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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Defect Equilibria from First Principles: From Widegap Oxides to Topological Semimetals

Materials functionality and performance is rarely determined by the ideal crystal alone but is usually affected by formation of imperfections and the solution of impurities. In some applications, such as solar thermochemical hydrogen generation, defect formation is the fundamentally enabling mechanism of the desired functionality. In other cases, such as Cd3As2 topological semimetals, unintentional self-doping presents an obstacle to the access to the unique electronic properties. In either case, a quantitative understanding of the relevant defect mechanism is essential for developing design strategies. This presentation will touch upon numerous aspects in the computational simulation of defect equilibria, including non-equilibrium design strategies, the coupling of solid state and gas-phase reactions, dopant-defect and defect-defect interactions, both attractive and repulsive, the accuracy of total energy functionals and electronic structure methods, and the role of the shape of the density of states for the charge balance condition and Fermi level position, as well as machine-learning prediction of defect energies (1). Specific materials systems include Ga2O3 (2), Cd3As2 (3), and (Sr,Ce)MnO3 (4). (1) M.D. Witman, A. Goyal, T. Ogitsu, A.H. McDaniel, S. Lany, Nat. Comput. Sci. 3, 675 (2023). (2) A. Goyal, A. Zakutayev, V. Stevanovic, S. Lany, J. Appl. Phys. 129, 245704 (2021). (3) C. Brooks, M. van Schilfgaarde, D. Pashov, J.N. Nelson, K. Alberi, D.S. Dessau, S. Lany, Phys. Rev. B 107, 224110 (2023). (4) A. Goyal, M.D. Sanders, R.P. O'Hayre, S. Lany, PRX Energy 3, 013008 (2024).

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS,M↗
DOE OSTI2020

Membrane-Free Zn/MnO 2 Flow Battery for Large-Scale Energy Storage

The traditional Zn/MnO 2 battery has attracted great interest due to its low cost, high safety, high output voltage, and environmental friendliness. However, it remains a big challenge to achieve long-term stability, mainly owing to the poor reversibility of the cathode reaction. Different from previous studies where the cathode redox reaction of MnO 2 /MnOOH is in solid state with limited reversibility, in this work a new aqueous rechargeable Zn/MnO 2 flow battery is constructed with dissolution–precipitation reactions in both cathodes (Mn 2+ /MnO 2 ) and anodes (Zn 2+ /Zn), which allow mixing of anolyte and catholyte into only one electrolyte and remove the requirement for an ion selective membrane for cost reduction. Impressively, this new battery exhibits a high discharge voltage of ≈1.78 V, good rate capability (10C discharge), and excellent cycling stability (1000 cycles without decay) at the areal capacity ranging from 0.5 to 2 mAh cm -2 . More importantly, this battery can be readily enlarged to a bench scale flow cell of 1.2 Ah with good capacity retention of 89.7% at the 500th cycle, displaying great potential for large-scale energy storage.

25 ENERGY STORAGE↗
DOE OSTI2025

Nanoporous Fe 2 O 3 and Soluble Fe(II) Intermediates Accelerate the Electrodeposition of Fe in NaOH(aq)

Electrochemical conversion of iron oxide to iron metal can enable low-cost batteries for long duration energy storage and zero-emissions ironmaking for steel. Iron oxides, such as hematite, can be electrochemically reduced to metallic iron in concentrated alkaline electrolytes at modest temperatures, but the relative influences of solid-state and dissolved intermediates at practical reaction rates remains unclear. Here, in this study, we prepare a homologous set of well-defined hematite particles to measure how the nanoscale morphology of oxides controls both their reactivity and apparent reduction mechanism in concentrated hydroxide. Correlated electron microscopy and rotating-ring-disk-electrode measurements revealed that nanoporous hematite and solid intermediates formed iron via a dissolution-redeposition pathway. In contrast, dense hematite particles directly formed iron metal via reactive fracture. While previous studies on iron electrowinning have primarily emphasized the role of particle diameter at the micron scale, these results demonstrate the importance of the dissolution-redeposition pathway to support rapid reaction rates and suggest that nanoscale porosity controls iron oxide reactivity at temperatures <100 °C. Therefore, iron-oxide-to-metal electrolyzers and fast-charging iron-air batteries supported by curtailed electricity can increase the rate of metal formation by accelerating fracture and dissolution in reactant oxides.

TEM↗
DOE OSTI2024

Does H 2 Temperature–Programmed Reduction Always Probe Solid–State Redox Chemistry? The Case of Pt/CeO 2

Redox reactions on the surface of transition metal oxides are of broad interest in thermo, photo, and electrocatalysis. H 2 temperature-programmed reduction (H 2 -TPR) is commonly used to probe oxide reducibility by measuring the rate of H 2 consumption during temperature ramps, assuming that this rate is controlled by oxide reduction. However, oxide reduction involves several elementary steps, such as H 2 dissociation and H-spillover, before surface reduction and H 2 O formation occur. In this study, we evaluated the kinetics of H 2 consumption over CeO 2 and Pt/CeO 2 with varying Pt loadings and structures to identify the elementary steps probed by H 2 -TPR. Literature often attributes changes in H 2 -TPR characteristics with Pt addition to increased CeO 2 reducibility. However, our analysis revealed that the H 2 consumption rate is measurement of the rate of H-spillover at Pt-CeO 2 interfaces and is determined by the concentration of Pt species on Pt nanoclusters that dissociate H 2 . Furthermore, lower temperature H 2 consumption observed with Pt addition does not indicate higher CeO 2 reducibility. Measurements on samples with mixtures of Pt single-atoms and nanoclusters demonstrated that H 2 -TPR can effectively quantify dilute Pt nanocluster concentrations, suggesting caution in directly linking H 2 -TPR characteristics to oxide reducibility while highlighting alternative material insights that can be gleaned.

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

Atomic layer deposited aluminum nitride for interface protection of lithium germanium thiophosphate solid electrolytes

Lithium germanium thiophosphate (LGPS) is an attractive solid-state electrolyte material due to its exceptionally high ionic conductivity (~1.2 × 10 –2 S cm –1 ), comparable to many organic liquid electrolytes commonly used in batteries. Despite the high conductivity of LGPS, the susceptibility of LGPS to deleterious degradation reactions has impeded its commercial adoption into solid-state batteries. In particular, the poor voltage stability of LGPS with high-voltage cathode or lithium metal potentials often results in dramatically increasing cell impedance during galvanic cycling. Here, we use aluminum nitride (AlN) as a protection layer for Li metal anode, applied directly to the LGPS at 250 °C using plasma-enhanced atomic layer deposition, to enhance cell performance by preventing LGPS-Li metal reactions. We compare the surface chemistry and electrochemical cycling performance of atomic layer-deposited AlN grown using both plasma N 2 and NH 3 precursors. Galvanostatic cycling and electrochemical impedance spectroscopy show that AlN-coated LGPS cells perform better than bare LGPS cells in contact with Li metal anodes, with the AlN able to improve cycling longevity by over a factor of 3 in certain cases. Finally, we utilize x-ray photoelectron spectroscopy (XPS) line scans to highlight the slow room-temperature reactivity between AlN and evaporated lithium metal, and a computational model is built to aid further XPS analysis.

25 ENERGY STORAGE↗
DOE OSTI2026

Pressure Heterogeneity and Material Utilization in Thin-Film Solid-State Cathodes

Intimate interfacial contact between the solid electrolyte and the cathode active material is critical for maximizing cathode utilization in solid-state batteries. However, volume changes during electrochemical cycling induce internal stresses that drive interfacial degradation, particularly under nonuniform stack pressure. In this study, we employ in situ energy-dispersive X-ray diffraction tomography to visualize and quantify reaction heterogeneities across a 3 mm-diameter solid-state cathode with a well-defined interface. Our results reveal that regions under a lower stack pressure exhibit reduced material utilization and reversibility, which negatively affect the high-pressure regions. Interfacial degradation further impedes lithium-ion transport and amplifies microscale reaction heterogeneity. These findings highlight the critical role of stack pressure distribution in governing interfacial stability and electrochemical performance, offering important design insights into practical solid-state battery systems.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Advancements in active filler-contained polymer solid-state electrolytes for lithium-metal batteries: A concise review

Lithium-metal batteries (LMBs) usually are regarded as the pinnacle of next-generation energy storage due to the high specific capacity and low redox potential of the Li-metal anode. However, their development is hindered by safety hazards related to flammable electrolytes and uncontrolled side reactions within the battery. Both polymer and solid-state inorganic electrolytes, despite their potential, exhibit shortcomings that limit their practical applications. Active filler-containing polymer electrolytes (AFPEs) offer a promising solution by combining the benefits of both types. Enhanced by supramolecular interactions between the polymer matrix and active fillers, AFPEs demonstrate superior electrochemical performance over traditional polymer electrolytes. This review discusses the progress in active fillers and various polymer matrices, examining the factors that enhance performance, particularly ionic conductivity. It also outlines the future research directions of AFPEs, aiming to broaden the application of solid electrolytes in high-performance LMBs.

All solid-state batteries↗
DOE OSTI2022

Transition Metal Carbo-Chalcogenide “TMCC:” A New Family of 2D Materials

A new family of 2D transition metal carbo-chalcogenides (TMCCs) is reported, which can be considered a combination of two well-known families, TM carbides (MXenes) and TM dichalcogenides (TMDCs), at the atomic level. Single sheets are successfully obtained from multilayered Nb 2 S 2 C and Ta 2 S 2 C using electrochemical lithiation followed by sonication in water. The parent multilayered TMCCs are synthesized using a simple, scalable solid-state synthesis followed by a topochemical reaction. Superconductivity transition is observed at 7.55 K for Nb 2 S 2 C. The delaminated Nb 2 S 2 C outperforms both multilayered Nb 2 S 2 C and delaminated NbS 2 as an electrode material for Li-ion batteries. Ab initio calculations predict the elastic constant of TMCC to be over 50% higher than that of TMDC.

superconductors↗
DOE OSTI2025

Disordered Rocksalts as High‐Energy and Earth‐Abundant Li‐Ion Cathodes

To address the growing demand for energy and support the shift toward transportation electrification and intermittent renewable energy, there is an urgent need for low‐cost, energy‐dense electrical storage. Research on Li‐ion electrode materials has predominantly focused on ordered materials with well‐defined lithium diffusion channels, limiting cathode design to resource‐constrained Ni‐ and Co‐based oxides and lower‐energy polyanion compounds. Recently, disordered rocksalts with lithium excess (DRX) have demonstrated high capacity and energy density when lithium excess and/or local ordering allow statistical percolation of lithium sites through the structure. This cation disorder can be induced by high temperature synthesis or mechanochemical synthesis methods for a broad range of compositions. DRX oxides and oxyfluorides containing Earth‐abundant transition metals have been prepared using various synthesis routes, including solid‐state, molten‐salt, and sol‐gel reactions. This review outlines DRX design principles and explains the effect of synthesis conditions on cation disorder and short‐range cation ordering (SRO), which determines the cycling stability and rate capability. In addition, strategies to enhance Li transport and capacity retention with Mn‐rich DRX possessing partial spinel‐like ordering are discussed. Finally, the review considers the optimization of carbon and electrolyte in DRX materials and addresses key challenges and opportunities for commercializing DRX cathodes.

Li-ion batteries↗
DOE OSTI2024

Does H 2 Temperature‐Programmed Reduction Always Probe Solid‐State Redox Chemistry? The Case of Pt/CeO 2

Abstract Redox reactions on the surface of transition metal oxides are of broad interest in thermo, photo, and electrocatalysis. H 2 temperature‐programmed reduction (H 2 ‐TPR) is commonly used to probe oxide reducibility by measuring the rate of H 2 consumption during temperature ramps, assuming that this rate is controlled by oxide reduction. However, oxide reduction involves several elementary steps, such as H 2 dissociation and H‐spillover, before surface reduction and H 2 O formation occur. In this study, we evaluated the kinetics of H 2 consumption over CeO 2 and Pt/CeO 2 with varying Pt loadings and structures to identify the elementary steps probed by H 2 ‐TPR. Literature often attributes changes in H 2 ‐TPR characteristics with Pt addition to increased CeO 2 reducibility. However, our analysis revealed that the H 2 consumption rate is measurement of the rate of H‐spillover at Pt‐CeO 2 interfaces and is determined by the concentration of Pt species on Pt nanoclusters that dissociate H 2 . Therefore, lower temperature H 2 consumption observed with Pt addition does not indicate higher CeO 2 reducibility. Measurements on samples with mixtures of Pt single‐atoms and nanoclusters demonstrated that H 2 ‐TPR can effectively quantify dilute Pt nanocluster concentrations, suggesting caution in directly linking H 2 ‐TPR characteristics to oxide reducibility while highlighting alternative material insights that can be gleaned.

Lee, Jaeha↗
DOE OSTI2026

Multi-material additive manufacturing of aluminum 6061-T6 alloy with stainless steel 304: Suppression of intermetallic compounds and interface growth mechanism

Fabricating integrated aluminum-steel structures is difficult because of metallurgical incompatibilities that promote intermetallic compound (IMC) formation at their interfaces. This work introduces a practical route for additively manufacturing 6061-T6 aluminum alloy (AA6061-T6) directly onto 304 stainless steel (SS304) using a high shear strain rate-assisted interfacial bonding mechanism. Through the friction extrusion deposition-based additive manufacturing method, both single- and multi-layer deposits of AA6061-T6 were successfully fabricated on SS304, yielding a robust hybrid multi-material structure. Comprehensive analyses of deposition quality, interface porosity, and bonding performance showed that the interface achieved a tensile strength exceeding 154 MPa under quasi-static loading. Microstructural observations revealed that the deposited aluminum layers experienced severe plastic deformation, resulting in pronounced grain refinement. Importantly, the interfacial zone was found to be free of brittle IMCs, instead containing a thin amorphous layer that evolved through a non-linear reaction-zone growth law. This solid-state additive strategy establishes a promising pathway for lightweight structural systems, nuclear energy component cladding, and multifunctional engineering components, redefining how dissimilar metals can be integrated for advanced applications.

Aluminum alloy↗
DOE OSTI2020

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

Intermetallic compounds are atomically ordered inorganic materials containing two or more transition metals and main-group elements in unique crystal structures. Intermetallics based on group 10 and group 14 metals have shown enhanced activity, selectivity, and durability in comparison to simple metals and alloys in many catalytic reactions. While high-temperature solid-state methods to prepare intermetallic compounds exist, softer synthetic methods can provide key advantages, such as enabling the preparation of metastable phases or of smaller particles with increased surface areas for catalysis. In this work, we study a generalized family of heterobimetallic precursors to binary intermetallics, each containing a group 10 metal and a group 14 tetrel bonded together and supported by pincer-like pyridine-2-thiolate ligands. Upon thermal decomposition, these heterobimetallic complexes form 10–14 binary intermetallic nanocrystals. Experiments and density functional theory (DFT) computations help in better understanding the reactivity of these precursors toward the synthesis of specific intermetallic binary phases. Using Pd 2 Sn as an example, we demonstrate that nanoparticles made in this way can act as uniquely selective catalysts for the reduction of nitroarenes to azoxyarenes, which highlights the utility of the intermetallics made by our method. Employing heterobimetallic pincer complexes as precursors toward binary nanocrystals and other metal-rich intermetallics provides opportunities to explore the fundamental chemistry and applications of these materials.

10-14 intermetallics↗
DOE OSTI2024

Surface and Bulk Stabilization of Silicon Anodes with Mixed-Multivalent Additives: Ca(TFSI) 2 and Mg(TFSI) 2

Here, silicon is drawing attention as the upcoming anode material for the next generation of lithium-ion batteries due to its higher capacity compared to commercial graphite. However, silicon anions formed during lithiation are highly reactive with binder and electrolyte components creating an unstable SEI layer and limiting the calendar life of silicon anodes. The reactivity of lithium silicide and the formation of an unstable SEI layer is mitigated by utilizing the use of a mixture of Ca and Mg multivalent cations as an electrolyte additive for Si anodes to improve their calendar life. The effect of mixed salts on the bulk and surface of silicon anodes was studied by multiple structural characterization techniques. Ca and Mg ions in the electrolyte formed relatively thermodynamically stable quaternary Li-Ca-Mg-Si Zintl phases in an in-situ fashion and more stable and denser SEI layer on the Si particles. These in turn protect silicon particles against side reactions with electrolytes in a coin cell. The full cell with the mixed cation electrolyte demonstrates enhanced calendar life performance with lower measured current and current leakage than that of the baseline electrolyte due to reduced side reactions. Electron Microscopy, HRXRD, and solid-state NMR results showed that electrodes with mixed cations tended to have less cracking on the electrode surface compared to Si electrodes with Gen2 + FEC and the presence of mixed cations enhances cation migration and formation of quaternary Zintl phases stabilizing bulk and forming a more stable SEI.

25 ENERGY STORAGE↗
DOE OSTI2020

Synthesis, transport properties and electronic structure of p-type Cu 1+x Mn 2–x InTe 4 ( x = 0, 0.2, 0.3)

The synthesis, electronic structure and temperature dependent transport properties of polycrystalline Cu 1+x Mn 2–x InTe 4 (x = 0, 0.2, 0.3) are reported for the first time. These quaternary chalcogenides were synthesized by direct reaction of the elements, followed by solid state annealing and hot press densification. The thermal conductivity is low for all specimens and intrinsic to the material system. Furthermore, the off-stoichiometry specimens illustrate the sensitivity of the transport properties to stoichiometry, with a greater than two-orders-of magnitude increase in carrier concentration with increased Cu content. First principles calculations of the electronic structure are also reported, and are in agreement with the experimental data. Here, this fundamental investigation shows the potential towards further optimization of the electrical properties that, in addition to the intrinsically low thermal conductivity, provides a basis for further research into the viability of this material system for potential energy-related applications.

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

Effects of diffusion barriers on reaction wave stability in Co/Al reactive multilayers

Bimetallic, reactive multilayers are uniformly structured materials composed of alternating sputter-deposited layers that may be ignited to produce self-propagating mixing and formation reactions. These nanolaminates are most commonly used as rapid-release heat sources. The specific chemical composition at each metal/metal interface determines the rate of mass transport in a mixing and formation reaction. The inclusion of engineered diffusion barriers at each interface will not only inhibit solid-state mixing but also may impede the self-propagating reactions by introducing instabilities to wavefront morphology. Here, this work examines the effect of adding diffusion barriers on the propagation of reaction waves in Co/Al multilayers. The Co/Al system has been shown to exhibit a reaction propagation instability that is dependent on the bilayer thickness, which allows for the occurrence of unstable modes in otherwise stable designs from the inclusion of diffusion barriers. Based on the known stability criteria in the Co/Al multilayer system, the way in which the inclusion of diffusion barriers changes a multilayer's heat of reaction, thermal conductivity, and material mixing mechanisms can be determined. These factors, in aggregate, lead to changes in the wavefront velocity and stability.

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

Prompt Photofission Neutron Detection in Depleted Uranium

The detection of prompt photofission neutrons during active interrogation is a strong indication of the presence of special nuclear materials. However, the high-energy photons used for interrogation create a very challenging radiation environment for the detection of prompt fission signatures. These challenges include detector saturation and pulse pile-up. Additionally, there is an elevated neutron background that further challenges the detection of prompt fission neutrons. This background is produced because of (γ, Xn) photonuclear reactions in the surrounding high-Z materials. Here, we demonstrate the detection of prompt photofission neutrons in these challenging environments. Depleted uranium (DU) and lead targets are interrogated with bremsstrahlung photons produced by a 9-MV electron linear accelerator. Fast neutrons are detected with trans-stilbene organic detectors, and scintillation pulses are analyzed using a previously developed and demonstrated artificial neural network system. We observe a 5 times higher photoneutron count rate when the lead target is replaced with the DU target. Additionally, we observe a difference in the photoneutron light-output distributions of lead and DU. Here, this difference in the measured distributions is due to the difference in the photoneutron-energy spectra; DU photoneutrons are emitted with (γ, n) and watt-energy spectra, whereas lead photoneutrons are emitted with only the (γ, n) spectrum.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗