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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 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
NASA NTRS1981

Creep and residual mechanical properties of cast superalloys and oxide dispersion strengthened alloys

Tensile, stress-rupture, creep, and residual tensile properties after creep testing were determined for two typical cast superalloys and four advanced oxide dispersion strengthened (ODS) alloys. The superalloys examined included the nickel-base alloy B-1900 and the cobalt-base alloy MAR-M509. The nickel-base ODS MA-757 (Ni-16CR-4Al-0.6Y2O3 and the iron-base ODS alloy MA-956 (Fe-20Cr-5Al-0.8Y2O3) were extensively studied, while limited testing was conducted on the ODS nickel-base alloys STCA (Ni-16Cr-4.5Al-2Y2O3) with a without Ta and YD-NiCrAl (Ni-16Cr-5Al-2Y2O3). Elevated temperature testing was conducted from 114 to 1477 K except for STCA and YD-NiCrAl alloys, which were only tested at 1366 K. The residual tensile properties of B-1900 and MAR-M509 are not reduced by prior creep testing (strains at least up to 1 percent), while the room temperature tensile properties of ODS nickel-base alloys can be reduced by small amounts of prior creep strain (less than 0.5 percent). The iron-base ODS alloy MA-956 does not appear to be susceptible to creep degradation at least up to strains of about 0.25 percent. However, MA-956 exhibits unusual creep behavior which apparently involves crack nucleation and growth.

Whittenberger, J. D.↗
DOE OSTI2026

Tuneable electronic coupling in linked bis(cubane) cobalt-oxo clusters

A family of cobalt-oxo bis(cubane) complexes wherein each subunit is derived from the Co 4 O 4 cubane, a known water oxidation catalyst, was synthesized. Both 4,4′-bipyrdine and pyrazine were demonstrated to serve as viable bridging ligands. Through an analysis of their half-wave splitting potentials, it was determined that pyrazine-bridged bis(cubane)s exhibit inter-cubane electronic coupling, and that this coupling may be tuned through ligand substitution. Electrostatic contributions to the half-wave splitting potentials were evaluated and found to result in “non-conformist” behavior related to the ion-pairing ability of the electrolytes.

Maddi, Vincent J. P. [University of California, Be↗
NASA NTRS1971

Oxidation screening at 1204 C /2200 F/ of candidate alloys for the space shuttle thermal protection system.

Evaluation of the oxidation resistance of 15 alloys under some of the environmental conditions that might be encountered by the shuttle thermal protection system. The alloys included nickel-, iron-, and cobalt-base wrought alloys. Specimens were self-resistively heated to 1204 C (2200 F) in a 10-torr still-air environment for 100 thirty-minute cycles. Specimen weight, thickness, and microstructural changes were noted, and surface scales were identified by room-temperature X-ray diffraction. Based on these observations, the behavior of the alloys was evaluated in terms of overall amount of metal consumption due to oxide formation and relative tendency toward oxide spalling and scale vaporization.

Sanders, W. A.↗
DOE OSTI2022

Artificial cathode electrolyte interphase for improving high voltage cycling stability of thick electrode with Co-free 5 V spinel oxides

Spinel-type cathode LiNi 0.5 Mn 1.5 O 4 (LNMO) has intrigued the transportation industry due to its high operating voltage and total elimination of the expensive cobalt element. However, LNMO cathode with high mass loading (> 3 mAh/cm 2 in areal capacity) has suffered from excessive capacity degradation upon long cycling. Here, a robust Al 2 O 3 surface layer is introduced to the thick LNMO electrode via atomic layer deposition (ALD). The capacity retention in full cells with the graphite anode is improved from 46.3% to 75.3% after 300 cycles with cutoff voltage up to 4.85 V, while enabling average Coulombic efficiency of 99.9% during the cycling. The post-mortem analyses reveal that the Al 2 O 3 surface layer would convert to Al-O-F /Al-F species upon cycling, offering stable interphase to protect the cathode material. Furthermore, these results demonstrate the significance of surface modification enabling high voltage cathode for next-generation LIBs.

25 ENERGY STORAGE↗
DOE OSTI2025

Topotaxially grown composite cathodes for cobalt-free high-energy long-life Li-ion batteries

The vehicle industry’s increasing demand for electrification necessitates the removal of expensive and rare cobalt from current high-energy batteries. However, eliminating cobalt poses challenges due to its vital role in maintaining the layered structural ordering and cycling stability of commonly used Li(NiMnCo)O 2 cathodes. As an alternative to conventional layered oxide designs, we report a lithium nickelate cathode with a composite structure comprising major stoichiometric layered and minor rocksalt phases within the same oxygen lattice. This material outperforms conventional designs by maintaining stable battery operation at voltages up to 4.8 V vs. Li|Li + , with 88% capacity retention after 1000 cycles at 2C. The topotaxial-growth-enabled interlock between the two components mitigates chemo-mechanical degradation, offering a promising pathway to cobalt-free cathodes. Additionally, we reveal a miscibility gap in the Li-Ni-O system that enables kinetic adjustment of composition and structure during sintering, thereby tuning the functionality of high-energy cathodes.

25 ENERGY STORAGE↗
DOE OSTI2022

On-Demand Designing of Cathode Internal Surface Architecture for Dramatic Enhancement of SOFC Performance and Durability

This project is aimed to design and modify the internal surfaces of porous composite cathode from currently commercially viable Solid Oxide Fuel Cells (SOFCs), using additive manufacturing process of Atomic Layer Deposition (ALD). The material systems being investigated are commercial composite electrodes complex three-dimensional topographies. In term of the chemistry of the ALD layer applied on the internal surface of the porous cathode, this project has employed commercially relevant electrolyte, electrocatalyst and noble metal materials set. Such materials are fully compatible with the commercial fuel cells, and this project has developed special nanostructure on the surface of the commercial composite cathodes. The formation of the designed nanoarchitecture on the surface of SOFC cathode has been achieved through precise control of ALD parameters and their effect on overall cell performance and resultant electrochemical reaction mechanism of cathodes has been investigated through full cell electrochemical performance testing and nanostructure characterization by transmission electron microscopy (TEM). Under the support of this award, following has been achieved: (1). For cathode materials in solid oxide fuel cells (SOFCs), such as perovskite mixed conductor La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-x (LSCF), cation surface segregation and consequently losing conductivity and active sites for the oxygen reduction reaction (ORR) are problematic. To mitigate the cation segregation and enhance SOFC durability, further decorating the internal backbone surface using the desired electrocatalysts could be a promoting approach. Commonly, the cation segregation such as Sr is very volatile, so the effective surface decoration is ideally conformal. Nevertheless, the conformal surface coating would inevitably alter the ORR pathways that initially take place on the surface of the backbone. To reveal the impact of the conformal coating on both the catalytic activity and the conductivity of the cathode, the unary electrocatalyst of Pt or CoO x , was applied to the LSCF/SDC composite electrode of inherently functional SOFCs, respectively. Both ALD coating layers evolve strong interaction with the LSCF composite cathode. Upon operations, the Pt coating layer remains conformal on LSCF grain surfaces but turns into discrete particles on SDC grain surfaces. Meanwhile, CoO x conformal coating grows to be the discrete nanograins on both the LSCF and SDC grains. ALD coating of the cathode alone reduces the ohmic resistance up to 28 % for the entire cells. The increased conductivity induced by the ALD coating of Pt or CoO x is ascribed to different mechanisms. For the inherent functional SOFCs, the present study presents a novel and feasible approach to apply a conformal, dense coating layer on the surface of a mixed conductor, simultaneously increasing the conductivity and durability of the SOFC cathode. (2). High resistance of the oxygen electrode still significantly hinders the state-of-the-art Solid Oxide Fuel Cells (SOFCs). In particular, for an oxygen electrode consisting of mixed electronic and ionic conductors, such as perovskite lanthanum strontium cobalt ferrite (LSCF), it deteriorates due to its low chemical stability of the grain surface. Such degradation is often associated with the segregation of cations. To prevent the cation surface segregation and its resultant perovskite phase decomposition, we demonstrate a conformal ultra-thin (7-10 nm) surface heterogeneous coating layer consisting of subjacent discrete Pt nanoparticles capped with a superjacent fully dense conformal CoO x layer. The performance studies indicate the ALD coating reduces the cell series resistance by up to 40 %. The conformal CoO x layer consists of randomly orientated but single-layered nanograins, with high-density intergranular and surface grain boundaries serving as the electrochemical reaction sites and facilitating mass transport. The conformal coating layer appears to have successfully suppressed the Sr outward diffusion and confined the Sr enriched layer to a ~ 2 nm interface perovskite phase between the coating layer and the LSCF grain surface. Moreover, this ultra-thin Sr enriched perovskite layer presumably possesses high oxygen vacancy and high ionic conductivity and further imposes tensile strain to the LSCF grain surfaces. With the combination of a conformal CoO x nanoionics, Sr enriched layer, and its strained interface, the ALD coating induced surface layer is estimated to have a conductivity of ~ 1.27x10 4 S/cm, which is over two orders magnitude of that from LSCF at 750 ºC.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

Cobalt-Free Cathodes for Next Generation Li-Ion Batteries

In this U.S. Department of Energy sponsored project Nexceris, in collaboration with project partners; The Ohio State University and Navitas Advanced Systems have advanced the technical maturity of a non-cobalt containing cathode for next-generation Li-ion batteries. The cathode is based on the lithium manganese nickel-titanium oxide, LiNi 0.5 Mn 1.5 TiO 4 (LNMTO) high voltage spinel. To address limitations with poor cycle and calendar life an microstucturally hierarchical LNMO/LNMTO core-shell cathode powder has been developed that enables the formation of a solid-electrolyte interface that effectively passivates the cathode surface. The microstructural enhancements of the cathode material focus on preferentially enriching the surface with titanium. In parallel, new, optimized binder and electrolyte chemistries have been incorporated to address degradation mechanisms associated with high-voltage systems. Single-layer pouch cell and large-format 2-Ah cell testing have shown that an optimized LNMO/LNMTO core-shell powder significantly improves initial cell capacity and cycle life compared to homogeneous LNMO powder. To support development and the fabrication of 2-Ah cells a novel Hybrid Alternative Wet-Chemical Synthesis (HAWCS) process have been developed. This low-cost, synthesis approach enables the excellent compositional and particle morphology control achieved with co-precipitation without the strict process controls and associated expensive process equipment.

25 ENERGY STORAGE↗
NASA NTRS1985

Slow plastic strain rate compressive flow in binary CoAl intermetallics

Constant-velocity elevated temperature compression tests have been conducted on a series of binary CoAl intermetallics produced by hot extrusion of blended prealloyed powders. The as-extruded materials were polycrystalline, and they retained their nominal 10-micron grain size after being tested between 1100 and 1400 K at strain rates ranging from 2 x 10 to the -4th to 2 x 10 to the -7th per sec. Significant plastic flow was obtained in all cases; while cracking was observed, much of this could be due to failure at matrix-oxide interfaces along extrusion stringers rather than to solely intergranular fracture. A maximum in flow strength occurs at an aluminum-to-cobalt ratio of 0.975, and the stress exponent appears to be constant for aluminum-to-cobalt ratios of 0.85 or more. It is likely that very aluminum-deficient materials deform by a different mechanism than do other compositions.

Whittenberger, J. D.↗
DOE OSTI2021

Nanostructured mixed metal oxides as catalysts and method of making thereof

A method of forming a metal oxide material having a rod shape or polyhedral nanostructure includes preparing a first reverse micro-emulsion system comprising an aqueous precipitating agent dispersion and a second reverse micro-emulsion system containing an aqueous metal salt dispersion; combining the micro-emulsions together to initiate a reaction; allowing the reaction to continue to form a product mixture comprising a metal oxide gel and aqueous media; separating the metal oxide gel from the aqueous media; collecting the metal oxide gel; and calcining the metal oxide gel to form the metal oxide material. The metal oxide material corresponds to the chemical formula of La2MxNi1-xO4, Pr2-yAyNiO4, or La2-zDzNiO4, wherein M is copper, cobalt, iron, manganese, chromium, aluminum, or platinum; A is lanthanum or neodymium; D is calcium, barium or strontium; x ranges from 0 to 1; y ranges from 0 to 2; and z ranges from 0 to 0.25.

Nikolla, Eranda↗
DOE OSTI2024

Optimizing Materials to Boost the Valorization of CO 2 : Tuning Cobalt–Cobalt Interactions on In 2 O 3 -Based Photothermal Catalysts

The valorization of CO 2 is an important challenge within the current panorama, since this molecule is probably the main contributor to climate change. In this study, the synthesis of materials based on a nanostructured batonnet-type indium oxide is carried out. In them, different amounts of Co are introduced, varying between 2 and 8% mol. It is verified that the most active sample in the transformation of carbon dioxide to carbon monoxide contains 6 mol %. of Co. This sample’s activity under dual excitation exceeds the thermal counterpart by more than 30%. After carrying out a complete physical and chemical characterization with the help of X-ray absorption spectroscopy and other techniques, it is shown that catalysts with amounts of cobalt equal to or below 4 mol % contain isolated single-atom species, while those with higher amounts of metal display a Co–Co interaction which triggers the evolution of the samples under reaction conditions. The optimum control of this Co–Co interaction and the nature of the final cobalt-containing species determine dual photothermal catalytic properties. In conclusion, this work establishes a structure–activity relationship to interpret the catalytic behavior of highly dispersed subnanometric cobalt species, and thus an avenue to optimize the photothermal valorization of carbon dioxide.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Exploiting the Marcus inverted region for first-row transition metal–based photoredox catalysis

Second- and third-row transition metal complexes are widely employed in photocatalysis, whereas earth-abundant first-row transition metals have found only limited use because of the prohibitively fast decay of their excited states. Here we report an unforeseen reactivity mode for productive photocatalysis that uses cobalt polypyridyl complexes as photocatalysts by exploiting Marcus inverted region behavior that couples increases in excited-state energies with increased excited-state lifetimes. These cobalt (III) complexes can engage in bimolecular reactivity by virtue of their strong redox potentials and sufficiently long excited-state lifetimes, catalyzing oxidative C(sp 2 )–N coupling of aryl amides with challenging sterically hindered aryl boronic acids. More generally, the results imply that chromophores can be designed to increase excited-state lifetimes while simultaneously increasing excited-state energies, providing a pathway for the use of relatively abundant metals as photoredox catalysts.

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

Creating and Preserving Nanoparticles during Co-Sintering of Solid Oxide Electrodes and Its Impact on Electrocatalytic Activity

A novel processing method that creates and preserves ceramic nanoparticles in solid oxide electrodes during co-sintering at traditional sintering temperatures is introduced. Specifically, carbon templated samarium-doped ceria nanoparticles (nSDC) were successfully integrated with commercial lanthanum strontium cobalt ferrite (LSCF) and commercial SDC powders, producing LSCF-SDC-nSDC cathodes upon processing. The effect of nSDC concentration on cathode electrocatalytic activity was investigated at low operational temperatures, 600 °C–700 °C, with symmetrical cells. Low nSDC loadings, ≤5 wt% nSDC, significantly decreased cell polarization resistance whereas higher loadings increased it. The best electrochemical performance was achieved with 5 wt% nSDC, lowering the polarization resistance by 41% at 600 °C. Fuel cell tests demonstrate that adding 5 wt% nSDC increased the maximum fuel cell power density by 38%. Electrochemical impedance spectra showed substantial improvements in both fuel cell polarization resistance and ohmic resistance, indicating that nSDC increased the electrocatalytically active area of the cathode. This work demonstrates a simple, novel method for effectively increasing electrocatalytic activity of solid oxide electrodes at low operational temperatures.

Muhoza, Sixbert P. (ORCID:0000000299864241)↗
DOE OSTI2025

Electron Inversion and Tunneling at Silicon Thermal Oxide Interfaces for Solar-Driven Molecular Catalysis to Syngas

Semiconductor photoelectrodes are regularly coupled to solid-state heterogeneous catalysts to perform solar-driven reduction of CO 2 . Less frequently, molecular catalysts are employed to better control the reactivity toward desired products, yet the development of robust semiconductor/molecule interfaces has proven challenging. Here, we demonstrate that a 2–3 nm thermal oxide layer on Si exhibits stability in aqueous solution, high photovoltage, and a photocurrent density of ∼10 mA/cm 2 for the solar-driven photoelectrochemical reduction of a homogeneous molecular catalyst, producing syngas with an ∼2:1 H 2 to CO ratio. Because of a low defect density, the oxide interface forms an electron inversion layer with metal-like electron density at cathodic potentials. This inversion layer facilitates electron transfer to redox-active molecules via tunneling even if the molecule’s reduction potential is beyond the semiconductor’s conduction band edge. Using an electrolyte solution composed of a homogeneous cobalt bis(terpyridine) catalyst in a water/organic solvent mixture, stable photoelectrochemistry was observed under 1-sun illumination, exhibiting an ∼30% Faradaic efficiency for CO that was similar to a glassy carbon electrode under comparable conditions. Furthermore, the results demonstrate that an ultrathin thermal oxide interface is a robust platform for development of aqueous-stable, molecule-driven photoelectrocatalysis.

Catalysts↗
DOE OSTI2020

Status of SRNL Radiological Field Lysimeter Experiment (RadFLEx) – Year 7

The Radiological Field Lysimeter Experiment (RadFLEx) began in 2012 and is a collaboration between the Savannah River National Laboratory (SRNL) and Clemson University. The purpose of this facility is to study the long-term (2 to 20 years) fate and transport of radionuclides in the Savannah River Site (SRS) vadose zone under natural field and meteorological conditions. The unique facility houses 48 5-L cores filled with sediments amended with various radionuclide sources. The results from these studies have been applied to the development of geochemical models used to assess the risk posed by subsurface nuclear waste disposal, environmental remediation, and waste form development. This report describes the refurbishment of the exterior of the RadFLEx facility and the synthesis and deployment of six plutonium(Pu) sources, four neptunium (Np) sources and one radium (Ra) source. It is anticipated that these newly installed lysimeter cores will be studied for up to 10 years.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS1987

Phase purity of NiCo2O4, a catalyst candidate for electrolysis of water

NiCo2O4 is shown to be difficult to obtain as a pure phase, and may never have been so obtained. High resolution x-ray diffractometry is required for its precise characterization. Film XRD is not likely to show the asymmetry in the spinel diffraction lines, caused by poorly crystallized NiO, as seen in diffractometer traces. The Co3O4 which is expected to accompany NiO as an impurity in NiCo2O4 syntheses has the same diffraction pattern as the binary oxide. Firings of the co-precipitated hydroxides at 300, 350, and 400 C, including one in pure O2, failed to produce single phase cobaltate. Scanning electron microscopy showed all the sintered products to range over several orders of magnitude in agglomerate/particle size. Surface areas by BET were all in the range 40 to 110 m sq/g, equivalent to particles of 200 to 100 Angstrom diameter. The spinel diffraction line breadths were compatible with those approximate dimensions.

Singer, J.↗
DOE OSTI2021

Effective reduction of PdCoO 2 thin films via hydrogenation and sign tunable anomalous Hall effect

PdCoO 2 , belonging to a family of triangular oxides called delafossite, is one of the most conducting oxides. Its in-plane conductivity is comparable to those of the best metals and exhibits hydrodynamic electronic transport with an extremely long mean free path at cryogenic temperatures. Nonetheless, it is nonmagnetic despite the presence of the cobalt ion. In this work, we show that a mild hydrogenation process reduces PdCoO 2 thin films to an atomically mixed alloy of PdCo with strong out-of-plane ferromagnetism and sign-tunable anomalous Hall effect. Considering that many other compounds remain little affected under a similar hydrogenation condition, this discovery may provide a route to creating novel spintronic heterostructures combining strong ferromagnetism, involving oxides and other functional materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Dithionite Inhibits Iron(III) (Hydr)oxide Formation during Olivine Dissolution Advancing Simultaneous CO 2 Mineralization and Nickel Recovery

Increasing CO 2 concentration poses significant global challenges, impacting both environmental and human health. As we strive for a carbon-neutral energy technology transition, the demand for critical elements (e.g., nickel and cobalt) continues to increase, while high-grade ores are depleting. Combining CO 2 mineralization with the recovery of critical elements from low-grade ores offers an innovative solution. Olivine, a magnesium-rich ultramafic with trace amounts of critical elements, is a promising mineral; however, its impurities, such as iron (Fe(III)), hinder the dissolution of Ni and Mg from olivine, reducing its carbonation and critical element recovery. Here, to address this challenge, this study examined Ni dissolution from San Carlos olivine at high temperatures and high CO 2 pressure. We found that iron(III) (hydr)oxide layers impeded olivine dissolution; however, with sodium dithionite (Na 2 S 2 O 4 ), a reducing agent, olivine dissolution is significantly improved by preventing iron(III) (hydr)oxide formation. With Na 2 S 2 O 4 , within 24 h, Mg and Ni dissolution from olivine increased 2.85-fold and 2.66-fold, respectively, compared to samples without Na 2 S 2 O 4 . After seven cycles, with solutions replaced every 24 h, 98.9% of the total Mg and 84.6% of the total Ni were recovered. This approach enhances olivine’s CO 2 mineralization and improves the sustainability of critical element supply.

54 ENVIRONMENTAL SCIENCES↗