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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

NMR and Theoretical Study of In-Pore Diffusivity of Ionic Liquid–Solvent Mixtures

We report despite having a lower energy density than common batteries, electric double-layer capacitors (EDLCs) offer several advantages for high-power applications, including high power density, quick charge and discharge time, and long cycle life. Room-temperature ionic liquids (RTILs) have been intensely studied as promising electrolytes for applications in ELDCs because of their wide potential window, low volatility, as well as thermal and chemical stability. The main deficiency of neat RTILs in such applications is the sluggish diffusivity, which restricts the EDLCs’ power density. To alleviate the slow diffusivity, RTILs can be used in a mixture with organic solvents. In this study, we applied two-dimensional exchange nuclear magnetic resonance spectroscopy (2D EXSY NMR) and molecular dynamics (MD) simulations to investigate the diffusivity of anions of an RTIL, namely, 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (BMIM + –TFSI – ), dissolved in five different organic solvents, in the micropores of activated carbon. We determined that the relative concentrations of ions in solutions in the micropores were higher than those in the bulk solutions and were also solvent-dependent. The ion diffusivities in the pores were found to be almost 2 orders of magnitude slower than in the bulk solutions, with methanol showing the largest relative disparity. These results suggested that the interactions of solvents with the activated carbon are critical not only to the power density of EDLCs but also to the energy density. The comparisons of ion diffusivities between the experiments and the MD simulations suggest the need to consider also the surface functionalities of activated carbon for the simulation of ion diffusion in the micropores of activated carbon.

electric double layer capacitors↗
NASA NTRS1983

An electrochemical rebalance cell for Redox systems

An electrochemical rebalance cell for maintaining electrochemical balance, at the system level, of the acidified aqueous iron chloride and chromium chloride reactant solutions in the redox energy storage system was constructed and evaluated. The electrochemical reaction for the cathode is Fe(+3) + e(-) yields Fe(+2), and that for the anode is 1/2H2 yields H(+) + e(-). The iron (carbon felt) electrode and the hydrogen (platinized carbon) electrode are separated by an anion exchange membrane. The performance of the rebalance cell is discussed as well as the assembly of a single rebalance cell and multicell stacks. Various cell configurations were tested and the results are presented and discussed. The rebalance cell was also used to demonstrate its ability, as a preparative tool, for making high purity solutions of soluble reduced metal ionic species. Preparations of titanium, copper, vanadium and chromium ions in acidified solutions were evaluated.

Acevedo, J. C.↗
DOE OSTI2020

Controlling Magnetization Vector Depth Profiles of La 0.7 Sr 0.3 CoO 3 /La 0.7 Sr 0.3 MnO 3 Exchange Spring Bilayers via Interface Reconstruction

The La 0.7 Sr 0.3 CoO 3–δ /La 0.7 Sr 0.3 MnO 3–δ (LSCO/LSMO) bilayer system is an ideal perovskite oxide platform for investigating interface reconstruction and its effect on their magnetic properties. Previous studies have shown that LSCO can separate into magnetic sublayers, which possess distinct trends as the total LSCO thickness increases. Here, we used polarized neutron reflectometry to quantify changes in the magnetic and chemical depth profiles, and it confirms the formation of ~12 Å-thick interfacial LSCO and LSMO layers, characterized by a decreased nuclear scattering length density compared to the bulk of the layers. This decrease is attributed to the combined effects of oxygen vacancy formation and interfacial charge transfer, which lead to magnetically active Co 2+ ions with ionic radii larger than the Co 3+ /Co 4+ ions typically found in bulk LSCO or single-layer films. The interfacial magnetization values, as well as Co 2+ ion and oxygen vacancy concentrations, depend strongly on the LSCO layer thickness. These results highlight the sensitive interplay of the cation valence states, oxygen vacancy concentration, and magnetization at interfaces in perovskite oxide multilayers, demonstrating the potential to tune their functional properties via careful design of their structure.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Enhanced Optical Contrast and Switching in Near‐Infrared Electrochromic Devices by Optimizing Conjugated Polymer Oligo(Ethylene Glycol) Sidechain Content and Gel Electrolyte Composition

Abstract A detailed investigation addressing the effects of functionalizing conjugated polymers with oligo(ethylene glycol) (EG n ) sidechains on the performance and polymer‐electrolyte compatibility of electrochromic devices (ECDs) is reported. The electrochemistry for a series of donor‐acceptor copolymers having near‐infrared (NIR)‐optical absorption, where the donor fragment is 3,4‐ethylenedioxythiophene (EDOT) or an EG n functionalized bithiophene (g2T) and the acceptor fragment is diketopyrrolopyrrole (DPP) functionalized with branched alkyl or EG n sidechains, is extensively probed. ECDs are next fabricated and it is found that EG n sidechain incorporation must be finely balanced to promote polymer‐electrolyte compatibility and provide efficient ion exchange. Proper electrolyte‐cation pairing and polymer structural tuning affords a 2x increase in optical contrast (from 12% to 24%) and >60x reduction in switching time (from 20 to 0.3 s). Atomic force microscopy (AFM)/grazing incidence wide‐angle X‐ray scattering (GIWAXS) characterization of the polymer film morphology/microstructure reveals that an over‐abundance of EG n sidechains generates large polymer crystallites, which can suppress ion exchange. Lastly, time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) indicates sidechain/electrolyte identity does not influence the electrolyte penetration depth into the films, and EG n sidechain inclusion increases electrolyte cation uptake. The material structural design insight and guidelines regarding the polymer‐electrolyte ion insertion/expulsion dynamics reported here should be of significant utility for developing next‐generation mixed ionic‐electronic conducting materials.

Chemistry↗
DOE OSTI2025

Electrostatic limits on charge selectivity in ultrahigh charge density polymer membranes

Ion-exchange membranes (IEMs) with ultrahigh charge densities offer the promise of enhanced ion transport for electrochemical technologies, yet the fundamental limits of this membrane design strategy are not yet understood. In this work, we present a systematic study of bis(1-vinyl-3-imidazolium) cross-linked polymer membranes with fixed charge contents ranging from 6 to 9 mol/L[dry polymer], synthesized to isolate the effects of charge density at constant membrane water content. While ionic conductivity increases monotonically with increasing charge density, a sharp decline in charge selectivity is observed for the most densely charged membranes, defying conventional expectations. Structural, thermal, and mechanical analyses reveal a critical onset of network disruption and anomalous ion partitioning behavior in these densely charged membranes. With proper consideration of cross-linker geometry, these results are interpreted using Manning's counter-ion condensation theory, which suggests that closely packed charged cross-linkers amplify inter-chain electrostatic interactions and trigger excess counter-ion condensation. Our findings suggest that, beyond a threshold spacing between fixed charges, increased functionalization may harm rather than help charge selectivity of IEMs.

36 MATERIALS SCIENCE↗
NASA NTRS1991

Organic acids and selected nitrogen species for ABLE-3

The NASA Global Tropospheric Experiment (GTE) executed airborne science missions aboard the NASA Wallops Electra (NA429) in the North American high latitude (greater than 45 deg North) atmosphere during Jul. to Aug. 1988 and Jul. to Aug. 1990. These missions were part of GTE's Atmospheric Boundary Layer Experiment (ABLE). The 1988 mission , ABLE-3A, examined the ecosystems of Alaska as a source and/or sink for important tropospheric gases and particles, and gained new information on the chemical composition of the Arctic atmosphere during the summertime. During 1990 the second high latitude mission, ABLE-3B, focused on the Hudson Bay Lowland and Labrador regions of Canada. Both of these missions provided benchmark data sets on atmosphere biosphere exchange and atmospheric chemistry over largely uninhabited regions of North America. In support of the GTE/ABLE-3A and -3B field missions, the University of New Hampshire flew instrumentation aboard the Wallops Electra research aircraft to provide measurements of the trace gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) acid. In addition, measurements were conducted to determine the major water soluble ionic composition of the atmospheric aerosol. For ABLE-3B, groundbased measurements of the acidic trace gases were also performed from the NASA micrometerological tower situated at Schefferville, Laborador. These measurements were aimed at assessing dry deposition of acidic gases to the taiga ecosystem in the Laborador region of Canada.

Talbot, Robert W.↗
DOE OSTI2020

Crystalline Aluminosilicates for Radionuclide Remediation

Crystalline aluminosilicates have a wide range of applications such as media for the capture and/or immobilization of radionuclides. Several different types of metal-exchanged zeolites have been successfully demonstrated as effective sorbents for gaseous, aqueous, or solid-state capture and immobilization of radionuclides including iodine [e.g., I2(g), CH3I(g)], xenon, krypton, radium (e.g., 226Ra and 228Ra), selenium (e.g., 79Se6+), technetium (e.g., 99TcO4-), strontium (e.g., 90Sr2+), cesium (e.g., 135Cs+, 137Cs+), mixed alkali halide streams (i.e., iodide and chloride salts), and actinides (e.g., U6+, Th4+). These zeolites include sodalite (SOD), mordenite (MOR or Z-type), faujasite (FAU), Linde type-A (LTA), cancrinite (CAN), gismondine (GIS), and heulandite (or clinoptilolite) (HEU). The structural building blocks of these seven materials vary from cages (e.g., a-cages, ß-cages, e-cages) to channels linking various cage types and these are mostly comprised of aluminosilicates. This chapter will delve into the crystallographic differences between these framework materials and provide a brief overview of literature data where these seven crystalline aluminosilicates have been utilized for the capture and/or immobilization of radionuclides. Metal-exchanged zeolites (e.g., MOR, FAU, LTA) have often been the source of study for gaseous capture of iodine where the more promising compositions include Ag-exchanged sorbents; these types of materials can be made in a variety of robust forms including berl saddles and extrudates. Sodalite can be used as an immobilization strategy for halide waste streams (e.g., Cl, I), including those from electrochemical reprocessing of used nuclear fuel, as well as TcO4–. Cancrinite has been demonstrated to enhance sorption capacity of sediments for several problematic ionic radionuclides including Cs+, SeO42–, and TcO4–. Actinides such as U6+ and Th4+ have been successfully captured from solutions using MOR, FAU, LTA, and HEU-type aluminosilicates. Finally, mixtures of aluminosilicates have been included in a set of zeolite materials that show promise as sorbents for 226Ra and 228Ra removal from mine waters.

zeolites, aluminosilicates, radionuclide remediati↗
DOE OSTI2020

Efficient Intermolecular Energy Exchange and Soft-ionization of Water at Nanoplatelet Interfaces

X-ray, energetic photon and electron irradiation can ionize and electronically excite target atoms and molecules. These excitations undergo complicated relaxation and energy transfer processes that ultimately determine the manifold of system responses to the deposited excess energy. In weakly bound gas- and solution-phase samples, intermolecular Coulomb decay (ICD) and electron-transfer mediated decay (ETMD) can occur with neighboring atoms or molecules leading to efficient transfer of the excess energy to the surroundings. In ionic solids such as metal-oxides, intra- and inter-atomic Auger decay produces localized final states that lead to lattice damage and typically removal of cations from the substrate. The relative importance of Auger stimulated damage (ASD) versus ICD and ETMD in micro-solvated nanoparticle interfaces is not known. Though ASD is generally expected, essentially no lattice damage and very efficient ICD and ETMD resulting from ionization and electronic excitation of micro-solvated boehmite (AlOOH) nanoplatelets has been observed. Efficient energy transfer and soft ionization of interfacial molecules is likely a general phenomenon at gas-oxyhydroxide nanoparticle interfaces where the density of states of the ionized chemisorbed species significantly overlap the core hole states of the solid.

Jones, Brant M.↗
DOE OSTI2024

Fast Room-Temperature Mg-Ion Conduction in Clay-Like Halide Glassy Electrolytes

The discovery of mechanically soft solid-state materials with fast Mg-ion conduction is crucial for the development of solid-state magnesium batteries. In this paper, novel magnesium gallium halide compounds are reported that achieve high ionic conductivity of 0.47 mS cm -1 at room temperature. These Mg-ion conductors obtained by ball milling Mg and Ga salts exhibit clay-like mechanical properties, enabling intimate contact at the electrode–electrolyte interface during battery cycling. With a combination of experimental and computational analysis, this study identifies that the soft-clay formation is induced by partial anion exchange during milling. This partial anion exchange creates undercoordinated magnesium ions in a chlorine-rich environment, yielding fast Mg-ion conduction. This work demonstrates the potential of clay-like halide electrolytes for all-solid-state magnesium batteries, with possible further extension to other multivalent battery systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Highly quaternized polystyrene ionomers for high performance anion exchange membrane water electrolysers

Alkaline anion exchange membrane (AEM) electrolysers to produce hydrogen from water remain at an early stage of development, and their performance is far lower than that of systems based on proton exchange membranes. Here, we report an ammonium-enriched anion exchange ionomer that improves the performance of an AEM electrolyser to levels approaching that of state-of-the-art proton exchange membrane electrolysers. Using rotating-disk electrode experiments, we show that a high pH (>13) in the electrode binder is the critical factor for improving the activity of the hydrogen- and oxygen-evolution reactions in AEM electrolysers. Based on this observation, we prepared and tested several quaternized polystyrene electrode binders in an AEM electrolyser. Using the binder with the highest ionic concentration and a NiFe oxygen evolution catalyst, we demonstrated performance of 2.7 A cm -2 at 1.8 V without a corrosive circulating alkaline solution. The limited durability of the AEM electrolyser remains a challenge to be addressed in the future.

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

Uncovering Structure–Conductivity Relationships in Anion Exchange Membranes (AEMs) Using Interpretable Machine Learning

Anion exchange membranes (AEMs) play a vital role in the performance of water electrolyzers and fuel cells, yet their discovery and optimization remain challenging due to the complexity of structure–property relationships. In this study, we introduce a machine learning framework that leverages conditional graph neural networks (cGNNs) and descriptor-based models and a hybrid graph neural network (HGARE) to predict and interpret ionic conductivity. The descriptor-based pipeline employs principal component analysis (PCA), ablation, and SHAP analysis to identify factors governing anion conductivity, revealing electronic, topological, and compositional descriptors as key contributors. Beyond prediction, dimensionality reduction and clustering are performed by employing t-SNE and KMeans as well as SOM, which reveal distinct membranes clusters, some of which were enriched with high anion conductivity. Among graph-based approaches, the graph convolutional (GCN) achieved strong predictive performance, while the Hybrid Graph Autoencoder-Regressor Ensemble (HGARE) achieved the highest accuracy. Additionally, atom-level saliency maps from GCN provide spatial explanations for conductive behavior, revealing the importance of polarizable and flexible regions. This work contributes to the accelerated and data-driven design of high-performance AEMs.

Naghshnejad, Pegah [Department of Chemical Enginee↗
NASA NTRS1975

An auroral F-region study using in situ measurements by the Atmosphere Explorer-C satellite

The ion densities observed as the Atmosphere Explorer-C satellite passed through an aurora at F-region altitudes are compared to those calculated from photochemical theory using in situ measurements of atmospheric parameters (ionic and neutral composition; electron flux; neutral temperature; ion temperature) along the satellite track together with current values for reaction rates. Good agreement is obtained for the ions O2(+), NO(+), and N2(+). The atomic nitrogen densities calculated from the observed NO(+)/O2(+) ratio are found to account for about 60% of the N(+) production through electron impact on N and the resonant charge exchange of O(+)(2P) with N(4S). The N density at about 280 km, the region of the most intense electron fluxes (20 erg/sq cm/sec), is between 20 and 70 million/cu cm.

Torr, M. R.↗
DOE OSTI2020

99 TcO 4 - removal from legacy defense nuclear waste by an alkaline-stable 2D cationic metal organic framework

Removal of 99 TcO 4 - from legacy defense nuclear tank waste at Savannah River Site is highly desirable for the purpose of nuclear safety and environmental protection, but currently not achievable given the extreme conditions including high alkalinity, high ionic strength, and strong radiation field. Herein, we present a potential solution to this long-term issue by developing a two-dimensional cationic metal organic framework SCU-103, showing ultrahigh stability in alkaline aqueous media and great resistance to both β and γ radiation. More importantly, it is very effective for 99 TcO 4 - separation from aqueous media as demonstrated by fast exchange kinetics, high sorption capacity, and superior selectivity, leading to the successful removal of 99 TcO 4 - from actual Savannah River Site high level tank waste for the first time, to the best of our knowledge. In addition, the uptake mechanism is comprehensively elucidated by molecular dynamics simulation and density functional theory calculation, showing a unique chemical recognition of anions with low charge density.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
NASA NTRS1973

Studies of a Halophilic NADH Dehydrogenase. 1: Purification and Properties of the Enzyme

An NADH dehydrogenase obtained from an extremely halophilic bacterium was purified 570-fold by a combination of gel filtration, chromatography on hydroxyapatite, and ion-exchange chromatography on QAE-Sephadex. The purified enzyme appeared to be FAD-linked and bad an apparent molecular weight of 64000. Even though enzyme activity was stimulated by NaCl, considerable activity (430 % of the maximum activity observed in the presence of 2.5 M NaCl) was observed in the absence of added NaCl. The enzyme was unstable when incubated in solutions of low ionic strength. The presence of NADH enhanced the stability of the enzyme.

Hochstein, Lawrence I.↗
DOE OSTI2023

Controlling swelling in mixed transport polymers through alkyl side-chain physical cross-linking

Semiconducting conjugated polymers bearing glycol side chains can simultaneously transport both electronic and ionic charges with high charge mobilities, making them ideal electrode materials for a range of bioelectronic devices. However, heavily glycolated conjugated polymer films have been observed to swell irreversibly when subjected to an electrochemical bias in an aqueous electrolyte. The excessive swelling can lead to the degradation of their microstructure, and subsequently reduced device performance. An effective strategy to control polymer film swelling is to copolymerize glycolated repeat units with a fraction of monomers bearing alkyl side chains, although the microscopic mechanism that constrains swelling is unknown. Here we investigate, experimentally and computationally, a series of archetypal mixed transporting copolymers with varying ratios of glycolated and alkylated repeat units. Experimentally we observe that exchanging 10% of the glycol side chains for alkyl leads to significantly reduced film swelling and an increase in electrochemical stability. Through molecular dynamics simulation of the amorphous phase of the materials, we observe the formation of polymer networks mediated by alkyl side-chain interactions. When in the presence of water, the network becomes increasingly connected, counteracting the volumetric expansion of the polymer film.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

High temperature conductivity of potassium-beta(double prime)-alumina

Potassium beta(double prime)-alumina (BDPA) single crystals have been reported by several groups to leave higher ionic conductivity than sodium BDPA crystals at room temperature, and similar conductivities are obtained at temperatures up to 600-700 K. Potassium BDPA ceramics have been reported to have significantly poorer conductivities than those of sodium BDPA ceramics, but conductivity measurements at temperatures above 625 K have not been reported. In this study, K(+)-BDPA ceramics were prepared from Na(+)-BDPA ceramic using a modified version of the exchange reaction with KCl vapor reported by Crosbie and Tennenhouse (1982), and the conductivity has been measured in K vapor at temperatures up to 1223 K, using the method of Cole et al. (1979). The results indicate reasonable agreement with earlier data on K(+)-BDPA ceramic measured in a liquid K cell, but show that the K(+)-BDPA ceramic's conductivity approaches that of Na(+)-BDPA ceramic at higher temperatures, being within a factor of four at 700 K and 60 percent of the conductivity of Na(+)-BDPA at T over 1000 K. Both four-probe dc conductivity and four probe ac impedance measurements were used to characterize the conductivity. A rather abrupt change in the grain boundary resistance suggesting a possible phase change in the intergranular material, potassium aluminate, is seen in the ac impedance behavior.

Williams, R. M.↗
DOE OSTI2022

Nafion Inhibits Polysulfide Crossover in Hybrid Nonaqueous Redox Flow Batteries

Here, we report on the effectiveness of sodium-exchanged Nafion membranes for inhibiting polysulfide crossover during redox flow battery operation. The solubility of polysulfides allows them to be used as a high-capacity catholyte for nonaqueous redox flow batteries (NARFB). The NARFB cathode capacity is controlled by the total tank catholyte volume and polysulfide concentration and, as such, is independent of polysulfide adsorption sites on carbon fibers or nanotubes as found within traditional Na or Li–S batteries. However, one of the major barriers to the realization of polysulfide NARFBs is associated with developing a robust membrane that has minimal polysulfide crossover under the operating conditions. We found that sodium-exchanged Nafion membrane separators effectively inhibit polysulfide crossover within a Na–sulfur NARFB. These membranes significantly improve both capacity retention (70%) and Coulombic efficiencies (99%) after 50 cycles. Commercial porous membranes showed a large crossover as detected by UV–vis spectroscopy and resulted in low capacity retention (20%) and Coulombic efficiency (74%) after 45 cycles. Electrochemical impedance spectroscopy (EIS) measurements highlighted the trade-off between innate reactivity and ionic conduction of the membranes. The results show that dense, single ion conducting Nafion enables a long cycle life; however, it reacts with Na metal to form a resistive passivation layer and increases the cell resistance. On the contrary, the open pore structure of Celgard allows for higher current charge/discharge, and its chemical nature is compatible with Na; however, it has a high degree of polysulfide crossover.

25 ENERGY STORAGE↗
NASA NTRS2003

Structural Basis for Flip-Flop Action of Thiamin Pyrophosphate-Dependent Enzymes Revealed by Human Pyruvate Dehydrogenase

Thiamin pyrophosphate (TPP), the biologically active form of vitamin BI, is a cofactor of enzymes catalyzing reactions involving the cleavage of a carbon-carbon bond adjacent to an oxo group. TPP-dependent enzymes show a common mechanism of TPP activation by: (1) forming the ionic N-H...O(sup -) hydrogen bonding between the N1' atom of the aminopirymidine ring of the coenzyme and intrinsic gamma-carboxylate group of glutamate and (2) imposing an "active" V-conformation that brings the N4' atom of the aminopirymidine to the distance required for the intramolecular C-H.. .N hydrogen bonding with the thiazolium C2 atom. Within these two hydrogen bonds that rapidly exchange protons, protonation of the N1' atom is strictly coordinated with the deprotonation of the 4' -amino group and eventually abstraction of the proton from C2. The human pyruvate dehydrogenase Elp, component of human pyruvate dehydrogenase complex, catalyzes the irreversible decarboxylation of the pyruvate followed by the reductive acetylation of the lipoyl group of dihydrolipoyl acyltransferase. Elp is alpha(sub 2)beta(sub2)-heterotetrameric with a molecular mass of I54 kDa, which has two catalytic sites, each providing TPP and magnesium ion as cofactors and each formed on the interface between the PP and PYR domains. The dynamic nonequivalence of two otherwise chemically equivalent catalytic sites has been observed and the flip-flop mechanism was suggested, according to which two active sites affect each other and in which different steps of the catalytic reaction are performed in each of the sites at any given moment. Based on specific futures of human pyruvate dehydrogenase including rigid and flexible connections between domains that bind the cofactor we propose a mechanistic model for the flip-flop action of this enzyme. We postulate that the dynamic protein environment drives the exchange of tautomers in the 4' -aminopyrimidine ring of the cofactor through a concerted shuttl-like motion of tightly connected domains. The dynamic exchange of those tautomers, in turns, is required during the reactions of pyruvate decarboxylation and reductive acetylation of lipoamide. Thus the shuttle-like motion of the domains is coordinated with the reactions of decarboxylation and acetylation, which are carried out in each of the cofactor sites resulting in a flip-flop action of the enzyme. The structure-derived mechanism of action of human pyruvate dehydrogenase may be likely common for other TPP-dependent enzymes.

Dominiak, Paulina↗