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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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Modifying perovskite into A-site deficient electrode: oxygen vacancy enhances surface kinetics and durability, enabling superior performance and stability for protonic ceramic cells.
Efforts have been underway for some time at Argonne National Laboratory to design structurally integrated and stabilized lithium-manganese-nickel-oxide cathode materials. The goal has been to find a cobalt-free, high-capacity cathode for a Li-ion battery that is competitive, both cost- and energy-wise, with lithium-nickel-manganese-cobalt-oxide (NMC) and lithium-iron-phosphate (LFP) products. This brief synopsis highlights the remarkable alchemy of LiMn 0.5 Ni 0.5 O 2 resulting from its well-known, slightly disordered layered structure and the recently discovered lithiated spinel phase and totally disordered rock-salt configurations. All three arrangements share a structurally compatible cubic-close-packed oxygen array. The lithiated spinel and layered components provide an intersecting network of two- and three-dimensional channels that facilitate Li + -ion transport, while a minor amount of an extensively disordered rock-salt component likely serves to enhance the structural and electrochemical stability of the electrode. The synopsis also encompasses the historical development of lithiated spinel electrode materials and structurally integrated systems.
Microscale thermophoresis (MST) is a technique used to measure the strength of molecular interactions. MST is a thermophoretic-based technique that monitors the change in fluorescence associated with the movement of fluorescent-labeled molecules in response to a temperature gradient triggered by an IR LASER. MST has advantages over other approaches for examining molecular interactions, such as isothermal titration calorimetry, nuclear magnetic resonance, biolayer interferometry, and surface plasmon resonance, requiring a small sample size that does not need to be immobilized and a high-sensitivity fluorescence detection. In addition, since the approach involves the loading of samples into capillaries that can be easily sealed, it can be adapted to analyze oxygen-sensitive samples. In this Bio-protocol, we describe the troubleshooting and optimization we have done to enable the use of MST to examine protein–protein interactions, protein–ligand interactions, and protein–nanocrystal interactions. The salient elements in the developed procedures include 1) loading and sealing capabilities in an anaerobic chamber for analysis using a NanoTemper MST located on the benchtop in air, 2) identification of the optimal reducing agents compatible with data acquisition with effective protection against trace oxygen, and 3) the optimization of data acquisition and analysis procedures. The procedures lay the groundwork to define the determinants of molecular interactions in these technically demanding systems.
Abstract Immunoisolation strategies that rely on porous membranes play an important role in cell transplantation therapies to protect cells from the host's immune system. These membranes must possess immunoprotective properties while facilitating the transport of nutrients and cell products to maintain the functional integrity of encapsulated cells. An easy and scalable process is described to fabricate a dual function porous polymeric membrane that shields cells against immune cell attack and promotes vascularization to address the nutritional and oxygen requirements of transplanted cells. The fabrication process results in a membrane cross‐section with a gradient of nanopores to micropores that support cell immunoisolation and interfacial vascularization requirements, respectively. The membranes demonstrate excellent cell compatibility and effectively prevent T cell transmigration without compromising glucose diffusion and oxygen permeability. In a murine subcutaneous implantation model, membranes are stable for 60 days and exhibit significantly reduced fibrous capsules, with enhanced vascularization near the membrane. These porous polymeric membranes can potentially be used as pro‐angiogenic immunoprotective membranes for cell transplantation applications where maximizing cell viability and function is of critical importance.
Triple oxygen isotopic compositions ( 16 O, 17 O, 18 O) have conventionally been measured via isotope ratio mass spectrometry using O 2 as an analyte. Conversion of sample oxygen to O 2 typically utilizes fluorination chemistry or catalytic equilibration between CO 2 and O 2 . Recently, laser spectroscopy has become a viable alternative for triple oxygen isotope (Δ' 17 O) measurements due to its ease and rapid throughput. Laser spectrometers are currently available for Δ' 17 O analysis of either H 2 O or CO 2 as the analyte gas. So far, these instruments have been used to measure Δ' 17 O of water, carbonate (CO 2 liberated by acid digestion), and atmospheric CO 2 samples. Here, we present a new method for high-precision Δ' 17 O analysis of CO 2 via tunable infrared laser direct absorption spectroscopy that is compatible with a wider range of geochemically important materials. This approach involves converting sample oxygen to CO 2 in two steps. First, the sample oxygen is liberated and reduced to CO by high-temperature conversion at 1450 °C in the presence of excess elemental carbon. Then, CO is catalytically converted to CO 2 over hot nickel at 350 °C. The conversion process is rapid (10 to 30 min) and quantitative. Spectroscopic Δ' 17 O analysis of the resulting CO 2 takes approximately 45 min. By measuring several oxygen isotope standards, we demonstrate that the method is precise (1σ = 12 per meg for procedural replicates) and accurate (within 11 per meg of previously reported values). The method can be applied to most pyrolytic materials where quantitative oxygen conversion is attainable, such as sulfate, phosphate, nitrate, and oxide minerals, water, and organic molecules.
Understanding crystallization in ambient environments is essential for scaling the fabrication of halide perovskite solar cells. Antisolvent-free perovskite deposition offers improved compatibility with high-throughput processing but introduces distinct crystallization dynamics relative to the more ubiquitous use of antisolvents in lab-scale perovskite fabrication. These dynamics are driven by interactions between solutes, solvent and the deposition environment. Using in situ wide-angle X-ray scattering during spin-coating and annealing, we demonstrate how relative humidity (RH) and oxygen, can be tuned to drive polytype evolution during ambient crystallization of formamidinium lead iodide to match that of inert synthesis and achieve comparable film and device quality. In an inert (N 2 ) environment, we find that perovskite films follow a well-established 2H → 3C phase transformation with a short period of coexistence of the 4H and 6H phase during heating. During crystallization in dry air (RH 0%), the added presence of oxygen leads to the dominance of 4H intermediate for an extended duration, establishing a 2H → 4H → 3C pathway. Introducing low humidity (RH 10%) suppresses the 4H phase to a short-lived intermediate above 100 °C, facilitating a more direct transition to the desired 3C phase and almost replicating the crystallization behavior observed under inert conditions. Interestingly, films crystallized under RH 10% show a lower onset temperature for the perovskite 3C phase than under N 2 . At higher humidity (RH 40%), the strong interaction of oxygen and moisture with iodoplumbates appears to stabilize higher order polytypes (4H and 6H). Devices fabricated under RH 10% achieve higher efficiency and enhanced stability compared to those produced under inert atmosphere. These findings provide mechanistic insight into crystallization pathways in different environments and provide a framework to transfer processes from inert to ambient conditions. The results highlight the critical role of controlled humidity in tuning antisolvent-free perovskite crystallization for scalable processing.
The Continuous Electron Beam Accelerator Facility (CEBAF) was the first large-scale accelerator to employ superconducting radiofrequency (SRF) cavities for continuous-wave operation. Ongoing research and development efforts continue to focus on increasing the intrinsic quality factor (Q 0 ) of these cavities in order to reduce cryogenic losses while maintaining operational gradients. Here, in this work, we report on the application of high-Q 0 surface treatments to single-cell and multicell C100 and C75 style 1.5 GHz niobium cavities used in the CEBAF accelerator. Nitrogen infusion and oxygen alloying via medium-temperature baking were applied under heat-treatment constraints relevant to existing cavity hardware. Both processes yielded substantial improvements in Q 0 at moderate accelerating gradients, achieving values of approximately 2 × 10 10 at 2.07 K and 20 MV/m. The effectiveness of nitrogen infusion at reduced annealing temperatures and the successful extension of oxygen alloying to multicell cavities are demonstrated. These results establish viable pathways for implementing high-Q 0 treatments in CEBAF-compatible cavities and support future integration into cryomodules for reduced operational cryogenic load.
The valorization of CO2 to chemicals beyond C1-2 products is receiving significant interest; however, the direct electrosynthesis of Cn molecules (n > 4) remains a challenge. Here, we present a two-step abiotic-biotic system for upgrading CO2 into the biopolymer, poly(3-hydroxybutyrate). In the electrolysis system, CO2 is converted into C2 oxygenates using a Cu-Ag tandem electrocatalyst. The electrolysis process generates a liquid stream containing ~ 200 mM acetate in a bio-compatible electrolyte. This electrosynthesized acetate is then fed to a bioreactor, where the substrate is upgraded by Cupriavidus necator to biopolymer with a maximum rate of 32 ± 3.5 mg L-1 h-1. We further demonstrate the purification of the resulting biopolymer into a powder. The high productivity of the abiotic-biotic system demonstrates its feasibility for sustainable chemical manufacturing.
Solid-state batteries are attractive energy storage systems as a result of their inherent safety, but their development hinges on advanced solid-state electrolytes (SSEs). Most SSEs remain largely confined to single-anion systems (e.g., sulfides, oxides, halides, and polymers). Through mixed-anion design strategy, we develop crystalline Li 3 Ta 3 O 4 Cl 10 (LTOC) and its derivatives with excellent ionic conductivities (up to 13.7 millisiemens per centimeter at 25°C) and electrochemical stability. The LTOC structure features mixed-anion spiral chains, consisting of corner-shared oxygen and terminal chlorine atoms, which induces continuous “tetrahedron-tetrahedron” Li-ion migration pathways with low energy barriers. Additionally, LTOC demonstrates holistic cathode compatibility, enabling solid-state batteries operation at 4.9 volts versus Li/Li + and low temperature, down to −50°C. In conclusion, these findings describe a promising class of superionic conductors for high-performance solid-state batteries.
Yttrium hydride is a promising material for a high-temperature neutron moderator in advanced micro and space reactors due to its high hydrogen density and relative thermal stability compared to other metal hydrides. However, yttrium hydride desorbs hydrogen rapidly at temperatures above 800°C, which is below the operational temperature range of some reactor designs. A hydrogen barrier coating of oxide on the hydride surface may inhibit hydrogen loss at 800°C and beyond, but the high-temperature compatibility between yttrium hydride and many oxides is currently unknown. The high-temperature compatibility of Al 2 O 3 , MgO, and Y 2 O 3 with YH 1.92 was examined by subjecting mixed oxide–hydride pellets to a 1200°C heat treatment then using a combination of diffractometry, microscopy, and spectroscopy to determine changes in the pellet composition as a result. Yttrium scavenged oxygen from both Al 2 O 3 and MgO to form Y 2 O 3 , resulting in significant loss of YH 1.92 . Yttrium reacted with reduced aluminum to form YAl 2 and several other compounds. Reduced magnesium volatilized above 1091°C and vacated the pellet. Only Y 2 O 3 did not appreciably react with YH 1.92 . Of the three oxides tested, only Y 2 O 3 was compatible with YH 1.92 at 1200°C based on the experimental criteria.
Concentrating solar power (CSP) with thermal energy storage (TES) has an estimated cost similar to solar photovoltaics (PV) with lithium-ion batteries (LIB), but CSP + TES has the potential for significantly reduced cost by operating above 700 degrees C. However, this requires a TES medium and containment infrastructure which are chemically compatible and do not degrade above 700 degrees C. MgCl2-KCl-NaCl (MKN) salt is a promising medium, but when MKN salt has small amounts of water and oxygen dissolved in it, it excessively corrodes conventional commercial alloys. Here, we consider refractory materials including graphite, carbon-carbon composite (C/C), and molybdenum because they maintain high mechanical strength at elevated temperatures and are expected to resist corrosion by MKN salt. While selection of refractory materials is often constrained by the need to remain chemically stable in air, this work uses an enclosure filled with inert gas to allow the use of materials like graphite and molybdenum. Notably, graphite components can seal against liquids unlike many brittle refractory materials. We demonstrate a centrifugal pump and mechanical seals made of refractory materials in a laboratory-scale circulation loop, which successfully operated continuously for more than 49 h at temperatures ranging from 750 degrees C to 950 degrees C with no mechanical failures or chemical degradation of the refractory materials. To the best of our knowledge, this is the highest temperature molten salt circulation loop that has been successfully developed, and this refractory infrastructure allows for operation at even much higher temperatures (<1600 degrees C) if a storage medium with a lower vapor pressure is used. The principles of this architecture are relevant to other applications with high temperature flowing metals and salts including Generation IV nuclear fission reactors for power production and molten salt electrolysis reactors for metallurgical processing.
Bicycloalkanes stand out as a replacement for aromatics from conventional jet fuel (CJF) because of their high energy density and lower freezing point. Most reports to date have focused on synthesizing bicycloalkanes using model compounds or single sugar components of lignocellulose. Here, we utilize all lignocellulosic sugars of corn stover (CS) to produce bicycloalkanes. First, furfural (FFR) and 5-hydroxymethyl furfural (5-HMF) are produced via acid-catalyzed dehydration, achieving combined FFRs molar yields ranging from 65% to 73%, respectively. The resulting FFRs are converted to cyclopentanones with molar yields within the range of 57%–63% via hydrogenation and Piancatelli rearrangement. Further aldol condensation of cyclopentanones yields C 10 -C 12 oxygenates with 80 mol %. Lastly, these oxygenates are directly hydrodeoxygenated to bicycloalkanes in a yield of 83.8 mol %. The resulting bicycloalkanes exhibit tier α fuel properties consistent with Jet A fuel (CJF) specifications and blend compatibility with CJF at a 37% volumetric ratio.
To describe the polar properties of nanosized Hf x Zr 1–x O 2–y , we evolve the “effective” Landau–Ginzburg–Devonshire (LGD) model based on the parametrization of the Landau expansion coefficients for polar and antipolar orderings. We have shown that the effective LGD model can predict the influence of screening conditions and size effects on phase diagrams, polarization reversal, and structural properties of nanosized Hf x Zr 1–x O 2–y of various shapes and sizes. To verify the model, we use the available experimental results for Hf x Zr 1–x O 2 thin films and oxygen-deficient HfO2–y nanoparticles prepared under different annealing conditions. X-ray diffraction, which was used to determine the phase composition of the HfO 2–y nanoparticles, revealed the formation of a ferroelectric orthorhombic phase in them. Micro-Raman spectroscopy was used to explore the correlation of lattice dynamics and structural changes that depend on the oxygen vacancy concentration in the HfO 2–y nanoparticles. Since our approach allows us to determine the conditions (shape, sizes, Zr content, and/or oxygen vacancy amount) for which nanosized Hf x Zr 1–x O 2–y are ferroelectric or antiferroelectric, we hope that the obtained results are useful for creation of next generation Si-compatible ferroelectric gate oxide nanomaterials.
Current encapsulation architectures for thin-film metal halide perovskite do not adequately eliminate all ambient stressors. Here, we develop low transmission rate barrier layers using atomic layer deposited (ALD) aluminum oxide grown directly on the completed photovoltaic (PV) device stack to provide an additional seal, prior to full packaging. We investigate the effect of deposition temperature and oxidant chemistries on the barrier growth for protection of perovskite photovoltaic devices. We characterize the layers individually, then integrate into devices to detail the tradeoff between protection and deposition compatibility. To enhance compatibility and impermeability, we present an approach using water as the aluminum oxidant during nucleation and switching from water to ozone for the remainder of the growth. At 50 nm, the barrier results in a water vapor transmission rate (WVTR) of 4.5·10 −4 g/m 2 /day, and 1,000-hour device stability under 45°C with 85% relative humidity without further packaging. This barrier provides sufficient protection to enable minimal degradation of the perovskite solar cells while completely submerged in water for 140 minutes. Additionally, we characterize the oxygen transmission rate (OTR) to be 0.49 cm 3 /m 2 /day at 23°C and 0% relative humidity, which is 1.5 orders of magnitude improvement over the OTR of the current encapsulation.
It has emerged as a potential candidate to improve the performance of monolithic-three-dimensional (M3D) integration of fused logic and memories through low-temperature in situ synthesis of high-performance metal–oxide–semiconductor (MOS) transistors. Here, we report the demonstration of the BEOL-compatible low thermal budget (350 °C) fabrication process of ultrathin-TiO2 transistors by the combination of RTA and UV-ozone treatment (RTA-UVOz). UV–ozone (UVOz) treatment of TiO2 anatase films significantly enhances stability, boosting ION current and field effect mobility (μ FE ) by two times of magnitude in TiO2 TFTs. UV ozone treatment helps to eliminate pre-existing oxygen vacancies and carbon contamination on TiO2 channels even at low temperature (100 °C), resulting in high-quality channel/dielectric interfaces with low interface states (D it ). During UVOz treatment, oxygen species (O x ) passivate the oxygen vacancies ($V$$^{2+}_{o}$), and hence low concentration of $V$$^{2+}_{o}$ would be left for ionization/de-ionization under PBS/NBS, leading to improved bias stress stability. Furthermore, the TiO 2 TFTs with thin ZrO 2 gate dielectric exhibited excellent performance including a lower subthreshold swing (SS) of 98 mV/dec with high drive I ON current ∼ 4.5 μA/μm, a high I ON /I OFF > 10 9 , and mobility μFE of 7 cm 2 /V-s under a battery powered voltage of 1 V. UV–ozone treatment enables high-performance, CMOS-compatible TiO 2 transistors with a low thermal budget, ideal for next-generation flexible, energy-efficient electronics.
This project aimed to develop a fundamental understanding of the factors that dictate activity and selectivity during electrochemical partial oxidation of multi-carbon organic molecules derived from biomass. Value-adding selective conversions of alcohols to aldehydes, and aldehydes to carboxylic acids were considered, with the ultimate goal to establish general principles for controlling selectivity in organic oxidations. Specific aims involved the use of furfural (FF) and 5-hydoxymethyfurfural (HMF) as model systems and seek to develop knowledge for control of mechanisms that permit selective conversions between oxygenate functional groups with prevention or control of C-C cleavage steps. Another major focus of the work was in achieving these transformations in acidic conditions, which contrasts most existing work (done in base), but is crucial toward compatibility with common pretreatments used to generate small molecules from lignocellulose (e.g. acid hydrolysis or pyrolysis). The work involved well-defined catalyst material synthesis, comparative kinetics, and operando spectroscopies (PI Holewinski), supported by quantum chemical simulations (PI Janik), enabling progress toward efficient, acid-stable oxidation catalysis for biomass upgrading.
Perovskite solar modules (PSMs) have emerged as a promising photovoltaic technology due to their high efficiency, low fabrication cost and compatibility with lightweight and flexible applications. However, ensuring long-term reliable performance under real-world conditions remains a critical barrier to commercialization. PSMs degrade through mechanisms that differ substantially from those affecting established technologies such as silicon, particularly under environmental stressors like ultraviolet light, oxygen, temperature cycling and reverse bias. Here we provide an analysis of the degradation pathways specific to perovskite modules and discuss why standard accelerated tests often fail to predict outdoor performance. We conceptualize challenges across material, device and module levels and evaluate strategies to mitigate ion migration, interfacial breakdown and encapsulation failure. By highlighting the need for realistic testing protocols and durable materials, we propose a framework highlighting key challenges, technological pathways and the trade-offs required to extend perovskite module lifetimes towards long-term operation, aiming to guide the development of PSMs capable of a 30-year operational lifetime.
Breaking the memory wall in advanced computing architectures will require complex 3D integration of emerging memory materials such as ferroelectrics─either within the back-end-of-line (BEOL) of CMOS front-end processes or through advanced 3D packaging technologies. Achieving this integration demands that memory materials exhibit high thermal resilience, with the capability to operate reliably at elevated temperatures, such as 125°C, due to the substantial heat generated by front-end transistors. However, silicon-compatible HfO 2 -based ferroelectrics tend to exhibit antiferroelectric-like behavior in this temperature range, accompanied by a more pronounced wake-up effect, posing significant challenges to their thermal reliability. Here, we report that by introducing a thin tungsten oxide (WO 3–x ) layer─known as an oxygen reservoir─and carefully tuning its oxygen content, ultrathin Hf 0.5 Zr 0.5 O 2 (5 nm) films can be made robust against the ferroelectric-to-antiferroelectric transition at elevated temperatures. This approach not only minimizes polarization loss in the pristine state but also effectively suppresses the wake-up effect, reducing the required wake-up cycles from 10 5 to only 10 at 125°C, a qualifying temperature for back-end memory integrated with front-end logic, as defined by the JEDEC standard. First-principles density functional theory (DFT) calculations reveal that WO 3 enhances the stability of the ferroelectric orthorhombic phase (o-phase) at elevated temperatures by increasing the tetragonal-to-orthorhombic phase energy gap and promoting favorable phonon mode evolution, thereby supporting o-phase formation under both thermodynamic and kinetic constraints.