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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 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Integrated three-dimensional characterization of reactive phase formation and coarsening during isothermal annealing of metastable Zn–3Mg–4Al eutectic

Microstructural instabilities associated with a metastable lamellar eutectic when exposed to an elevated temperature were analyzed in a Zn-3Mg-4Al alloy as a model system. X-ray diffraction and scanning electron microscopy showed that annealing at a temperature 43 K below the equilibrium eutectic temperature converted the metastable ternary MgZn 2 /η-Zn/β-ZnAl eutectic to a stable mixture of Mg 2 Zn 11 /η-Zn/α-Al. 3D EBSD suggested that supersaturation of η-Zn with Mg and Al eased difficulties in nucleation of Mg 2 Zn 11 and α-Al at the MgZn 2 /η-Zn phase interfaces. Quasi-in-situ X-ray nanotomography revealed that a reactive diffusion process prevailed in an early stage of annealing leading to rapid consumption of MgZn 2 for growth of Mg 2 Zn 11 and concomitant thinning and pinch-off of η-Zn lamellae. The reactive diffusion process also brought about significant and quantifiable changes in the topological characteristics of the η-Zn phase at remarkably shorter time scales compared to Rayleigh instability and Ostwald ripening mechanisms. Overall, the present results provide fresh insights on the short-term annealing effects on metastable eutectics, with relevance to structural evolution in additive manufacturing.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Room temperature sodium diffusion in sodium iron phosphate investigated with neutron scattering

Sodium iron phosphate, Na x FePO 4 , is currently one of the most promising cathode materials for sodium ion batteries. Here we employ a systematic approach using three neutron scattering techniques to investigate temperature dependent properties with a focus on the charge transfer processes. Two distinct Na + diffusive motions are observed with quasielastic neutron scattering, including room temperature motion. These processes correspond to rapid double jumps through extrinsic vacancy sites of ∼6 Å along with the more fundamental nearest neighbor jumps of 3.1 Å. Experimental observations of room temperature ionic diffusion are highly desirable, as the diffusion pathways are naturally well suited for efficient transport. Inelastic neutron scattering was used to probe the vibrational density of states that assist in the ionic and electronic (polaronic) transport processes, which are further supported with density functional theory. Neutron diffraction examines the disordering of the sodium sublattice upon transition to the solid-solution phase, which is believed to enhance the overall kinetics during sodium insertion/extraction. Finally, 57 Fe Mössbauer spectroscopy measurements probes polaron hopping and the local structural evolution that modifies the electron density surrounding the redox active iron sites. This study sheds light on the temperature induced atomic scale dynamics that occur in olivine Na x FePO 4 .

Novak, Eric [Swarthmore College, Swarthmore, PA (U↗
DOE OSTI2020

Size effect on the growth and pulverization behavior of Si nanodomains in SiO anode

Silicon monoxide (SiO) as a promising silicon-based anode electrode of lithium-ion batteries (LIBs) has been the subject of many recent investigations. However, the complex microstructural features of SiO hinder attempts to link the microstructure changes in SiO with its electrochemical performances upon electrochemical cycling. This study employs X-ray pair distribution function (PDF), with a high-resolution transmission electron microscope (HRTEM), to investigate the microstructure of Si nanodomains in SiO and its structural evolution over the electrochemical cycling process. The experiment results reveal the size evolution of Si nanodomains in SiO during the electrochemical cycling and find it highly dependent on the initial Si domain size in SiO. If the initial Si domain size is too large, the average size of Si nanodomains would increase at first and then decrease after a certain number of cycles, which indicates the pulverization of Si domains after the electrochemical-driven growth of Si nanodomains reaches a critical point. Furthermore, these results suggest that an optimal initial Si nanodomain size of 4-6 nm for SiO anode materials is essential to retard the growth and subsequent pulverization process of Si nanodomains and thus to improve the cyclability of SiO during long-term cycling.

25 ENERGY STORAGE↗
DOE OSTI2020

On the irreversible sodiation of tin disulfide

Tin disulfide is considered as a promising electrode material for sodium-ion batteries because of its two-dimensional layered structural characteristics allowing the intercalation of Na ions. Understanding the underlying reaction mechanisms and the decisive step of the reaction reversibility is critical for its applications. Herein, we investigate the sodiation and desodiation processes of SnS 2 by employing in situ transmission electron microscopy (TEM). After the initial intercalation reaction, a rock-salt Na y SnS 2 phase with disordering Na and Sn cations is observed, followed with a conversion reaction and an alloying reaction. Additionally, the disordering reaction occurs along <1-10> direction of pristine SnS 2 phase which is correlated with local bonding rearrangements induced by the exchange of Sn and Na cations. In-situ TEM studies and first-principles calculations indicate that the original 2D SnS 2 structure could not be recovered during desodiation. Instead, the disordered Na y SnS 2 phase is finally formed, which indicates that the irreversible disordering transition is the determining step of irreversible cycling. This work probes the structural evolution of sodiation, providing a fundamental understanding of the electrochemical properties of metal sulfides and inspiring rational designs of high performance electrodes for sodium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Dual-pace transient heat conduction in vertically aligned carbon nanotube arrays induced by structure separation

Vertically aligned arrays of carbon nanotubes (CNTs) are attractive for a wide range of macroscopic applications which can exploit the remarkable properties of individual nanotubes. In this work, an abnormal behavior of CNT bundles in heat conduction is discovered under the transient electro-thermal characterization. The measured voltage change over the sample shows a dual-pace thermal response (DTR), which could not be fitted using a single thermal diffusivity heat transfer model. Instead, two thermal diffusivities are determined from the DTR phenomenon. Three rounds of cryogenic experiments are conducted to investigate the physics behind DTR phenomenon. It starts to emerge when the temperature is reduced to a certain level. After two rounds of cryogenic experiments, the DTR phenomenon becomes permanent from 295 K to 10 K. The nano-scale structure separation induced by the increased thermal strain leads to macroscale structure separation, which results in two parallel heat conduction paths responsible for the DTR phenomenon. By building a new parallel heat transfer model taking both the transient and steady-state electrical and thermal response into consideration, the area ratio of separated CNTs is determined. Furthermore, this result uncovers the existence of coiled morphology and nano-structure evolution of CNTs under cryogenic state and its effect on thermal and electrical transport, especially on their transient behaviors. Knowledge of the thermal transport in these CNTs arrays is important considering the fact that transient thermal response strongly affects their mechanical, optical, and electrical behaviors.

42 ENGINEERING↗
DOE OSTI2020

In-situ and In-operando Cobalt Oxidation Studied by Atom Probe Tomography

Heterogeneous catalysis is one of the pillars of the chemical industry and the “green chemistry” concept. However, the sparse understanding of surface mechanisms at molecular scale impedes development of high-performance catalysts and requires development of new tools and methodologies. Cobalt is notably able to dissociate CO 2 into CO(g) and O 2 (g), allowing further conversion to higher value compounds such as long-chain hydrocarbons. Such application leads inevitably to Co surface oxidation. Finally, from its pure form (Co(0)) to oxidized ones (CoO and Co 3 O 4 ) the formation mechanism remains unclear as well as the surface structure evolution and its influence on the chemical reaction.

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

Elucidating the Origins of High Capacity in Iron-Based Conversion Materials: Benefit of Complementary Advanced Characterization toward Mechanistic Understanding

Lithium-ion batteries are recognized as an important electrochemical energy storage technology due to their superior volumetric and gravimetric energy densities. Graphite is widely used as the negative electrode, and its adoption enabled much of the modern portable electronics technology landscape. However, developing markets, such as electric vehicles and grid-scale storage, have increased demands, including higher energy content and a diverse materials supply chain. Alternatives that provide the opportunity to increase capacity and address supply chain concerns are of interest. Understanding the fundamental mechanisms that govern battery function is crucial to driving further improvements in the field. Advanced characterization techniques, such as those enabled by synchrotron light sources and high-resolution electron microscopes, that can uncover these mechanisms have become a necessity for elucidating structural evolution upon electrochemical conversion at the nano- to mesoscales. Performing these experiments with relevant electrochemistry using in situ and operando experiments imparts the ability to identify critical reaction pathways and capture intermediate (dis)charge products not discernible by traditional experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Direct Observation of Electron Beam-Induced Phase Transition in MgCrMnO 4

Irreversible structural transformation in intercalation-type cathode materials, which has been frequently observed, has been perceived as a principal cause of capacity fading and voltage decay in (uni) multivalent batteries. Herein, we explored the electron beam-induced spinel to defective rocksalt phase transitions in MgCrMnO 4 , a potential multivalent cation intercalation cathode, using atomic-resolution imaging and spectroscopy in an aberration-corrected scanning transmission electron microscope. This dynamic electron beam irradiation study of specific structural transformations provides an atomistic understanding of the structural evolution observed in transition-metal oxide spinels during electrochemical cycling using multivalent cations, such as Mg 2+ . By combining an imaging study with first-principles modeling, we demonstrate that the mechanism of the spinel to defective rocksalt transformation in MgCrMnO 4 nanostructures is enabled by the presence of oxygen vacancies and is, therefore, very similar to that observed in transition-metal oxide spinels upon Li intercalation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

First-Principles Modeling of Sodium Ion and Water Intercalation into Titanium Disulfide Interlayers for Water Desalination

Recent experiments revealed the possibility of using titanium disulfide (TiS 2 ) as the cathode material in capacitive deionization (CDI) devices for water desalination. Although it performed stably up to 70 cycles with a salt removal capacity of 14 mg/g (corresponding to a sodium ion removal capacity of 35.8 mg/g) at high molar concentration (600 mM NaCl), the maximum capacity of TiS 2 as a CDI electrode was much lower (~70 mAh/g) than as a supercapacitor (239 mAh/g). Understanding why the ion capacities of these two configurations of the same material differ will entail elucidating detailed charge/discharge mechanisms at the atomic scale. Here, we present density functional theory simulations of sodium intercalation into TiS 2 interlayers in order to gain such understanding. We systematically investigated TiS 2 stacking patterns and ion intercalation sites, energetics of the intercalated compounds, and phase transformation during sodium intercalation. The calculated structural evolution and capacitance–voltage curve agree quite well with previous measurements. We conclude that the different maximum capacities of TiS 2 measured in aqueous and dry environments originate from weaker interlayer interactions with respect to shear strain after ~33% intercalation of Na + –H 2 O pairs, which is detrimental to the mechanical stability of TiS 2 . In conclusion, this study sheds light on the underlying mechanisms of ion intercalation into layered materials and contributes to understanding requirements for future design and optimization of CDI electrode materials for water desalination.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Understanding the Reactions Between Fe and Se Binary Diffusion Couples

Spurred by recent discoveries of high-temperature superconductivity in Fe-Se based materials, the magnetic, electronic, and catalytic properties of iron-chalcogenides have drawn significant attention. Furthermore, much remains to be understood about the sequence of phase formation in these systems. In this work, we shed light on this issue by preparing a series of binary Fe-Se ultrathin diffusion couples via designed thin film precursors and investigating their structural evolution as a function of composition and annealing temperature. Two previously unreported Fe-Se phases crystallized during the deposition process on a nominally room-temperature Si substrate in the 27-33% and 37-47% Fe (atomic percent) composition regimes. Both phases completely decompose after annealing to 200°C in a nitrogen glovebox. At higher temperatures, the sequence of phase formation is governed by Se loss in the annealing process, consistent with what would be expected from the phase diagram. Films rich in Fe (53-59% Fe) crystalized during deposition as β-FeSe (P4/nmm) with preferred c-axis orientation to the amorphous SiO 2 substrate surface, providing a means to non-epitaxial self-assembly of crystallographically aligned, iron-rich β-FeSe for future research. Our findings suggest the crystallization of binary Fe-Se compounds at room temperature via near diffusionless transformations should be a significant consideration in future attempts to prepare metastable ternary and higher order compounds containing Fe and Se.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Hybrid Absorption–Crystallization Strategies for the Direct Air Capture of CO2 Using Phase-Changing Guanidium Bases: Insights from in Operando X-ray Scattering and Infrared Spectroscopy Measurements

Efforts to limit rising concentrations of CO 2 have motivated the development of negative emission technologies. Direct air capture (DAC) of CO 2 is one of the negative emissions technologies that has been proposed for the direct removal of CO 2 from the atmosphere. Phase-changing bis(iminonoguanidine) (BIG) sorbents have been developed for the direct air capture of CO 2 . These phase changing sorbents, specifically glyoxal-bis(iminoguanidine) (GBIG), involve (1) CO 2 absorption with aqueous amino acid salts, such as K- or Na-glycinate to yield bicarbonate-rich solutions, (2) crystallization of the bicarbonate anions with a BIG solid, which regenerates the amino acid, and (3) solid-state CO 2 release from the carbonate crystals and BIG regeneration. Despite the promising potential of these materials, their structural evolution during the thermal regeneration of the BIG solids, chemical regeneration of the sodium or potassium glycinate solvents, and the crystallization behavior of CO 2 -loaded BIG bicarbonate remain to be evaluated and understood in detail. The aim of this study is to probe these knowledge gaps. In situ wide-angle X-ray Scattering (WAXS) results show that CO 2 and water molecules in GBIG bicarbonate are simultaneously released in a single step during the thermal regeneration of the sorbent at 97 – 134 °C. In situ ATR-FTIR measurements showed that sodium glycinate and GBIG bicarbonate are simultaneously generated when GBIG, glycine, and sodium bicarbonate are reacted. The crystallization of GBIG bicarbonate from GBIG and CO 2 -loaded monoethanolamine (MEA) occurs rapidly in the first 10 min of the reaction, as determined using in situ GI-SAXS measurements. Overall, the insights from these studies are essential for the scalable implementation of CO 2 capture technologies using these phase-changing sorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

CoSn-type NiIn1–xSbx (0 ≤ x ≤ 0.17): Site-Selective Substitution, Electronic Structure, Chemical Bonding, and Structural Transformation

CoSn-type intermetallic compounds have emerged as a model platform for Kagome-derived flat-band physics, where subtle chemical perturbations can strongly influence electronic structure and phase stability. Here, we present a combined experimental and theoretical study of Sb-substitution in CoSn-type NiIn1–xSbx (0 ≤ x ≤ 0.17) to elucidate the interplay between site selectivity, solubility limit, chemical bonding, and electronic structure. Rietveld refinements on Neutron powder diffraction data confirmed the selective Sb-substitution at the electron-rich In2 (2d) site forming the honeycomb substructure, while the In1 (1a) site within the Kagome layer remains exclusively occupied by In. Density functional theory (DFT) calculations revealed that pristine CoSn-type NiIn hosts Ni 3d-dominated flat bands near the Fermi level (EF), originating from the Kagome-like Ni substructure. Partial replacement of In by Sb within the honeycomb layer alters these flat-band features below EF, reducing the density of states and suppressing the flat-band topology near the Fermi level. Orbital-resolved electronic structure and chemical-bonding analyses show that Sb-substitution enhances Ni-p-block (In/Sb) covalency and optimizes charge compensation, stabilizing the CoSn-type structure up to the solubility limit x ≈ 0.17. Beyond the limit, the higher-Sb compositions show satellite reflections consistent with an incommensurately modulated phase. These results establish a link between site-selective chemical substitution, bonding optimization, and flat-band electronic structure evolution, providing fundamental insights into how chemical substitution influences the electronic properties of Kagome-based intermetallic compounds.

Roy, Nilanjan [National Institute of Technology Si↗
DOE OSTI2026

Evidence for Photoinduced Polaron Generation in a High Persistence Length Low Bandgap Conjugated Polymer in Solution

Using ultrafast time-resolved infrared (TRIR) spectroscopy, we studied the solution-phase excited-state structural evolution of an indacenodithiophene-co-benzothiadiazole polymer (C8-IDTBT). Following band gap excitation, the TRIR spectra reveal vibrational features that develop within 10 ps and decay over 4 ns. Using pulse radiolysis measurements, charge-modulation spectroscopy, and quantum-chemical calculations, the IR features are assigned to polaron pairs. Interestingly, these features appear on an evolving broad mid-IR electronic absorption background, with kinetics correlating with the formation and decay of the cationradical vibrational bands. A three-state kinetic model successfully reproduces the spectral evolution, revealing that the polaron and exciton populations exist in dynamic equilibrium on picosecond time scales, with time constants for exciton dissociation in the range of 3− 5 ps and polaron-to-exciton reformation between 20 and 100 ps, while both species decay to the ground state on much slower nanosecond time scales (∼1 ns), yielding a remarkably high polaron-generation efficiency, higher than 50%. These findings provide fundamental insights into intramolecular charge photogeneration mechanisms in conjugated polymers, demonstrating efficient bound-polaron formation in isolated polymer chains.

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

Vapor-Phase Intercalation of Cesium into Black Phosphorous

Cesium vapors were charged into black phosphorous (BP) flakes at varied times and at a temperature gradient of 150 °C. The X-ray diffraction (XRD) measurements of these samples suggest a reduction in the strength of van der Waal interactions between BP layers leading to the loss of coherence of out-of-plane peaks. At the same time, the three main Raman modes of BP (A g 1 , B 2 g , and A g 2 ) steadily redshifted as exposure times were increased, with modes B 2 g and A g 2 shifting faster than A g 1 . After initial rapid downshifts of active BP phonon modes, this intercalation strategy showed its limits following prolonged exposure times. Saturation of BP flakes by Cs vapors ensued and the kinetics was fitted with an exponential decay function. Furthermore, the thermoelectric power (TEP) of cesiated BP exhibited an inversion in sign from positive to negative around 400 K, lending credence to the transformation of as-prepared BP which is a p-type semiconductor to an n-type equivalent due to Cs atom intercalation driven shifting of the Fermi level toward the conduction band of BP and the donation of electrons from Cs. Furthermore, density functional theory (DFT) calculations were used to delve deeper into understanding Cs intercalation on the structural evolution of BP.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Spatially Offset Femtosecond Stimulated Raman Spectroscopy: Observing Exciton Transport through a Vibrational Lens

To design better molecular electronic devices, we need a strong understanding of how charges or excitons propagate, as many efficiency losses arise during transport. Exciton transport has been difficult to study because excitons tend to be short-lived, have short diffusion lengths, and can easily recombine. Here, we debut spatially offset femtosecond stimulated Raman spectroscopy (SO-FSRS), a three-pulse ultrafast microscopy technique. By offsetting the photoexcitation beam, we can monitor Raman spectral changes as a function of both time and position. We used SO-FSRS on 6,13-bis(triisopropylsilylethynyl) pentacene, a well-studied organic semiconductor used in photovoltaics and field-effect transistors. Furthermore, we demonstrated that the fast exciton and free charge carrier transport axes are identical and observed that exciton transport is less anisotropic by a factor of ~3. SO-FSRS is the first technique that directly tracks molecular structural evolution during exciton transport, which can provide roadmaps for tailor-making molecules for specific electronic devices.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2026

Electron–Ion Covariance Reveals Geometry-Resolved Inner-Shell Spectra in CS 2 Photodissociation

The chemical shifts of inner-shell atomic orbitals are highly sensitive to chemical bonding and molecular structure. In evolving systems, however, the spectra of distinct molecular species and geometries overlap, obscuring the underlying chemical dynamics. Here we demonstrate the use of electron–ion covariance analysis to combine the structural sensitivity of Coulomb explosion imaging with inner-shell spectroscopy, yielding geometry-specific spectra of transient and product species. We apply this approach to the excited state dynamics of CS 2 probed by ionization above the S 2p edge. Electron–ion covariance with time- and momentum-selected S + and S 2+ ions isolates distinct S 2p photoelectron spectra for ground-state CS 2 , bent photoexcited CS 2 , the CS photoproduct, and bare atomic sulfur ─ species whose spectra overlap strongly in the channel-averaged measurement. Clear chemical shifts are observed in the covariance photoelectron spectrum for each of these species, all of which are consistent with high-level calculations. Here, by extracting the atomic S contribution to the photoelectron spectrum in a finely time-resolved manner we can disentangle this contribution to the overall time-resolved photoelectron spectrum as the photodissociation proceeds. These results demonstrate the promise of electron–ion covariance as a general approach to geometry-resolved inner-shell spectroscopy, opening a route to tracking structural evolution through chemical shifts in complex photoexcited molecules.

Ionization↗
DOE OSTI2022

Operando Nanoscale Imaging of Electrochemically Induced Strain in a Locally Polarized Pt Grain

Developing new methods that reveal the structure of electrode materials under polarization is key to constructing robust structure-property relationships. However, many existing methods lack the spatial resolution in structural changes and fidelity to electrochemical operating conditions that are needed to probe catalytically relevant structures. Here, we combine a nanopipette electrochemical cell with three-dimensional X-ray Bragg coherent diffractive imaging to study how strain in a single Pt grain evolves in response to applied potential. During polarization, marked changes in surface strain arise from the Coulombic attraction between the surface charge on the electrode and the electrolyte ions in the electrochemical double layers, while the strain in the bulk of the crystal remains unchanged. The concurrent surface redox reactions have a strong influence on the magnitude and nature of the strain changes under polarization. In conclusion, our studies provide a powerful blueprint to understand how structural evolution influences electrochemical performance at the nanoscale.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Multinonmetal-Doped V 2 O 5 Nanocomposites for Lithium-Ion Battery Cathodes

Lithium-ion batteries (LIBs) are critical for portable electronics and electric vehicles, demanding higher energy density to meet increasing energy storage needs. Current commercial cathode materials, such as LiFePO 4 and LiCoO 2 , are limited by a single electron transfer, restricting their energy density. Vanadium pentoxide (V 2 O 5 ) emerges as a promising high-capacity cathode due to its high theoretical capacity of 443 mA h g –1 with three Li storage capacities, significantly surpassing conventional materials. However, the practical application of V 2 O 5 is hindered by a large structural evolution and rapid capacity fading during full lithium intercalation. Here, this study introduces a multinonmetal doping (MNM) strategy to enhance V 2 O 5 cathodes by incorporating all-nonmetal dopants (B, P, and Si) and graphene (G). MNM-V 2 O 5 -G exhibits increased surface oxygen defects, improving charge transfer kinetics and thus enhancing the rate performance and cycling stability. Our results provide valuable insights into the role of surface oxygen defects in stabilizing V 2 O 5 with element doping. This research highlights the potential of multinonmetal doping to improve LIB cathode materials, offering a promising pathway for design of high-energy-density V 2 O 5 cathodes and advancing the development of next-generation energy storage solutions.

25 ENERGY STORAGE↗