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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

High Li + Transference Number Electrolyte Enabled by Fluoride Acceptor for Low-Temperature Li-Ion Batteries

To enable wide-temperature operation of lithium-ion batteries (LIBs), new electrolyte formulations have been developed to enhance the performance, particularly at low temperatures. A key challenge lies in achieving both high ionic conductivity and a high lithium-ion transference number due to their inherent trade-off. In this study, we designed an electrolyte system comprising tris(pentafluorophenyl)borane (TPFPB), a fluoride acceptor, and LiF salt in ethylene carbonate (EC)-free solvents. TPFPB, with its electron-deficient boron center, facilitates fluoride transfer reactions that promote the dissociation of otherwise insoluble LiF. When methyl acetate (MA) was used as the solvent, the electrolyte exhibited a high transference number (t Li + = 0.85) and ionic conductivity (σ = 5.0 × 10 –3 S cm –1 ). The optimized electrolyte demonstrated excellent performance at −20 °C, with no evidence of lithium plating. This work presents a new strategy for electrolyte design by leveraging cation desolvation to achieve high-performance LIBs for low-temperature and high-power applications.

anions↗
DOE OSTI2025

Molecular Insights into Geochemical Reactions of Iron-Bearing Minerals: Implications for Hydrogen Geo-Storage

Here, this study investigates the reaction of hydrogen (H 2 ) with pyrite (FeS 2 ), focusing on how temperature and the presence of water influence the reaction pathways and kinetics. Utilizing computational molecular simulations and kinetic analyses, we explore the impact of these factors on the formation of hydrogen sulfide (H 2 S) and related species. First, grand canonical Monte Carlo/molecular dynamics (GCMC/MD) simulations reveal that physical H 2 adsorption occurs in distinct layers on the pyrite surface. In addition, increased temperatures reduce the absolute adsorption capacities. Reactive MD simulations demonstrate that H 2 interacts differently with pyrite under varying conditions. At 298 K, H 2 reacts with pyrite to form HS – , leading to the formation of HS – through covalent bonding with sulfur of pyrite. However, no H 2 S is produced at this temperature, suggesting that a kinetic barrier (i.e., activation energy) may prevent this reaction. At higher temperatures, H 2 S production significantly increases. The presence of water introduces additional complexity to the reaction mechanism. Unlike dry conditions, water enhances H 2 S generation, even at low temperatures. Water also facilitates the formation of additional products, such as SOH, indicating a more intricate chemical environment on the pyrite surface. Our findings identify the association of HS – ions to form H 2 S as the rate-limiting step, with temperature influencing this process. This finding suggests that while the presence of water can create a more dynamic reaction environment, the overall mechanisms leading to H 2 S formation remain consistent. These outcomes suggest the need for developing targeted strategies to manage and control H 2 S emissions within the context of underground hydrogen storage.

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

Modeling the electrochemical behavior and interfacial junction profiles of bipolar membranes at solar flux relevant operating current densities

A 1-dimensional, multi-physics model that accounts for the migration and diffusion of solution species, electrostatics, and chemical reactions, in particular water dissociation (WD), at bipolar membrane (BPM) interfaces was developed to study the electrochemical behavior of bipolar membranes (BPMs) at solar flux relevant operating current densities (tens of mA cm -2 ). Significant partial current densities for WD were observed at BPM voltages much less than the equilibrium voltage, e.g., 59 mV × ΔpH from both experiments and modeling. The co-ion leakage across the BPM at pH differentials accounted for the early presence of the partial current density for WD. Two distinctive electric field dependent WD pathways, the un-catalyzed pathway and the catalyzed pathway, were quantitatively and parametrically studied to improve the turn-on potential of the BPM. The catalyzed pathway accounted for the majority of the partial current density for WD at low voltages, while the un-catalyzed pathway dominated the WD at relatively high voltages. Significant WD was observed only within the interfacial CL (<5 nm), in which a large electric field was present. To improve the electrochemical behavior and the turn-on potential of BPMs, the impacts of the pKa of the immobilized WD catalysts, the electric-field dependent rate constant, the thickness of the catalyst layer and fixed charge density in BPMs on the partial current densities for WD were studied systematically. In addition, the electrochemical behavior and concentration profiles of BPMs in a buffered electrolyte were studied and contrasted with those in an un-buffered electrolyte from both modeling and experiments.

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

Structural water in amorphous carbonate minerals: ab initio molecular dynamics simulations of X-ray pair distribution experiments

Water is known to play a controlling role in directing mineralization pathways and stabilizing metastable amorphous intermediates in hydrous carbonate mineral MCO 3 ·nH 2 O systems, where M 2+ is a divalent metal cation. Despite this recognition, the nature of the controls on crystallization is poorly understood, largely owing to the difficulty in characterizing the dynamically disordered structures of amorphous intermediates at the atomic scale. Here, we present a series of atomistic models, derived from ab initio molecular dynamics simulation, across a range of experimentally relevant cations (M = Ca, Mg, Sr) and hydration levels (0 ≤ n ≤ 2). Theoretical simulations of the dependence of the X-ray pair distribution function on the hydration level n show good agreement with available experimental data and thus provide further evidence for a lack of significant nanoscale structure in amorphous carbonates. Upon dehydration, the metal coordination number does not change significantly, but the relative extent of water dissociation increases, indicating that a thermodynamic driving force exists for water dissociation to accompany dehydration. Mg strongly favors monodentate conformation of carbonate ligands and shows a marked preference to exchange monodentate carbonate O for water O upon hydration, whereas Ca and Sr exchange mono- and bidentate carbonate ligands with comparable frequency. Finally, water forms an extensive hydrogen bond network among both water and carbonate groups that exhibits frequent proton transfers for all three cations considered suggesting that proton mobility is likely predominantly due to water dissociation and proton transfer reactions rather than molecular water diffusion.

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

Can Third-Body Stabilization of Bimolecular Collision Complexes in Cold Molecular Clouds Happen?

For more than half a century, networks of radiative association, dissociative recombination, and bimolecular reactions have been postulated to drive the low-temperature chemistry of cold molecular clouds. Third-body stabilizations of collision complexes have been assumed to be 'irrelevant' due to short lifetime of such complexes. Here, we conduct crossed molecular beam studies of ground state atomic silicon with diacetylene in combination with electronic structure calculations and microcanonical kinetics models operating under cold molecular cloud conditions. Our combined experimental, electronic structure, and microcanonical kinetics modelling investigations provide compelling evidence that three-body collisions of molecular hydrogen with long-lived reaction intermediates accessed through intersystem crossing are prevalent deep inside molecular clouds. This concept might be exportable to reactions involving polycyclic aromatic hydrocarbons thus affording a versatile machinery to complex organics via third-body stabilizations of bimolecular collision complexes deep inside cold molecular clouds.

astrochemistry↗
DOE OSTI2020

Atomic-Scale Dynamic Interaction of H 2 O Molecules with Cu Surface

Atomic-scale interaction of water vapor with metal surfaces beyond surface adsorption under technologically relevant conditions remains mostly unexplored. Using aberration-corrected environmental transmission electron microscopy, we reveal the dynamic surface activation of Cu by H 2 O at elevated temperature and pressure. In this study, we find a structural transition from flat to corrugated surface for the Cu(011) under low water-vapor pressure. Increasing the water-vapor pressure leads to the surface reaction of Cu with dissociated H 2 O, resulting in the formation of a metastable “bilayer” Cu-O-H phase. Corroborated by density functional theory and ab initio molecular dynamics calculations, the cooperative O and OH interaction with Cu is responsible for the formation and subsurface propagation of this phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1972

The diurnal heat budget of the thermosphere

Detailed numerical calculations of thermospheric heat sources and sinks are presented and their relative importance is discussed in reference to the energy balance phenomena of the neutral atmosphere. It is shown that the thermal energy available from the absorption in the Schumann-Runge continuum leading to photodissociation of O2 is by far the largest energy source in the lower thermosphere. Other sources of varying importance in different altitude ranges are: (1) energy from photoelectrons, (2) energy exchange from thermal plasma, (3) chemical reactions (ion-electron dissociative recombination) energy gain, and (4) kinetic and dissipative energy associated with the neutral wind. The energy sinks of importance are thermal conduction at the lower boundary (120 km) and radiative cooling of atomic oxygen. It is shown that the combined energy from processes 2 to 4 constitute only a small fraction of the total energy available from photoelectrons and are in phase with the latter. It is suggested that a choice of a lower boundary much below 120 km, e.g. near the mesopause level (90 km), should be more appropriate for general thermospheric studies.

Chandra, S.↗
NASA NTRS1975

Hydrogen chemistry - Perspective on experiment and theory

A review is presented of the advantages and limitations of various experimental methods for the investigation of the kinetics of hydrogen chemistry, including classic thermal and photochemical methods and the crossed molecular beam method. Special attention is given to the flash photolysis-resonance fluorescence apparatus developed by Braun et al, in which repetitive vacuum UV flashes result in the photolytic generation of the desired species, and to the discharge-flow technique. The use of various theoretical methods for the selection or elimination of kinetic data is considered in a brief discussion of the rate theory of two-body encounters and recombination-dissociation processes in neutral reactions. Recent kinetic studies of a series of OH reactions and of a major loss process for odd H in the stratosphere are summarized.

Kaufman, F.↗
NASA NTRS1975

OGO-6 observations of 5577 A

A brief review is given of the data obtained by the horizon-scanning 5577-A airglow photometer flown aboard OGO 6. Data are presented which show the contributions to the 5577-A emission from the F-1 region and the Chapman airglow layer. Emission rates are calculated for both regions on the basis of the dissociative-recombination and Chapman reactions, and the atomic oxygen density and downward flux are inferred from the emission rates and several assumptions concerning the temperature dependence of the rate constants. Latitude variations in the emission rates are discussed along with variations in the altitude of the 5577-A airglow. It is shown that there is a large semiannual variation in the average effective transport properties of the lower thermosphere, that the atomic oxygen profiles near 110 km suggest a maximum in eddy diffusion at about that altitude, and that systematic variations in the altitude of the atomic oxygen maximum probably do not exceed 2 km.

Donahue, T. M.↗
NASA NTRS1976

Effects of atomic oxygen on graphite ablation

It is shown that a previously derived semiempirical equation for describing observed ablation rates of isotropic graphites cannot be applied to low-density flows containing dissociated oxygen. Experimentally determined reaction probabilities of isotropic graphites to molecular and atomic oxygen are used to calculate heat-transfer rates and stagnation-point ablation rates for typical conditions. Integrated mass losses are computed for a group of flight trajectories which start from geosynchronous orbit and enter earth's atmosphere in a skipping motion following near-elliptic decaying orbits. A comparison of the results with those obtained by the equation under question shows excellent agreement for steep trajectories, but large discrepancies for shallow trajectories. The differences are attributed to surface oxidation by atomic oxygen.

Park, C.↗
NASA NTRS1991

Monte Carlo analysis of dissociation and recombination behind strong shock waves in nitrogen

Computations are presented for the relaxation zone behind strong, 1D shock waves in nitrogen. The analysis is performed with the direct simulation Monte Carlo method (DSMC). The DSMC code is vectorized for efficient use on a supercomputer. The code simulates translational, rotational and vibrational energy exchange and dissociative and recombinative chemical reactions. A model is proposed for the treatment of three body-recombination collisions in the DSMC technique which usually simulates binary collision events. The model improves previous models because it can be employed with a large range of chemical-rate data, does not introduce into the flow field troublesome pairs of atoms which may recombine upon further collision (pseudoparticles) and is compatible with the vectorized code. The computational results are compared with existing experimental data. It is shown that the derivation of chemical-rate coefficients must account for the degree of vibrational nonequilibrium in the flow. A nonequilibrium-chemistry model is employed together with equilibrium-rate data to compute the flow in several different nitrogen shock waves.

Boyd, I. D.↗
NASA NTRS2017

Development of a Detailed Surface Chemistry Framework in DSMC

Many of the current direct simulation Monte Carlo (DSMC) codes still employ only simple surface catalysis models. These include only basic mechanisms such as dissociation, recombination, and exchange reactions, without any provision for adsorption and finite rate kinetics. Incorporating finite rate chemistry at the surface is increasingly becoming a necessity for various applications such as high speed re-entry flows over thermal protection systems (TPS), micro-electro-mechanical systems (MEMS), surface catalysis, etc. In the recent years, relatively few works have examined finite-rate surface reaction modeling using the DSMC method.In this work, a generalized finite-rate surface chemistry framework incorporating a comprehensive list of reaction mechanisms is developed and implemented into the DSMC solver SPARTA. The various mechanisms include adsorption, desorption, Langmuir-Hinshelwood (LH), Eley-Rideal (ER), Collision Induced (CI), condensation, sublimation, etc. The approach is to stochastically model the various competing reactions occurring on a set of active sites. Both gas-surface (e.g., ER, CI) and pure-surface (e.g., LH, desorption) reaction mechanisms are incorporated. The reaction mechanisms could also be catalytic or surface altering based on the participation of the bulk-phase species (e.g., bulk carbon atoms). Marschall and MacLean developed a general formulation in which multiple phases and surface sites are used and we adopt a similar convention in the current work. Microscopic parameters of reaction probabilities (for gas-surface reactions) and frequencies (for pure-surface reactions) that are require for DSMC are computed from the surface properties and macroscopic parameters such as rate constants, sticking coefficients, etc. The energy and angular distributions of the products are decided based on the reaction type and input parameters. Thus, the user has the capability to model various surface reactions via user-specified reaction rate constants, surface properties and parameters.

Gas↗
NASA NTRS1977

The structure of cometary ionospheres. II - CO-rich comets

The structure of the ionosphere of a CO-rich comet is computed using two different models. The first one, the photochemical model, assumes that the dissociation and ionization of cometary neutrals and ions are due to photoionization, and photodissociation by solar UV radiation together with dissociative recombinations and ion-neutral reactions. The second one, the internal source model, also incorporates the ionization and dissociation effects of an electric current discharging through the inner coma. The generation of this current has been discussed in earlier papers. It is concluded that the internal source model can explain qualitatively the basic morphology of the ionospheres of CO-rich comets such as Humason (1962, VIII) and Morehouse (1908, III), whereas the photochemical model cannot. The main aim of this paper is not so much to provide accurate numerical estimates as to draw attention to a process which may very well dominate the structures of cometary ionospheres.

Ip, W.-H.↗
NASA NTRS1981

Photochemistry of acetylene at 1470 A

The considered study was conducted to assess the importance of the major primary photochemical process of acetylene at 1470 A, to clarify the role of the metastable excited state, and to obtain information on the rates of C2H reactions with H2 and CH4. Concerning the photodissociation process of acetylene, it was found that at acetylene pressures below 0.8 Torr the direct dissociation process (C2H2 yields C2H + H) is the most important primary photochemical process with a quantum yield of 0.3. Another primary process may be the production of H2 with a quantum yield of approximately 0.1 (C2H2 yields C2 + H2). At acetylene pressures above 0.8 Torr diacetylene is formed by the direct dissociation process followed by the reaction: C2H + C2H2 yields C4H2 + H. At pressures above 20 Torr benzene becomes an important product with a concomitant decrease of diacetylene. The role of acetylene in the photochemistry of the Jovian atmosphere is also considered

Okabe, H.↗
NASA NTRS1976

Photocatalytic generation of hydrogen from water

A concept designed to overcome the problems encountered when using photodissociation for the generation of hydrogen is discussed. The problems limiting the efficiency of photodissociation of water are the separation of the photolysis products and the high energy photons necessary for the reaction. It is shown that the dissociation energy of a large number of molecules is catalytically reduced when these molecules are in intimate contact with the surface of certain metals. It is proposed to develop a surface which will take advantage of this catalytic shift in dissociation energies to reduce the photon energy required to produce hydrogen. This same catalytic surface can be used to separate the reaction products if it is made so that one of the dissociations products is soluble in the metal and others are not. This condition is met by many metal systems such as platinum group metals which have been used commercially to separate hydrogen from other gases and liquids.

Bottoms, W. R.↗