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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

New Insights into the Charge-Transfer-to-Solvent Spectrum of Aqueous Iodide: Surface versus Bulk

Liquid phase charge-transfer-to-solvent (CTTS) transitions are important, as they serve as photochemical routes to solvated electrons. Here in this work, broadband deep-ultraviolet electronic sum frequency generation (DUV-ESFG) and two-photon absorption (2PA) spectroscopic techniques were used to assign and compare the nature of the aqueous iodide CTTS excitations at the air/water interface and in bulk solution. In the one-photon absorption (1PA) spectrum, excitation to the 6s Rydberg-like orbital (5p → 6s) gives rise to a pair of spin–orbit split iodine states, 2 P 3/2 and 2 P 1/2 . In the 2PA spectra, the lower-energy 2 P 3/2 peak is absent and the observed 2PA peak, which is ~0.14 eV blue-shifted relative to the upper 2 P 1/2 CTTS peak seen in 1PA, arises from 5p → 6p electronic promotion. The band observed in the ESFG spectrum is attributed to mixing of excited states involving 5p → 6p and 5p → 6s promotions caused by both vibronic coupling and the external electric field generated by asymmetric interfacial solvation.

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

Carbon Electrodes from Powder River Basin Coal Development of Competitive Supercapacitor Electrodes of Diverse Compositions from Coal Extract

Recent demand for coal as a thermal energy source has decreased significantly and will likely continue to decrease as renewable sources of energy become more available and environmental concern and cost from burning coal makes it more costly than renewables. Given that Powder River Basin (PRB) coal in Wyoming has relatively low thermal energy, it is critical for Wyoming to employ coal in other capacities at the current energy transition period in history. Among many potential non-thermal applications, PRB coal can be utilized for membrane and electrode applications through the formation of carbon fibers. Coal-derived membranes can become low-cost, conductive membranes for use in electrodialysis separation processes. Carbon fiber derived electrodes have been shown be a cost-effective alternative to typical electrode materials that can meet or exceed the performance of current carbon electrode materials. In this talk, we demonstrate the manufacture of supercapacitor electrodes from Powder River Basin (PRB) coal-derived precursors. Specifically, PRB coal was treated in cheap solvents, partitioned into liquid extract and solid residue. An electropinning process has been developed that can convert either the liquid extract or the solid residue into carbon fiber mats. The electrospinning process is versatile with many tunable process parameters to achieve desirable physiochemical properties. For example, the coal residue can be manipulated by additional heat treatment, or by adding binders, salts, or surfactants to create a solution that can be electrospun into advanced carbon electrodes with desirable structural and surface properties. Similarly, some of the liquid extract (tar fraction) can be subsequently reacted with toluene diisocyanate to create resinous coal-derived polyurethane (PUs) as a spinnable ink. Carbon nanofiber mats made from our proprietary electrospinning process were further carbonized at temperature ranging from 700°C to 900°C before they are used as electrodes in supercapacitors. Galvanostatic charge-discharge (GCD) results show that the best performing PU fiber mats can deliver a specific capacitance of 604 F g -1 at the current density of 1 A g -1 . A carbon fiber mat from a different solvent extraction residue also delivered the specific capacitance of 508 F g -1 . These specific capacitance values are comparable to or better than commercial activated carbons, demonstrating the viability of manufacturing carbon nanofiber electrodes from coal without the use of a commercial polymer as binder in the spinning ink.

Cincotta, Robert↗
NASA NTRS1990

Structure of the polymer-solvent interface

The first measurements of ellipticities from the liquid-liquid interface between polymer and solvent mixtures near their consolute points are reported. When scaled according to theory the ellipticities of high molecular weight polystyrene + solvent mixtures are consistent with those from simple, low molecular weight mixtures. The universal value of the scaled ellipticity is approximately 20 percent lower than that predicted by present theories.

Miles, Danny G., Jr.↗
DOE OSTI2025

Unlocking liquid chemisorption in solid matrices: immobilized deep eutectic solvent-ZIF-8 composites for next-generation CO 2 capture

Achieving net-zero emissions by 2050 requires scalable and durable CO 2 capture solutions, with direct air capture (DAC) gaining increasing prominence. Deep eutectic solvents (DESs) have emerged as promising candidates due to their strong chemisorptive properties, but their liquid-phase nature limits integration into solid systems. In this study, we introduce a solid–liquid hybrid approach by immobilizing [TEAB][TEPA] 2 , a highly CO 2 -reactive DES, onto various supports via non-covalent immobilization. This strategy induces solid-like behavior while retaining molecular-level reactivity of the DES. Among the supports including ZIF-8, zeolite Y, zirconia, and alumina, the [TEAB][TEPA] 2 @ZIF-8-56% composite demonstrated promising CO 2 uptake capacity of 2.00 mmol g −1 adsorbent at 1 bar, 1.48 at 0.15 bar, 0.96 at 0.01 bar, and 0.59 at 0.4 mbar. Particularly, we can observe that the chemisorption capacity under 400 ppm conditions is successfully introduced into ZIF-8, whereas pristine ZIF-8 showed negligible uptake under these same conditions. Breakthrough experiments confirmed robust capture behavior under humid conditions. The composite exhibited excellent cycling stability over 100 capture-release cycles, supported by thermogravimetric analysis. In situ DRIFTS verified that the chemisorptive nature of the DES remained intact after immobilization. Additional characterization studies, including FTIR, PXRD, N 2 physisorption, and XPS depth profiling, revealed partial DES infiltration and strong interfacial interactions. Comparative results using alumina-based composites underscored the importance of microporosity in stability. Finally, these findings suggest that DES-MOF composites hold promise as carbon capture materials, bridging liquid-phase functionality and solid-state robustness.

Yoo, Yunsung [Northwestern Univ., Evanston, IL (Un↗
DOE OSTI2025

Non-solvents as physical blowing agents in printable silicone foams

Silicone foams were produced by dispersing an incompatible liquid phase (i.e. a non-solvent) into an uncured, liquid silicone. The formulation and processing parameters were varied to see the effect on porosity and pore morphology. Specifically, two fluorosilanes were added to stabilize the inclusion of fluorinated solvents as blowing agents. As the floruosilane content increased, the void content increased up to about 44 vol. % when the fluorosilane comprised 18 wt. % of the initial formulation. Fumed silica that was treated with a fluorinated silane was also used to try to stabilize the dispersed liquid. While the fumed silica content did not have a strong effect on the total void content, the morphology changed when silica content changed. Various fluorinated solvents with distinct chemical structures were used as the non-solvent and then removed after curing of the silicone. The interaction of the internal non-solvent phase and the silicone phase was expected to influence the porosity. These insights highlight how the manipulation of formulation and processing parameters, focusing on the inclusion of fluorosilanes and fluorinated solvents, contributes to the understanding of how incompatible liquid phases interact with silicone matrices to control porosity and pore morphology. Additionally, these interactions also influenced processability, leading to formulations that could be printed. Higher content of non-solvent inclusions could increase the yield stress and storage modulus of an uncured formulation, leading to the ability to tune intrastrand porosity while a 3D printed architecture could be modified to introduce porosity between the strands. Furthermore, in addition to fluorinated solvents, we also considered non-fluorinated solvents since these may be more industrially relevant in the future. Overall, this approach provides an alternative route to producing porous foams that can be 3D printed, which could be useful for applications like cushioning and protective gear.

physical blowing agent↗
DOE OSTI2022

Mass transfer intensification through increased surface wetting and liquid turbulence using 3D printing structured packing for CO2 capture

The absorber column is one of the most expensive pieces of equipment to construct in the solvent-based post-combustion carbon capture unit. In order to decrease the absorber size and reduce capital costs, novel polymer packings were proposed by enhancing surface wettability and local turbulence within liquid solvent. The novel packings intensify the mass transfer in CO2 absorption and show better separation efficiency than traditional structured packings. In this work, the economic influence of applying the more efficient packing with a shorter absorber column is studied in a techno-economic analysis for a carbon capture unit at a coal-fired power plant. The baseline case includes CO2 capture unit in a supercritical pulverized coal power plant to generate 650 MWe (net) of electricity, where the additional CO2 capture unit leads to 63.4% increase of LCOE. While implementing UK PCC with traditional and novel packings, there will be 47.2% and 46.4% LCOE increase separately, both of which are lower than the baseline value. Applying more efficient packing and smaller absorber could further lessen the LCOE increase. The UK PCC with traditional packings reduces CO2 capture cost by 23.4% and the application of the advanced packings allows to the reduction increases to 24.4%.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

In-situ ionothermal synthesis of nanoporous carbon/oxide composites: A new key to functional separators for stable lithium-sulfur batteries

Lithium-sulfur batteries (LSBs) with high energy density are promising for energy storage. However, conventional polypropylene-based separator cannot avoid polysulfides shuttling which impedes the practical application of LSBs. Herein, an in-situ ionothermal synthesis strategy that concurrently applies ionic liquid as the solvent, template and high-yield carbon source is proposed for the facile preparation of nanoporous carbon/oxide composite separator modifiers. The composites exhibit features of high polarity, self doping, oxygen vacancy, heteroatom doping, abundant defects and high electronic conductivity. Theoretical and experimental studies suggest that the composites can efficiently trap and convert polysulfides for high-performance LSBs. Indeed, in the composite-modified LSBs with next-generation roll-to-roll dry-processed high-loading sulfur cathodes, enhanced performance is achieved, revealing the effectiveness of the composites as functional materials towards separator modification. Therefore, the proposed strategy and its delivered nanoporous composites exhibit excellent versatility and practicality for high-performance LSBs.

25 ENERGY STORAGE↗
DOE OSTI2021

Using a Chromatographic Pseudophase Model To Elucidate the Mechanism of Olefin Separation by Silver(I) Ions in Ionic Liquids

Silver(I) ions undergo selective olefin complexation and have been utilized in various olefin/paraffin separation techniques such as argentation chromatography and facilitated transport membranes. Ionic liquids (ILs) are solvents known for their low vapor pressure, high thermal stability, low melting points, and ability to promote a favorable solvation environment for silver(I) ion–olefin interactions. To develop highly selective separation systems, a fundamental understanding of analyte partitioning to the stationary phase and the thermodynamic driving forces behind solvation is required. In this study, a chromatographic model treating silver(I) ions as a pseudophase is constructed and employed for the first time to investigate the olefin separation mechanism in silver(I) salt/IL mixtures. Stationary phases containing varying amounts of noncoordinated silver(I) salt ([Ag + ][NTf 2 – ]) dissolved in the 1-decyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C 10 MIM + ][NTf 2 – ]) IL are utilized to determine the partition coefficients of various analytes including alkanes, alkenes, alkynes, aromatics, aldehyde, esters, and ketones. As ligand coordination to silver(I) ions is known to lower its olefin complexation capability, this study also examines two different types of coordinated silver(I) ion pseudophases, namely, monocoordinated silver(I) salt ([Ag + (1-decyl-2-methylimidazole, DMIM)][NTf 2 – ]) and dicoordinated silver(I) salt ([Ag + (1-methylimidazole, MIM)(DMIM)][NTf 2 – ]). The extent of olefin partitioning to the coordinated silver(I) ion pseudophases over the carrier gas and IL decreased by up to two orders of magnitude. Values for enthalpy, entropy, and free energy of solvation were determined for the three silver(I) ion-containing systems. Olefin retention was observed to be enthalpically dominated, while ligand coordination to the silver(I) ion pseudophase resulted in variations for both enthalpic and entropic contributions to the free energy of solvation. Furthermore, the developed model can be used to study chemical changes that occur in silver(I) ions over time as well as identify optimal silver(I) salt/IL mixtures that yield high olefin selectivity.

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

Double-Crucible Vertical Bridgman Technique for Stoichiometry-Controlled Chalcogenide Crystal Growth

Precise stoichiometry control in single-crystal growth is essential for both technological applications and fundamental research. However, conventional growth methods often face challenges such as non-stoichiometry, compositional gradients, and phase impurities, particularly in non-congruent melting systems. Even in congruent melting systems like Bi₂Se₃, deviations from the ideal stoichiometric composition can lead to significant property degradation, such as excessive bulk conductivity, which limits its topological applications. In this study, we introduce the double-crucible vertical Bridgman (DCVB) method, a novel approach that enhances stoichiometry control through the combined use of continuous source material feeding, traveling-solvent growth, and liquid encapsulation, which suppresses volatile element loss under high pressure. Using Bi₂Se₃ as a model system, we demonstrate that crystals grown via DCVB exhibit enhanced stoichiometric control, significantly reducing defect density and achieving much lower carrier concentrations compared to those produced by conventional Bridgman techniques. Moreover, the continuous feeding of source material enables the growth of large crystals. As a result, this approach presents a promising strategy for synthesizing high-quality, large-scale crystals, particularly for metal chalcogenides and pnictides that exhibit challenging non-congruent melting behaviors.

Crystal structure↗
DOE OSTI2023

Transition Metal Dissolution in Lithium-Ion Cells: A Piece of the Puzzle

Static leaching tests were performed using the chemically delithiated positive electrode materials, LiFePO 4 , LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , and LiNi 0.8 Mn 0.1 Co 0.1 O 2 . Instead of the common electrolyte, which contains LiPF 6 , the solvent consisted of only ethylene carbonate (EC) and ethyl methyl carbonate (EMC), limiting the possible reactions to only those that depend on the solvent. The product liquids from these experiments showed that there were lithium-bearing species in common, such as Li(EC) + and Li(EMC) + . Interestingly, we found evidence of electrolyte degradation products in both the positive-and negative-ion mass spectral results. The positive-ion results showed that the products tended to coordinate to lithium. In conclusion, the negative-ion results showed that most of the products tended to complex with transition metals. It was difficult to discern which positive ion was associated with which negative ion.

25 ENERGY STORAGE↗
DOE OSTI2023

Structural elucidation of polydopamine facilitated by ionic liquid solvation

Minimal understanding of the formation mechanism and structure of polydopamine (pDA) and its natural analogue, eumelanin, impedes the practical application of these versatile polymers and limits our knowledge of the origin of melanoma. The lack of conclusive structural evidence stems from the insolubility of these materials, which has spawned significantly diverse suggestions of pDA's structure in the literature. We discovered that pDA is soluble in certain ionic liquids. Using these ionic liquids (ILs) as solvents, we present an experimental methodology to solvate pDA, enabling us to identify pDA's chemical structure. The resolved pDA structure consists of self-assembled supramolecular aggregates that contribute to the increasing complexity of the polymer. The underlying molecular energetics of pDA solvation and a macroscopic picture of the disruption of the aggregates using IL solvents have been investigated, along with studies of the aggregation mechanism in water.

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

Improving nanoparticle superlattice stability with deformable polymer gels

The self-assembly of colloidal nanoparticles into ordered superlattices typically uses dynamic interactions to govern particle crystallization, as these non-permanent bonds prevent the formation of kinetically trapped, disordered aggregates. However, while the use of reversible bonding is critical in the formation of highly ordered particle arrangements, dynamic interactions also inherently make the structures more prone to disassembly or disruption when subjected to different environmental stimuli. Thus, there is typically a trade-off between the ability to initially form an ordered colloidal material and the ability of that material to retain its order under different conditions. Here, we present a method for embedding colloidal nanoparticle superlattices into a polymer gel matrix. This encapsulation strategy physically prevents the nanoparticles from dissociating upon heating, drying, or the introduction of chemicals that would normally disrupt the lattice. However, the use of a gel as the embedding medium still permits further modification of the colloidal nanoparticle lattice by introducing stimuli that deform the gel network (as this deformation in turn alters the nanoparticle lattice structure in a predictable manner). Moreover, encapsulation of the lattice within a gel permits further stabilization into fully solid materials by removing the solvent from the gel or by replacing the solvent with a liquid monomer that can be photopolymerized. This embedding method therefore makes it possible to incorporate ordered colloidal arrays into a polymer matrix as either dynamic or static structures, expanding their potential for use in responsive materials.

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

Ion Transport in Concentrated Crosslinked Solid Polymer Electrolytes

Crosslinking polymers is a common approach to create mechanically stable solid materials such as polymer electrolytes for lithium batteries. In conventional liquid electrolytes, the solvent molecules move freely to accommodate the field-induced motion of ions. However, in crosslinked polymer electrolytes, the rearrangement of polymer segments is constrained by the deformation limits of the network. Herein, we develop a new transport model that accounts for both the formation of concentration gradients and the elasticity of the electrolyte. The elasticity is incorporated by adding an additional term related to the entropy of crosslinked strands to the electrochemical potential of the salt. The resulting Crosslink Model contains two adjustable parameters: $\mathcal{N}$, the average number of monomers in a strand, and λ crit , the maximum strain the network can sustain. These solid-like constraints produce singularities in the governing transport equations, fundamentally altering the concentration profiles. Plateaus in salt concentrations emerge near the electrodes, and network elasticity introduces a strain overpotential. When compared to a Baseline Model ($\mathcal{N}$ → ∞, equivalent to concentrated solution theory), which predicts steepest gradients near the electrodes, both models yield similar current–voltage relationships. Model predictions are compared to electrochemical data for a poly(ethylene oxide)-based crosslinked polymer electrolyte.

Patel, Vivaan [University of California, Berkeley,↗
DOE OSTI2022

Preliminary Assessment of Elemental Analysis of X-Ray Fluorescence with Genetic Algorithm

X-ray fluorescence (XRF) spectroscopy is a promising approach to elemental analysis of forensic samples. Elements in the mixture can be identified from the XRF data because chemical elements are associated with unique spectra. This report consists of preliminary assessment of automated identification of unknown mixtures of elements from XRF spectra using a genetic algorithm (GA). The XRF spectra are measured at the Advanced Photon Source (APS) at the liquid-liquid interface during solvent extraction process. Possible advantages of using GA for identifying elements at the interface from XRF data are discussed, and a path for implementation of GA is outlined.

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

Progress in Genetic Algorithm Fitting of X-Ray Fluorescence Data for Absorption Spectroscopy of Liquid Surfaces

X-ray fluorescence (XRF) spectroscopy of liquid surfaces is a promising approach to elemental analysis of forensic samples. Elements in the mixture can be identified from the XRF data because chemical elements are associated with unique spectra. This report describes progress in the development of automated identification of unknown mixtures of elements from XRF spectra using a genetic algorithm (GA). The XRF spectra are measured at the Advanced Photon Source (APS) at the liquid-liquid interface during solvent extraction process. The usage of the GA is demonstrated and future implementation for related problems are then discussed.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Nuclear Magnetic Resonance Relaxation Pathways in Electrolytes for Energy Storage

Nuclear Magnetic Resonance (NMR) spin relaxation times have been an instrumental tool in deciphering the local environment of ionic species, the various interactions they engender and the effect of these interactions on their dynamics in conducting media. Of particular importance has been their application in studying the wide range of electrolytes for energy storage, on which this review is based. Here we highlight some of the research carried out on electrolytes in recent years using NMR relaxometry techniques. Specifically, we highlight studies on liquid electrolytes, such as ionic liquids and organic solvents; on semi-solid-state electrolytes, such as ionogels and polymer gels; and on solid electrolytes such as glasses, glass ceramics and polymers. Although this review focuses on a small selection of materials, we believe they demonstrate the breadth of application and the invaluable nature of NMR relaxometry.

25 ENERGY STORAGE↗
DOE OSTI2023

The Role of the Anion in Imidazolium-Based Ionic Liquids for Fuel and Terpenes Processing

The potentialities of methylimidazolium-based ionic liquids (ILs) as solvents were evaluated for some relevant separation problems—terpene fractionation and fuel processing—studying selectivities, capacities, and solvent performance indices. The activity coefficients at infinite dilution of the solute (1) in the IL (3), γ13∞, of 52 organic solutes were measured by inverse gas chromatography over a temperature range of 333.2–453.2 K. The selected ILs are 1-butyl-3-methylimidazolium hexafluorophosphate, [C4mim][PF6], and the equimolar mixture of [C4mim][PF6] and 1-butyl-3-methylimidazolium chloride, [C4mim]Cl. Generally, low polar solutes follow γ1,C4mimCl∞ > γ1,C4mimPF6+C4mimCl∞ > γ1,C4mimPF6∞ while the opposite behavior is observed for alcohols and water. For citrus essential oil deterpenation, the results suggest that cations with long alkyl chains, such as C12mim+, promote capacity, while selectivity depends on the solute polarity. Promising results were obtained for the separation of several model mixtures relevant to fuel industries using the equimolar mixture of [C4mim][PF6] and [C4mim]Cl. This work demonstrates the importance of tailoring the polarity of the solvents, suggesting the use of ILs with mixed anions as alternative solvents for the removal of aliphatic hydrocarbons and contaminants from fuels.

Zambom, Aline (ORCID:0000000324512716)↗