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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
NASA NTRS2016

12Cao-7Al2o3 Electride Hollow Cathode

The use of the electride form of 12CaO-7Al.sub.2O.sub.3, or C12A7, as a low work function electron emitter in a hollow cathode discharge apparatus is described. No heater is required to initiate operation of the present cathode, as is necessary for traditional hollow cathode devices. Because C12A7 has a fully oxidized lattice structure, exposure to oxygen does not degrade the electride. The electride was surrounded by a graphite liner since it was found that the C12A7 electride converts to it's eutectic (CA+C3A) form when heated (through natural hollow cathode operation) in a metal tube.

Rand, Lauren P.↗
NASA NTRS2017

12CaO-7Al2O3 Electride Hollow Cathode

The use of the electride form of 12CaO-7Al2O3, or C12A7, as a low work function electron emitter in a hollow cathode discharge apparatus is described. No heater is required to initiate operation of the present cathode, as is necessary for traditional hollow cathode devices. Because C12A7 has a fully oxidized lattice structure, exposure to oxygen does not degrade the electride. The electride was surrounded by a graphite liner since it was found that the C12A7 electride converts to it's eutectic (CA+C3A) form when heated (through natural hollow cathode operation) in a metal tube.

Rand, Lauren P.↗
DOE OSTI2020

A First–Principles–Based Sub–Lattice Formalism for Predicting Off–Stoichiometry in Materials for Solar Thermochemical Applications: The Example of Ceria

Theoretical models that reliably can predict off-stoichiometry in materials via accurate descriptions of underlying thermodynamics are crucial for energy applications. For example, transition-metal and rare-earth oxides that can tolerate a large number of oxygen vacancies, such as CeO 2 and doped CeO 2 , can split water and carbon dioxide via a two-step, oxide-based solar thermochemical (STC) cycle. The search for new STC materials with a performance superior to that of state-of-the-art CeO 2 can benefit from predictions accurately describing the thermodynamics of oxygen vacancies. The sub-lattice formalism, a common tool used to fit experimental data and build temperature-composition phase diagrams, can be useful in this context. Here, sub-lattice models are derived solely from zero-temperature quantum mechanics calculations to estimate fairly accurate temperature- and oxygen-partial-pressure-dependent off-stoichiometries in CeO 2 and Zr-doped CeO 2 . Physical motivations for deriving some of the “excess” sub-lattice model parameters directly from quantum mechanical calculations, instead of fitting to minimize deviations from experimental and/or theoretical data, are identified. As a result, important limitations and approximations of the approach used are specified and extensions to multi-cation oxides are also suggested to help identify novel candidates for water and carbon dioxide splitting and related applications.

08 HYDROGEN↗
DOE OSTI2025

Atomically Revealing Bulk Point Defect Dynamics in Hydrogen‐Driven γ‐Fe 2 O 3 → Fe 3 O 4 → FeO Transformation

Understanding how point defects in the bulk govern redox transformations is essential for advancing hydrogen-based metal production and designing high-performance oxide materials. This study reveals the atomic-scale mechanisms driving hydrogen-induced reduction of γ-Fe 2 O 3 to Fe 3 O 4 , focusing on how bulk vacancy dynamics dictate structural evolution and reaction kinetics. A key finding is the pronounced contrast in defect behavior between the two oxides: in γ-Fe 2 O 3 , intrinsic Fe vacancies promote oxygen vacancy clustering, destabilizing the local lattice and driving nanopore formation. In contrast, Fe 3 O 4 exhibits a higher oxygen vacancy formation energy and lacks intrinsic Fe vacancies, suppressing vacancy aggregation and maintaining a dense, pore-free structure. This divergence governs distinct reduction pathways—γ-Fe 2 O 3 undergoes an interface-reaction-limited transformation confined to the γ-Fe 2 O 3 /Fe 3 O 4 boundary, while Fe 3 O 4 supports a uniform increase in oxygen vacancy concentration, enabling bulk-phase reduction to lower-oxide FeO. Integrated in situ electron microscopy and density functional theory modeling uncover a vacancy-mediated mechanism, where synergistic cation-anion vacancy dynamics steer microstructure evolution and phase progression. These insights highlight the critical role of vacancy dynamics in controlling oxide reactivity and offer a pathway toward vacancy engineering to enhance reduction kinetics in hydrogen metallurgy and to tailor porosity, reactivity, and structural resilience in oxide-based catalysts and energy materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Asymmetric Lattice Disorder Induced at Oxide Interfaces

Control of order-disorder phase transitions is a fundamental materials science challenge, underpinning the development of energy storage technologies such as solid oxide fuel cells and batteries, ultra-high temperature ceramics, and durable nuclear waste forms. At present, the development of promising complex oxides for these applications is hindered by a poor understanding of how interfaces affect lattice disordering processes and defect transport. Here we explore the evolution of local disorder in ion-irradiated La 2 Ti 2 O 7 /SrTiO 3 thin film heterostructures using a combination of high-resolution scanning transmission electron microscopy (STEM), position-averaged convergent beam electron diffraction (PACBED), electron energy loss spectroscopy (STEM-EELS), and ab initio theory calculations. We observe highly non-uniform lattice disordering driven by asymmetric oxygen vacancy formation across the interface. Our calculations indicate that this asymmetry results from differences in the polyhedral connectivity and vacancy formation energies of the two interface components, suggesting ways to manipulate lattice disorder in functional oxide heterostructures.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2025

Ab initio calculations of the carbon and oxygen isotopes: Energies, correlations, and superfluid pairing

We perform ab initio nuclear lattice calculations of the neutron-rich carbon and oxygen isotopes using high-fidelity chiral interactions. We find good agreement with the observed binding energies and compute correlations associated with each two-nucleon interaction channel. For the isospin T = 1 channels, we show that the dependence on T z provides a measure of the correlations among the extra neutrons in the neutron-rich nuclei. For the spin-singlet S-wave channel, we observe that any paired neutron interacts with the nuclear core as well as its neutron pair partner, while any unpaired neutron interacts primarily with only the nuclear core. For the other partial waves, the correlations among the extra neutrons grow more slowly and smoothly with the number of neutrons. These general patterns are observed in both the carbon and oxygen isotopes and may be universal features that appear in many neutron-rich nuclei.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Sr 2 Fe 2–X Mo X O 6 double perovskites as electrocatalysts for oxidative dehydrogenation of ethane: Effect of B-site stoichiometry

The oxidative dehydrogenation of ethane (ODHE) was investigated using a solid oxide electrocatalytic cell with Sr 2 Fe 2–X Mo X O 6–δ (SFM) double perovskite as the anode electrocatalyst. As shown in the XRD patterns, SFM perovskites maintained their cubic structure upon modifying the B-site ratios of Mo and Fe. Increasing the Mo content of the perovskite structure resulted in a lower water signal intensity at low temperatures in TPR profiles, indicative of moderate oxygen transport through the perovskite structure. Because Mo–O bonds are stronger than Fe–O bonds, the electrical conductivity of SFM perovskites decreased with increasing Mo content. When operated at 100 mA cm –2 , ODHE activity improved four times compared to open circuit voltage, resulting in 16.1% conversion of C 2 H 6 and 83.1% selectivity to C 2 H 4 . It has been demonstrated that oxygen ions provided by perovskite lattices were the key species involved in activating C 2 H 6 based on the in-situ DRIFTS experiments. In conclusion, the SFM perovskite with higher Mo content showed the highest conversion and selectivity due moderate oxygen ion mobility and fast desorption of C 2 H 4 .

25 ENERGY STORAGE↗
DOE OSTI2023

Impact of Dopants on Suppressing Gas Evolution from High-Nickel Layered Oxide Cathodes

Gas release from high-Ni layered-oxide cathodes (LiNi x Mn 1-x-y-z Co y Al z O 2 ; x > 0.8) can jeopardize the overall performance and safety characteristics of the cell. A comprehensive assessment of rational cathode design with common dopants, such as Ni, Co, Al, and Mn, to suppress gas evolution is crucial for battery safety, yet it remains to be conducted. Furthermore, we present an in-situ gas analysis on nine high-Ni cathode materials with online electrochemical mass spectrometry (OEMS). We show that regardless of the dopant, reactive oxygen release from the cathode lattice remains a critical process for gas evolution. A series of comparisons reveals that the intensity and onset point of gas release is strongly dependent on the cathode composition. Notably, Al and Mn are the most effective dopants to suppress gas evolution from the cathode at 4.4 V. We further highlight lattice stability limits, across these nine compositions, between 85 % to 93 % state of charge.

25 ENERGY STORAGE↗
DOE OSTI2022

Mechanistic pathways and role of oxygen in oxidative coupling of methane derived from transient kinetic studies

Oxidative coupling of methane (OCM) is a promising industrial process to upgrade natural gas to high value chemicals. In this study, Temporal Analysis of Products (TAP) and steady-state experiments were conducted to distinguish how the composition of surface and gas phase oxygen influence mechanistic details of the selective conversion of CH 4 to C 2 H 4 over the Mn-Na 2 WO 4 /SiO 2 catalyst. The results from TAP studies indicate that methane activation on this catalyst proceeds predominantly via a short-lived, transient surface oxygen species and there is a competition for this species to form either CO or methyl radicals on the surface. This active species has a total lifetime of 3 s and is identified to have a dioxygen (e.g. O 2 2- or O 2 -) form. We show that the concentration of the transient surface oxygen species significantly impacts the OCM performance. Oxygen attributed to the catalyst lattice (in a singular form e.g., O - ), is found to activate methane to a lesser degree, but exclusively forms CO 2 . Evidence for these surface pathways for methyl radical, CO and CO 2 formation identified by TAP are also validated through steady-state experiments. Finally, by distinguishing different catalyst oxygen species and their role in selective/nonselective pathways, important screening criteria have been identified for the advancement of superior catalyst formulations.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Migration Kinetics of Surface Ions in Oxygen-Deficient Perovskite During Topotactic Transitions

Oxygen diffusivity and surface exchange kinetics underpin the ionic, electronic, and catalytic functionalities of complex multivalent oxides. Towards understanding and controlling the kinetics of oxygen transport in emerging technologies, it is highly desirable to reveal the underlying lattice dynamics and ionic activities related to oxygen variation. In this study, the evolution of oxygen content is identified in real-time during the progress of a topotactic phase transition in La 0.7 Sr 0.3 MnO 3-δ epitaxial thin films, both at the surface and throughout the bulk. Using polarized neutron reflectometry, a quantitative depth profile of the oxygen content gradient is achieved, which, alongside atomic-resolution scanning transmission electron microscopy, uniquely reveals the formation of a novel structural phase near the surface. Surface-sensitive X-ray spectroscopies further confirm a significant change of the electronic structure accompanying the transition. The anisotropic features of this novel phase enable a distinct oxygen diffusion pathway in contrast to conventional observation of oxygen motion at moderate temperatures. The results provide insights furthering the design of solid oxygen ion conductors within the framework of topotactic phase transitions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The role of water vapor during the synthesis of hydrogen doped In 2 O 3

Hydrogen-doped In 2 O 3 synthesized using magnetron sputtering or atomic layer deposition in the presence of water vapor has high transparency in the near infra-red region and mobility values that are almost three to four times of those in commercially used In 2 O 3 :Sn at a much lower carrier concentration. However, simple questions like what happens when water molecules enter In 2 O 3 or why the dominant charge carrier changes from an oxygen vacancy in In 2 O 3 :Sn to H + in In 2 O 3 are not clear. Using hybrid functional based density functional theory calculations, in this study we show that water molecules spontaneously split into H + and OH – . The H + interstitial bonds with an oxygen in In 2 O 3 , and the OH – interstitial occupies a vacant lattice site or is trapped by an oxygen vacancy. Thus, in agreement with experimental findings, our results suggest that the concentration of oxygen vacancies decreases as the partial pressure of water increases. The charge transition level, ϵ ( – / + ) , of a hydrogen interstitial and the Fermi level at which the formation energies of OH – and H + are equal lie above the conduction band minimum, suggesting that the H + interstitial has a lower formation energy. In addition, water molecules do not exhibit any propensity to form clusters, meaning that H + ions can diffuse and remain spatially separated from each other.

36 MATERIALS SCIENCE↗
NASA NTRS1976

Dissolution kinetics of small amounts of oxygen in tantalum alloy T-111 and internal oxide displacement reactions during annealing

Oxygen was added to T-111 (Ta-8W-2Hf, wt. %) at 820 and 990 C at an oxygen pressure of about 0.0003 torr. The technique employed permitted predetermined and reproducible doping of T-111 up to 3.0 at. % oxygen. Based on the temperature dependence of the doping reaction, it is concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the latter oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and of other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high-temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C. The vaporization of WO3 has no apparent affect on the doping reaction.

Stecura, S.↗
NASA NTRS1975

Addition of oxygen to and distribution of oxides in tantalum alloy T-111 at low concentrations

Oxygen was added at 820 and 990 C at an oxygen pressure of about .0003 torr. The technique permitted predetermined and reproducible oxygen doping of the tantalum alloy (T-111). Based on the temperature dependency of the doping reaction, it was concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the tantalum and tungsten oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and oxygen from other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C but not at 820 C. The vaporization of WO3 has no apparent effect on the doping reaction.

Stecura, S.↗
DOE OSTI2025

Direct observation of oxygen vacancy ordering evolution in cerium oxide at varying concentrations via high-resolution transmission electron microscopy

Under illumination by a 300 keV electron beam, oxygen vacancy ordering structures are induced within cerium oxide grains. Here, our high-resolution transmission electron microscopy (HRTEM) study, supported by image simulation, reveals the evolution of these structures as vacancy concentration increases. The observed fluorite-type superlattice structures are identified as CeO 1.825 , CeO 1.75 , Ce 2 O 3 , displaying a gradient in oxygen vacancy concentration moving away from the grain surface. Correspondingly, the structural sequence transitions from Ce 2 O 3 to CeO 1.75 and then to CeO 1.825 . Without the constraints of surrounding grains, fluorite-type Ce 2 O 3 nanocrystals show a preference for transformation into an A-type trigonal structure. Notably, at temperatures up to 200°C, only the perfect fluorite structure is observed. Structural models were validated through both [110] and [001] projections. Our findings further confirm lattice expansion associated with local oxygen vacancy enrichment, which can be compensated by the formation of stacking faults, where a {111} oxygen plane is lost at defect sites.

Cerium oxide↗
DOE OSTI2024

Achieving a high-performance sodium-ion pouch cell by regulating intergrowth structures in a layered oxide cathode with anionic redox

In P2-type layered transition metal (TM) oxides, which are typical cathode materials for Na-ion batteries, the presence of Li within the TM layer could lead to the formation of specific Na–O–Li configurations that trigger additional oxygen redox at high charging voltages. However, the prismatic-type (P-type) to octahedral-type (O-type) phase transition and irreversible TM migration could be simultaneously aggravated in high state of charge, resulting in structural distortion. Here we demonstrate that excessive desodiation of P2-Na 0.67 Li 0.1 Fe 0.37 Mn 0.53 O 2 (NLFMO) induces the formation of neighbouring O-type stacking faults with an intergrowth structure (that is, interlacing of O- and P-type layers), which leads to out-of-lattice Li migration and irreversible oxygen loss. We show that, by controlling the depth of charge to tailor the intergrowth structure, a P-type stacking state can be uniformly interspersed between the O-type stacking state, thereby avoiding neighbouring O-type stacking faults. Adjusting the O/P intergrowth structure leads to both reversible migration of Li/TM ions and reversible anionic redox in the NLFMO cathode. In conclusion, we thereby achieve a high-performance pouch cell (with an energy density of 165 W h kg −1 based on the entire weight of the cell) with both cationic and anionic redox activities.

25 ENERGY STORAGE↗
DOE OSTI2024

Tailored (La 0.2 Pr 0.2 Nd 0.2 Tb 0.2 Dy 0.2 ) 2 Ce 2 O 7 as a Highly Active and Stable Nanocatalyst for the Oxygen Evolution Reaction

Abstract Designing highly active and robust catalysts for the oxygen evolution reaction is key to improving the overall efficiency of the water splitting reaction. It has been previously demonstrated that evaporation induced self‐assembly (EISA) can be used to synthesize highly porous and high surface area cerate‐based fluorite nanocatalysts, and that substitution of Ce with 50% rare earth (RE) cations significantly improves electrocatalyst activity. Herein, the defect structure of the best performing nanocatalyst in the series are further explored, Nd 2 Ce 2 O 7 , with a combination of neutron diffraction and neutron pair distribution function analysis. It is found that Nd 3 + cation substitution for Ce in the CeO 2 fluorite lattice introduces higher levels of oxygen Frenkel defects and induces a partially reduced RE 1.5 Ce 1.5 O 5 +x phase with oxygen vacancy ordering. Significantly, it is demonstrated that the concentration of oxygen Frenkel defects and improved electrocatalytic activity can be further enhanced by increasing the compositional complexity (number of RE cations involved) in the substitution. The resulting novel compositionally‐complex fluorite– (La 0.2 Pr 0.2 Nd 0.2 Tb 0.2 Dy 0.2 ) 2 Ce 2 O 7 is shown to display a low OER overpotential of 210 mV at a current density of 10 mAcm −2 in 1M KOH, and excellent cycling stability. It is suggested that increasing the compositional complexity of fluorite nanocatalysts expands the ability to tailor catalyst design.

Chemistry↗
DOE OSTI2021

Real-Time Identification of Oxygen Vacancy Centers in LiNbO 3 and SrTiO 3 during Irradiation with High Energy Particles

Oxygen vacancies are known to play a central role in the optoelectronic properties of oxide perovskites. A detailed description of the exact mechanisms by which oxygen vacancies govern such properties, however, is still quite incomplete. The unambiguous identification of oxygen vacancies has been a subject of intense discussion. Interest in oxygen vacancies is not purely academic. Precise control of oxygen vacancies has potential technological benefits in optoelectronic devices. In this review paper, we focus our attention on the generation of oxygen vacancies by irradiation with high energy particles. Irradiation constitutes an efficient and reliable strategy to introduce, monitor, and characterize oxygen vacancies. Unfortunately, this technique has been underexploited despite its demonstrated advantages. This review revisits the main experimental results that have been obtained for oxygen vacancy centers (a) under high energy electron irradiation (100 keV–1 MeV) in LiNbO 3 , and (b) during irradiation with high-energy heavy (1–20 MeV) ions in SrTiO 3 . In both cases, the experiments have used real-time and in situ optical detection. Moreover, the present paper discusses the obtained results in relation to present knowledge from both the experimental and theoretical perspectives. Our view is that a consistent picture is now emerging on the structure and relevant optical features (absorption and emission spectra) of these centers. One key aspect of the topic pertains to the generation of self-trapped electrons as small polarons by irradiation of the crystal lattice and their stabilization by oxygen vacancies. What has been learned by observing the interplay between polarons and vacancies has inspired new models for color centers in dielectric crystals, models which represent an advancement from the early models of color centers in alkali halides and simple oxides. The topic discussed in this review is particularly useful to better understand the complex effects of different types of radiation on the defect structure of those materials, therefore providing relevant clues for nuclear engineering applications.

36 MATERIALS SCIENCE↗