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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
DOE OSTI2023

Precise Tailoring of Lithium-Ion Transport for Ultralong-Cycling Dendrite-Free All-Solid-State Lithium Metal Batteries

All-solid-state lithium metal batteries can address crucial challenges regarding insufficient battery cycling life and energy density. The demonstration of long-cycling dendrite-free all-solid-state lithium metal batteries requires precise tailoring of lithium-ion transport of solid-state electrolytes (SSEs). Here, in this work, a proof of concept is reported for precise tailoring of lithium-ion transport of a halide SSE, Li 3 InCl 6 , including intragranular (within grains) but also intergranular (between grains) lithium-ion transport. Lithium-ion migration tailoring mechanism in crystals is developed by unexpected enhanced Li, In, and Cl vacancy populations and lower energy barrier for hopping. The lithium-ion transport tailoring mechanism between the grains is determined by the elimination of voids between grains and the formation of unexpected supersonic conducting grain boundaries, boosting the lithium dendrite suppression ability of SSE. Due to boosted lithium-ion conduction and dendrite-suppression ability, the all-solid-state lithium metal batteries coupled with Ni-rich LiNi 0.83 Co 0.12 Mn 0.05 O 2 cathodes and lithium metal anodes demonstrate breakthroughs in electrochemical performance by achieving extremely long cycling life at a high current density of 0.5 C (2000 cycles, 93.7% capacity retention). This concept of precise tailoring of lithium-ion transport provides a cost, time, and energy efficient solution to conquer the remaining challenges in all-solid-state lithium-metal batteries for fast developing electric vehicle markets.

25 ENERGY STORAGE↗
DOE OSTI2024

Li Stripping Behavior of Anode‐Free Solid‐State Batteries Under Intermittent‐Current Discharge Conditions

Anode‐free manufacturing holds promise to enable high energy densities and lower Lithium (Li)‐metal solid‐state batteries (LMSSBs). Nevertheless, in contrast to thick Li foil (>50 µm), the stripping capacity of in situ‐formed Li (10–30 µm) is limited due to diminished creep flow, resulting in reduced accessible capacity. This study explores the correlation between stripping capacity and surface roughness of garnet Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte. The results reveal that stripping capacity can be enhanced through the surface modification of solid electrolytes. Additionally, this study scrutinizes the stripping behavior of in situ Li under intermittent‐current discharge conditions, which are more relevant to the operational conditions of electric vehicles (EVs). It is demonstrated that, when compared to constant‐current stripping, intermittent‐current stripping effectively suppresses void formation and enhances the stripping capacity of in situ Li by 40%. It is considered that the intermittent current inhibits the accumulation of Li vacancies, thereby delaying the void formation. These findings provide valuable insights into the development of high‐performance anode‐free LMSSBs for EVs.

25 ENERGY STORAGE↗
DOE OSTI2025

Be₂C as a neutron moderator for molten salt reactors: A first-principles study of structural, electronic, and defect properties

Beryllium carbide (Be 2 C), valued for its high neutron moderation efficiency and low absorption cross section, is a promising high-temperature neutron moderator for molten salt reactors. Its practical adoption, however, demands significant technological maturation, requiring comprehensive theoretical and experimental studies of its response to different conditions, including high temperature and irradiation. Here, we report initial results on the fundamental properties and radiation-induced defects of Be 2 C, focusing on antisites, vacancies, interstitial atoms, and Frenkel pairs in the Be and C sublattices. Using density functional theory (DFT) and ab initio molecular dynamics (AIMD), we calculate the defects formation and binding energies, evaluating their dependence on the supercell size, charge states, and chemical environment. In general, carbon defects exhibit higher formation energies, greater sensitivity to cell size, and stronger impacts on the density of states compared to beryllium defects, with charged state the effects being more pronounced. Static DFT reveals multiple metastable interstitial configurations, while AIMD identifies ground states as C-C <100> dumbbells and octahedral Be interstitials. In conclusion, the diversity of metastable configurations and defect states complicates the diffusion mechanisms, requiring further molecular dynamics analysis to elucidate the mechanisms and rates of radiation-induced atomic transport, as well as the structural stability of Be2C.

Ab initio modeling↗
DOE OSTI2023

Materials Design Directions for Solar Thermochemical Water Splitting

The sustainable, economical production of molecular hydrogen is a crucial component of a net zero-greenhouse-gas-emissions future. Solar thermochemical water splitting (STWS) offers a renewable route to hydrogen with the potential to help decarbonize several industries, including transportation, manufacturing, mining, metals processing, and electricity generation, as well as provide sustainable hydrogen as a chemical feedstock. STWS uses high temperatures generated from concentrated sunlight or other sustainable means for high-temperature heat to produce hydrogen and oxygen from steam. For example, in its simplest form of a two-step thermochemical cycle, a redox-active metal oxide is heated to ≈1700-2000 K, driving off molecular oxygen while producing oxygen vacancies in the material. The reduced metal oxide then cools (ideally with the extracted heat recuperated for re-use) and, in a separate step, comes into contact with steam, which reacts with oxygen vacancies to produce molecular hydrogen while recovering the original state of the metal oxide. Despite its promising use of the entire solar spectrum to split water thermochemically, the current estimated cost of hydrogen produced via STWS is ≈4-6× the U.S. Department of Energy (DOE) Hydrogen Shot target value of $1/kg. One contributing approach to bridging this cost gap is the design of new materials with improved thermodynamic properties to enable higher efficiencies. The state-of-the-art (SOA) redox-active metal oxide for STWS is ceria (CeO 2 ), due to its close to optimal, although too high, oxygen vacancy formation enthalpy and large configurational and electronic entropy of reduction. However, ceria requires high operating temperatures and its efficiency is insufficient. Therefore, efforts to increase the efficiency of STWS cycles have focused on further optimizing oxygen vacancy formation enthalpies and augmenting the reduction entropy via substitution or doping and materials discovery schemes. Examples of the latter include the perovskites BaCe 0.25 Mn 0.75 O 3 and (Ca,Ce)(Ti,Mn)O 3 . These efforts and others have revealed intuitive chemical principles for the efficient and systematic design of more effective materials, such as the strong correlation between the enthalpies of crystal bond dissociation and solid-state cation reduction with the enthalpy of oxygen vacancy formation, as well as configurational entropy augmentation via the coexistence of two or more redox-active cation sublattices. The purpose of this chapter is to prepare the reader with an up-to-date account of STWS redox-active materials, both the SOA and promising newcomers, as well as to provide chemically intuitive strategies for improving their cycle efficiencies through materials design – in conjunction with ongoing efforts in reactor engineering and gas separations – to reach the cost points for commercial viability. First, we will introduce the thermodynamics of STWS using a two-step, metal-oxide, thermochemical cycle with economics in mind. We also will compare the pros and cons of processes that do or do not involve phase changes. Second, we will describe the qualities that make ceria the SOA STWS redox-active material, as well as its limitations. Third, we will survey some of the most promising candidates to date in the search for materials to supplant ceria, emphasizing the post-ternary, metal-oxide-perovskite alloys. Lastly, we will enumerate and discuss the following materials design directions for STWS redox-active materials: crystal reduction potentials as a proxy for oxygen vacancy formation enthalpies, engineering the electronic and configurational entropy of reduction via f-shells and simultaneous redox, and vetting materials stability via temperature-dependent phase diagrams and melting-point prediction.

08 HYDROGEN↗
DOE OSTI2023

Ultrahigh-Capacity Rocksalt Cathodes Enabled by Cycling-Activated Structural Changes

Mn-redox-based oxides and oxyfluorides are considered the most promising earth-abundant high-energy cathode materials for next-generation lithium-ion batteries. While high capacities are obtained in high-Mn content cathodes such as Li- and Mn-rich layered and spinel-type materials, local structure changes and structural distortions ( often lead to voltage fade, capacity decay, and impedance rise, resulting in unacceptable electrochemical performance upon cycling. In the present study, structural transformations that exploit the high capacity of Mn-rich oxyfluorides while enabling stable cycling, in stark contrast to commonly observed structural changes that result in rapid performance degradation, are reported. Here, it is shown that upon cycling of a cation-disordered rocksalt (DRX) cathode (Li 1.1 Mn 0.8 Ti 0.1 O 1.9 F 0.1 , an ultrahigh capacity of ≈320 mAh g –1 (energy density of ≈900 Wh kg –1 ) can be obtained through dynamic structural rearrangements upon cycling , along with a unique voltage profile evolution and capacity rise. At high voltage, the presence of Mn 4+ and Li + vacancies promotes local cation ordering, leading to the formation of domains of a “δ phase” within the disordered framework. On deep discharge, Mn 4+ reduction, along with Li + insertion transform the structure to a partially ordered DRX phase with a β'-LiFeO 2 -type arrangement. At the nanoscale, domains of the in situ formed phases are randomly oriented, allowing highly reversible structural changes and stable electrochemical cycling. These new insights not only help explain the superior electrochemical performance of high-Mn DRXbut also provide guidance for the future development of Mn-based, high-energy density oxide, and oxyfluoride cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2021

Preferential hole defect formation in monolayer W Se 2 by electron-beam irradiation

Monolayer transition-metal dichalcogenides (TMDCs) have been extensively studied due to their wide range of physical properties and applications. It has been demonstrated that the electron beam in a transmission electron microscope (TEM) or scanning TEM (STEM) generates chalcogen vacancies that agglomerate into dispersed linelike or holelike defects. Here we employ a STEM electron beam and demonstrate that, in WSe 2 , beam-induced chalcogen vacancies initially form certain dispersed multivacancy structures, as seen in TMDCs in prior work. However, with suitable control of the STEM focused electron beam, these multivacancies gradually evolve into a dense network of ten-, 12-, 14-, and 16-member ring round holes, whereas the same process leads predominantly to chalcogen-vacancy line defects in other trigonal-prismatic TMDCs. Density functional theory calculations find that the underlying atomic-scale processes lead preferentially to defect structures that lower the total energy so that we are able to track the formation of the observed multivacancy complexes, which then lead to the formation of dense large round holes in WSe 2 . The same processes in WS 2 , however, are energetically unfavorable, while linear multivacancy defects are preferred, as observed. The demonstrated control of the formation of unique high-density round holes in WSe 2 has potential for applications such as atomic and molecular sieving.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Rhodium Single–Atom Catalysts on Titania for Reverse Water Gas Shift Reaction Explored by First Principles Mechanistic Analysis and Compared to Nanoclusters

The thermocatalytic reduction of CO2 by H2 often proceeds via two competing reaction mechanisms—the reverse water gas shift reaction (rWGSR, CO2 + H2 ⇌ CO + H2O) and methanation (CO2 + 4H2 ⇌ CH4 + 2H2O). Atomically dispersed Rh1 catalysts on TiO2 show high selectivity toward the rWGSR compared with larger Rh nanoclusters, but the origin of this size-dependent selectivity has not been fully explained. Here we report density functional theory (DFT) calculations and microkinetic simulations that clarify the Rh1 active sites and rWGSR pathway on anatase TiO2(101), as well as the high rWGSR selectivity of Rh1 compared with supported Rhx (x = 2–8 atoms) nanoclusters. DFT-computed formation energies, vibrational frequency analysis, and microkinetic modeling suggest three plausible active sites: Rh1 on titania (Rh1/TiO2(101)), Rh1 with a nearby hydroxyl group (Rh1OH/TiO2(101)), and Rh1 near an oxygen vacancy at a three-fold coordinated site (Rh1 near O3cvac). Predicted turnover frequencies and apparent activation barriers for Rh1 indicate a faster reaction involving CO2 dissociation assisted by a support oxygen vacancy via Rh1 near O3cvac, as well as slower reactions involving Rh1OH/TiO2(101) or Rh1/TiO2(101) through a COOH intermediate. Furthermore, these Rh1 sites are selective toward CO rather than CH4 because of the weak adsorption of CO, large barrier for C-O bond dissociation, and the lack of nearby metal sites for H2 dissociation, in contrast to Rhx nanoclusters, including Rh2 dimers.

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

Factors Governing Oxygen Vacancy Formation in Oxide Perovskites

The control of oxygen vacancy (V O ) formation is critical to advancing multiple metal-oxide-perovskite-based technologies. In this work, we report the construction of a compact linear model for the neutral V O formation energy in ABO 3 perovskites that reproduces, with reasonable fidelity, Hubbard-U-corrected density functional theory calculations based on the state-of-the-art, strongly constrained and appropriately normed exchange-correlation functional. We obtain a mean absolute error of 0.45 eV for perovskites stable at 298 K, an accuracy that holds across a large, electronically diverse set of ABO 3 perovskites. Our model considers perovskites containing alkaline-earth metals (Ca, Sr, and Ba) and lanthanides (La and Ce) on the A-site and 3d transition metals (Ti, V, Cr, Mn, Fe, Co, and Ni) on the B-site in six different crystal systems (cubic, tetragonal, orthorhombic, hexagonal, rhombohedral, and monoclinic) common to perovskites. Physically intuitive metrics easily extracted from existing experimental thermochemical data or via inexpensive quantum mechanical calculations, including crystal bond dissociation energies and (solid phase) reduction potentials, are key components of the model. Beyond validation of the model against known experimental trends in materials used in solid oxide fuel cells, the model yields new candidate perovskites not contained in our training data set, such as (Bi,Y)(Fe,Co)O 3 , which we predict may have favorable thermochemical water-splitting properties. The confluence of sufficient accuracy, efficiency, and interpretability afforded by our model not only facilitates high-throughput computational screening for any application that requires the precise control of V O concentrations but also provides a clear picture of the dominant physics governing V O formation in metal-oxide perovskites.

08 HYDROGEN↗
DOE OSTI2022

Probing Electronic and Structural Transformations during Thermal Reduction of the Promising Water Splitting Perovskite BaCe 0.25 Mn 0.75 O 3

Here, in this report, we investigate the thermal reduction of the octahedral perovskite BaCe 0.25 Mn 0.75 O 3 (BCM) using in situ electron energy loss spectroscopy (EELS) in an aberration-corrected transmission electron microscope (TEM). The 12R-polytype of BCM is known to demonstrate high solar thermochemical hydrogen production capacity. In situ EELS measurements show that Mn is the active redox cation in BCM, undergoing thermal reduction from Mn 4+ to Mn 3+ during heating to 700 °C inside the TEM under a high vacuum. The progressive reduction of Mn 4+ during oxygen vacancy (O v ) formation was monitored as a function of temperature. Additionally, atomic-resolution scanning transmission electron microscopy identified two different types of twin boundaries present in the oxidized and reduced form of 12R-BCM, respectively. These two types of twin boundaries were shown, via computational modeling, to modulate the site-specific O v formation energies in 12R-BCM. It is concluded that these types of atomic defects provide sites more energetically favorable for O v formation during thermal reduction.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Insights into oxygen diffusion in rare earth disilicate environmental barrier coatings

Environmental barrier coatings (EBC) are crucial for the use of SiC-based ceramic matrix composites in high-temperature combustion environments, yet knowledge of oxygen diffusion in these coatings is limited. This study investigates oxygen diffusion dynamics in the β-RE 2 Si 2 O 7 system to minimize oxygen penetration in rare earth disilicates. We analyze defect formation energy under varying oxygen conditions, identifying key diffusion mechanisms. In oxygen-rich environments, the most favorable neutral interstitial oxygen diffuses along the [110] direction. In oxygen-poor conditions, neutral oxygen vacancies rotate around Y and Si atoms, exhibiting a diffusivity of 6.59×10 −22 m 2 /s at 1500 K for β-Yb 2 Si 2 O 7 . Under intermediate oxygen levels, charged interstitial oxygen diffuses via concerted interstitialcy along the [001] direction with a diffusivity of 6.21×10 −17 m 2 /s. Additionally, alloying rare earth Y with Er and Yb increases diffusion barriers, contributing to improved EBC performance in extreme environments. The insights gained provides valuable guidance for designing robust coatings tailored to withstand extreme operational environments.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Atomic-scale vacancy engineering unlocks basal-plane catalytic activity in metallic WSe 2 for reversible oxygen electrocatalysis

Two-dimensional metallic transition metal dichalcogenides offer high electrical conductivity and large surface areas for electrocatalysis, yet their inherent basal planes are catalytically inert. Here, we present an atomic-scale vacancy engineering strategy to activate the basal surfaces of metallic WSe 2 for reversible oxygen electrocatalysis. This approach, based on intentionally designed substitutional metal doping, promotes the spontaneous formation of selenium vacancies while preserving the metallic 1 T′ phase, thereby creating highly reactive and oxygen-affinitive sites. Density functional theory calculations reveal that these vacancy-mediated metal complexes dramatically lower the energy barriers for initial oxygen adsorption, enabling dissociative oxygen adsorption. Operando and ex-situ spectroscopic analyses confirm that vacancy-mediated metal complexes transform into dynamic Se/W-oxide intermediates under operating conditions. Se/W-oxides on the surface experimentally and theoretically prove electrocatalytic activity and reversibility. Applying this strategy in lithium–oxygen batteries, the basal-plane activated WSe 2 shows high discharge capacities (9868 mA h g −1 , corresponding to 3947 mA h g$^{-1}_{cathode}$), impressive cycle retention over 550 cycles at 1000 mA h g −1 , and outstanding rate–capability over a wide current–density range (100–3000 mA g −1 ) during 256 cycles.

2D materials↗
DOE OSTI2025

Development of interatomic potential and effect of ordering on defect properties in CrMnV

Developing materials that can withstand extreme environments, such as high radiation doses and elevated temperatures, is crucial for next-generation particle accelerators, including the 2.4 MW Long-Baseline Neutrino Facility. High-Entropy Alloys have emerged as promising candidates for beam window materials due to their superior mechanical strength, corrosion resistance, and radiation tolerance. In this study, we focus on the Cr–Mn–V alloy system, developing and employing machine-learning interatomic potentials (MLIPs) to investigate the formation of an ordered phase and its influence on defect properties. Using hybrid Monte Carlo-Molecular Dynamics simulations, we observe the formation of a B2-ordered phase at lower temperatures, consistent with Density Functional Theory (DFT) predictions. Ordered structures display a bimodal distribution of migration energies and reduced mean square displacement values, indicating suppressed vacancy diffusion. Our results also show that the migration energy barrier varies based on the atomic species, with Mn and V exhibiting the highest and lowest average barriers, respectively. These findings suggest that atomic ordering inhibits defect mobility, potentially enhancing the radiation resistance of CrMnV alloys. The validated MLIP provides a reliable framework for simulations that are faster than traditional DFT while maintaining the accuracy required to study defect and ordering properties.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Determination of Thermal Expansion, Defect Formation Energy, and Defect-Induced Strain of α-U Via ab Initio Molecular Dynamics

Uranium (U) is often alloyed with molybdenum (Mo) or zirconium (Zr) in order to stabilize its high-temperature body-centered cubic phase for use in nuclear reactors. However, in all metallic fuel forms, the α phase of U remains in some fraction. This phase decomposition due to temperature or compositional variance can play an outsized role on fuel performance and microstructural evolution. Relatively little is known about fundamental point defect properties in α -U at non-zero temperatures, from either computational or experimental studies. This work performs the first thorough evaluation of the α phase of U via ab initio molecular dynamics (AIMD). A number of thermophysical properties are calculated as a function of temperature, including equilibrium lattice parameters, thermal expansion, and heat capacity. These results indicate a two-region behavior, with the transition at 400 K. The thermal expansion/contraction in the a / b direction occurs rapidly from 100 up to 400 K, after which a more linear and gradual change in the lattice constant takes place. The volumetric expansion matches experiments quantitatively, but the individual lattice constant expansion only matches experiments qualitatively. Point defect formation energies and induced lattice strains are also determined as a function of temperature, providing insight on defect populations and the fundamentals of irradiation growth in α -U. Interstitials induce significantly more strain than vacancies, and the nature of that strain is highly dependent on the individual lattice directions. The direction of point defect-induced lattice strain is contrary to the irradiation growth behavior of α -U. This work shows that isolated point defects cannot be the primary driving force responsible for the significant irradiation-induced growth of α -U observed experimentally.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Influence of strain on SrFeO 3-δ oxidation, reduction, and water dissociation: Insights from ambient pressure X-ray photoelectron spectroscopy

The oxidation and reduction of metal oxides and their interaction with the environment play a critical role in their use for energy storage and conversion applications. The formation of surface adsorbates and their impact on oxide electronic structure can be challenging to probe experimentally, particularly for thin films which enable the study of epitaxial strain but have low surface areas. Here we present a detailed study using ambient pressure X-ray photoelectron spectroscopy of the reduction and oxidation of strained SrFeO 3-δ , induced by changes in temperature, oxygen partial pressure, and water vapor exposure. We find that in comparison to the oxidized lattice, application of tensile strain promotes the formation of oxygen vacancies at the surface, facilitating the subsequent incorporation of oxygen into the lattice in an oxygen environment. While tensile strain does promote the formation of hydroxyls from water dissociation, the kinetics of this process appear more sluggish than on less-strained surfaces, likely due to a competitive surface interaction with oxygen or bulk absorption of hydroxyl species. These findings relating strain, oxygen vacancies, and surface reactivity yield important insight into the surface functionality of oxides for energy conversion and storage applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Structural Instability in Electrically Stressed, Oxygen Deficient BaTiO 3 Nanocrystals

The dynamics of oxygen vacancies under external stimuli dominates the performance of many solid-state devices, including capacitors, oxide memristors, anionic conductors, etc. By means of in-situ Transmission Electron Microscopy, we found in BaTiO 3 perovskite nanocrystals that formation of oxygen vacancies due to electrical stressing renders the oxide amorphizable under electron beam illumination, suggesting the presence of a threshold concentration of oxygen vacancy affecting the structural stability of BaTiO 3 crystals upon high energy radiation. In contrast to the structural change, the resistivity of the nanocrystal seems not liable to the amorphization prior to dielectric breakdown at higher voltage bias. Here, we propose that an increase in oxygen vacancy content promotes oxygen mobility in the perovskite structure allowing electron beam induced electric field to modify the local structural and composition. Our in-situ observations reveal the central role of oxygen vacancies in the structural stability of perovskites which is of paramount importance to their applications in extreme environments and suggest a potential new route to micro-processing perovskite oxides using the electron beam via oxygen vacancy management without severely compromising the electric property.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Defect physics in 2D monolayer I-VII semiconductor AgI

As a brand new two-dimensional (2D) material with promising electronic properties, monolayer I-VII silver iodide (AgI) has the potential for future 2D electronic devices. To advance the development of such devices, the exploration of n-type and p-type conductivities of AgI is indispensable. With first-principles calculations, we systematically investigate the properties of intrinsic defects and extrinsic dopants in monolayer AgI, including atomic structural pictures, formation energies, and ionization energies to offer carriers. Considering the divergence in energies of charged defects in 2D materials when the traditional jellium scheme is used, we adopt an extrapolation approach to overcome the problem. The Ag vacancy (VAg) and Be substitution on Ag site (BeAg) are found to be the most promising p-type and n-type doping candidates, respectively. They could provide bound carriers for transport through the defect-bound band edge states, although the ionization energies are still larger than thermal energy at room temperature. Furthermore, negative-U behaviors are demonstrated in I vacancy (VI), Zn substitution on Ag site (ZnAg), and Cd substitution on Ag site (CdAg). The present work, for the first time, offers a detailed study of the defect physics in 2D I-VII monolayer semiconductor, laying the foundation for subsequent physics and device explorations based on these brand new 2D materials.

36 MATERIALS SCIENCE↗