostructure, thermal, electrical, and physical properties making them a prime candidate for use in the additive manufacturing process. Furthermore, the new process allows us to tailor-make a high strength polymer that can be used to fabricate filament feedstock instead of pellets for 3D printing. The primary objective of this proposal is to determine the relationship between molecular structure, physical properties, and performance of ionic polyimides. Further, we seek to determine their utility as materials suitable for additive manufacturing of components used in aerospace vehicles, with an emphasis on characterizing and simulating their thermal behaviors and properties. This proposal addresses the need for fundamental research on a customizable polymer filament feedstock for 3-D printing with tailor-made properties potentially making it superior to the commercial blends offered in industry today. The deliverables for this project are the creation of a database that will detail the relationships between the molecular structure and physical properties for the ionic polyimide of interest (e.g. Tg/Tm (Glass Transition Temperature divided by Melting Point)) relative to different ionic polyimide structures). This new database will provide a “road map” to the development of the first generation of materials and ultimately proof-of-concept.

Jackson, Enrique↗
DOE OSTI2021

Recent Developments in High-Performance Membranes for CO 2 Separation

In this perspective article, we provide a detailed outlook on recent developments of high-performance membranes used in CO 2 separation applications. A wide range of membrane materials including polymers of intrinsic microporosity, thermally rearranged polymers, metal–organic framework membranes, poly ionic liquid membranes, and facilitated transport membranes were surveyed from the recent literature. In addition, mixed matrix and polymer blend membranes were covered. The CO 2 separation performance, as well as other membrane properties such as film flexibility, processibility, aging, and plasticization, were analyzed.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2020

Ionic Polyimides: New High Performance Polymers for Additive Manufacturing

There is currently a very limited set of engineering polymers that have been demonstrated as viable for use in 3-D printing. Additive manufacturing of custom components will require a much larger array of polymers, especially those with physical, thermal, chemical, and mechanical properties that can be tailor-made. The development of ‘Ionic Polyimides’ offers a solution to this shortage by combining the well understood and widely accepted properties of conventional polyimides, with a new approach to polymer synthesis. Polyimides and polymeric ionic liquids (poly(ILs)) are at the forefront of advanced polymer materials, each with their own set of advantages and disadvantages. While it is clear that more types of polymer materials are needed for fused deposition modeling (FDM) additive manufacturing, there is a need to explore these classes of materials. The synthesis process developed by the Bara Research Group at the University of Alabama allows full control over polymer structure, nanostructure, thermal, electrical, and physical properties making them a prime candidate for use in the additive manufacturing process.

Jackson, Enrique↗
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 OSTI2020

Synthesis and characterization of imidazolium-mediated Tröger's base containing poly(amide)-ionenes and composites with ionic liquids for CO 2 separation membranes

Considerable attention has been given to polymeric membranes either containing, or built from, ionic liquids (ILs) in gas separation processes due to their selective separation of CO 2 molecules. Achieving high-performance CO 2 separation membranes with enhanced permeability and selectivity relies mainly on rationally designing the molecular substructure and molecular composition of the polymer matrix. In this work, we have exclusively explored a facile synthetic route to incorporate aromatic amide linkages onto an ionene backbone derived from imidazolium-mediated Tröger's base moieties, yielding a novel rigid polyamide-ionene material (“Im-TB-PA ionene”). We have optimized two novel Im-TB-PA ionene polymers via Menshutkin reactions between N,N'-(1,4-phenylene)bis(4-(chloromethyl)benzamide) and equimolar amounts of two isomeric diimidazole-functionalized Tröger's base monomers with ‘ortho’ or ‘para’ regiochemistry. The two resulting Im-TB(o&p)-PA ionenes exhibited high molecular weights and excellent solubilities in polar organic solvents, serving homogeneous and mechanically stable blend membranes with “free” ILs. The structural and physical properties, as well as the gas separation behaviors of both the Im-TB(o&p)-PA ionenes and their IL composite counterparts ([Im-TB(o&p)-PA] + [IL]), were further extensively investigated. The membrane with an optimal composition and polymer architecture ([Im-TB(o)-PA] + [IL]) exhibited outstanding permselectivites for CO 2 /CH 4 (46.73), CO 2 /N 2 (51.74), and CO 2 /H 2 (4.38) gas pairs together with the best CO 2 permeability of 47.2 barrer. Altogether, this study provides a promising strategy to explore the benefits of Im-TB-PA ionenes to separate CO 2 from flue gas, natural gas, and syngas streams, while opening new possibilities in polymer design with strong candidate materials for other practical applications.

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

Minimal implicit-solvent coarse-grained simulation of Pluronic block copolymers with ionic liquids

Pluronic block copolymers, composed of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) in a triblock structure (PEO–PPO–PEO), are well known for their amphiphilic character and ability to self‐assemble into micelles in aqueous solution. The addition of ionic liquids (ILs) can further modulate the core–shell structures of these copolymers, influencing their stability, critical micellization temperature, and size. However, fully atomistic simulations often become prohibitively expensive due to the size and complexity of these systems. In this work, coarse‐grained simulations using a minimal implicit‐solvent model were performed to examine how two classes of ILs, namely, 1‐alkyl‐3‐methylimidazolium ([C n C 1 im]) and 1‐alkyl‐3‐methylpyrrolidinium ([C n C 1 pyrr]), change the micellization of Pluronic block copolymers in aqueous solution. The effects of IL concentration and alkyl group length were investigated, and the model greatly improved the efficiency of simulating large‐scale micelle systems. Furthermore, the numerical simulations are qualitatively compared with experimental investigations. Our results show that adding ILs expands the micelle core by embedding IL tails among the PPO blocks, thereby increasing overall micelle size. Less polar ILs generally induce more pronounced micellar growth. However, the effect of IL tail length on conformation and micellar packing is non‐monotonic. Up to moderate chain lengths (around C8–C10), the IL tails can extend sufficiently to increase local separation within the micelle; at longer tail lengths, enhanced hydrophobic clustering and steric hindrance cause the tails to bend or fold, capping further expansion. In addition, although block copolymer chains tend to pack more closely in the presence of longer‐tailed ILs, the random coil size of an individual polymer chain does not necessarily shrink. Meanwhile, these insights provide a deeper understanding of how Pluronic/IL systems interact, informing applications in drug delivery, cosmetics, food, and environmental engineering. Finally, our minimal implicit‐solvent model can be applied to larger systems and longer timescales, substantially reducing computational cost while reproducing key structural trends observed experimentally.

Atomistic simulations↗
DOE OSTI2023

Role of surface wetting on tribological behavior for laser nanotextured steel using ionic liquid lubricants

Here, this research evaluates the effect of surface wettability on the tribological performance through ball-on-flat tribology testing. The substrate material, M2 tool steel, is laser processed and then functionalized with fluorocarbon and nitrile chemistry to achieve distinct oleophobicity and oleophilicity, respectively, but with a similar nanoscale surface texture. The baseline lubricant is poly-alpha-olefin (PAO) oil, and ionic liquids (ILs) are used as additives for this study. The interaction between the nanoscale textured steel surface and ionic liquid-based oils is investigated. A set of reciprocating wear tests are performed to investigate the tribological behavior of the tribo-system consisting of the surface-engineered, flat M2 tool steel specimen and a standard, surface-polished steel ball. Results show that the oleophobic flat surface results in a lower friction, while the oleophilic surface modification leads to a better wear protection to the flat surface. Ammonium-based IL provides the highest friction reduction, while the phosphonium-based ILs provide an improved wear protection.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Poly(diallylmethylammonium) proton conducting membranes with high ionic conductivity at intermediate temperatures

High temperature proton exchange membrane fuel cells are being lately investigated because of their high energy efficiency, their superior heat/water management, CO tolerance, and electrode reaction kinetics. To further advance this technology, the polymer membrane portfolio and performance should be improved for intermediate or high temperature operation (>100 °C). In this work we present new poly(diallylmethylammonium) proton conducting membranes with high ionic conductivity at 120 °C. First, new protic ionic liquids, hereafter called DAMAH + X - , were synthesized leading to diallylmethylammonium monomers with different counter-anions. By radical cyclopolymerization through thermal and photoinitiation mechanisms, self-standing protic polymeric membranes of poly(diallylmethylammonium X - ) were obtained. Membranes showed good thermal stability (>250 °C) and mechanical properties without the need of additives such as (protic) ionic liquids, solvents or inorganic charges. Great attention was paid to understand the effect of the different counter-anions on the membrane properties. As a general trend, fluorinated anions coming from strong acids confer high ionic conductivity and allow to reduce the hygroscopic properties on the protic polymeric membranes. Proton structural and dynamical stability at different temperatures and humidification conditions were investigated by Neutron Scattering (QENS and NR). The optimized poly(diallylmethylammonium X - ) shows similar ionic conductivity values than Nafion 212 under varying relative humidity conditions at 80 °C. Furthermore, it shows a high ionic conductivity value of 1.9 × 10 -3 Scm -1 at 120 °C under dry conditions.

08 HYDROGEN↗
NASA NTRS2007

Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers

Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.

Tigelaar, Dean M.↗
DOE OSTI2021

Room Temperature to 150 °C Lithium Metal Batteries Enabled by a Rigid Molecular Ionic Composite Electrolyte

Molecular ionic composites (MICs), made from ionic liquids and a rigid-rod polymer poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) (PBDT), are a new type of rigid gel electrolyte that combine fast ion transport with high thermal stability and mechanical strength. In this work, a MIC electrolyte membrane is prepared that is composed of PBDT, lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr 14 TFSI) in a mass ratio of 10:10:80. The ionic conductivity at 25 °C is 0.56 mS cm –1 with no added flammable/volatile components. Although the polymer content is only 10 wt%, this MIC membrane is rigid with a tensile modulus of 410 MPa at room temperature. The MIC membrane remains stable and rigid at 200 °C with the shear storage modulus (G') only slightly decreasing by 35%. Li/MIC/LiFePO 4 cells demonstrate stable cycling performance over a wide temperature range from 23 to 150 °C. The specific discharge capacity at 100 and 150 °C at 1 C rate exceeds 160 mAh g –1 . The discharge capacity retention is 99% after 50 cycles at 150 °C. Furthermore, this stable battery performance shows that this low polymer content MIC membrane qualifies for use as a solid electrolyte in lithium metal batteries operating over a wide temperature range.

25 ENERGY STORAGE↗
DOE OSTI2020

Ion Exchange Gels Allow Organic Electrochemical Transistor Operation with Hydrophobic Polymers in Aqueous Solution

Conjugated-polymer-based organic electrochemical transistors (OECTs) are being studied for applications ranging from biochemical sensing to neural interfaces. While new polymers that interface digital electronics with the aqueous chemistry of life are being developed, the majority of high-performance organic transistor materials are poor at transporting biologically relevant ions. Here, the operating mode of an organic transistor is changed from that of an electrolyte-gated organic field-effect transistor (EGOFET) to that of an OECT by incorporating an ion exchange gel between the active layer and the aqueous electrolyte. This device works by taking up biologically relevant ions from solution and injecting more hydrophobic ions into the active layer. Using poly[2,5-bis(3-tetradecylthiophen-2-yl) thieno[3,2-b]thiophene] as the active layer and a blend of an ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and poly(vinylidene fluoride-co-hexafluoropropylene) as the ion exchange gel, four orders of magnitude improvement in device transconductance and a 100-fold increase in kinetics are demonstrated. The ability of the ion-exchange-gel OECT to record biological signals by measuring the action potentials of a Venus flytrap is demonstrated. These results show the possibility of using interface engineering to open up a wider palette of organic semiconductors as OECTs that can be gated by aqueous solutions.

Bischak, Connor G.↗