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Cobalt-free and high-rate stable 5V lithium nickel manganese oxide spinel cathodes enabled via surface oxygen vacancies

Spinel LiNi 0.5 Mn 1.5 O 4 offers both the high-rate, low-cost and safety advantages of LiFePO 4 and the high energy density of LiNiₓMnᵧCo₁₋ₓ₋ᵧO₂ and LiNiₓCoᵧAlzO₂ cathodes. However, the large operating voltage of these materials induces electrolyte oxidation, which degrades the interface and drives Mn dissolution. These reactions are further exacerbated at high rates due to temperature rise. In this study, we discover that ammoniacal treatment followed by annealing introduces a high density of oxygen vacancies in the “near-surface region” of LiNi 0.5 Mn 1.5 O 4 particles. These vacancies release electrons changing the oxidation state of Mn and suppressing its tendency to oxidize the electrolyte. Further, these vacancies enhance the electrode’s electronic conductivity (by ∼3-fold) and Li + diffusivity (by ∼2-fold) greatly improving charge transport, especially when operated at high rates. This results in an across-the-board improvement in self-discharge, specific capacity, energy density, rate capability, coulombic efficiency and cycling stability. When cycled at ∼200 mA g −1 , the capacity fade averaged over 3000 cycles for the surface vacancy-enriched material is ∼0.0167% per cycle compared to an order of magnitude higher fade rate for the baseline material. In conclusion, these findings reveal the potential of targeted surface oxygen vacancy doping to develop cobalt-free and high energy density cathodes that tolerate fast charging and deliver improved cycle life.

Cobalt-free cathodes

Technology Demonstrator of an Americium-Fuelled Radioisotope Stirling Generator

Americium-241 is used as the fuel of choice in European Radioisotope Power Systems. The University of Leicester have developed a number of systems using this fuel type, including a 200 Wth heat source. To maximise the electrical output that can be generated from the heat source, the University of Leicester and NASA Glenn Research Center have collaborated on a radioisotope Stirling generator concept, building on the long heritage of dynamic power conversion developments at NASA GRC. Here we present the design of a technology demonstrator of the Americium-fuelled Radioisotope Stirling Generator (Am-RSG).

Americium-241

Ammonolysis with N 2 -diluted NH 3 suppresses Ta( IV ) defects in BaTaO 2 N and enhances photocatalytic water oxidation

BaTaO 2 N stands out among oxynitride photocatalysts because of its ability to capture visible light and to drive the photoelectrochemical water oxidation reaction. However, its solar energy conversion performance is limited by electron–hole recombination at Ta( IV ) defects in the material. These defects are formed by overreduction of the Ta(v) oxide precursor by excess ammonia under the high temperature conditions during ammonolysis. Here we show for the first time that Ta( IV ) defect concentrations can be lowered by conducting the ammonolysis reaction in mixed NH 3 /N 2 gas. The obtained BaTaO 2 N samples crystallize in the cubic CaTiO 3 structure type and form 200–300 nm faceted nanocrystals, based on X-ray diffraction, scanning electron microscopy, and HRTEM. Electron paramagnetic resonance spectra observe the Ta( IV ) defects at g = 1.999 and confirm an 11-fold reduction for the product synthesized in mixed (0.13 : 1.0 vol) NH 3 /N 2 gas, equivalent to 1.14 × 10 16 cm −3 Ta( IV ) ions. This optimized BaTaO 2 N has nearly twice the photocatalytic oxygen evolution activity (AQE of 6.78% at 400 nm) of a reference material made with 1.0 atm ammonia and 78% higher photoelectrochemical water oxidation photocurrent (0.9 mA cm −2 at 1.23 V vs. RHE) under simulated sunlight. According to X-ray photoelectron spectroscopy, remaining Ta( IV ) defects are concentrated in the surface region of the BaTaO 2 N particles, where >50% of all Ta ions are found in the +4 oxidation state. This surface Ta( IV ) population can be directly observed in Vibrating Kelvin Probe Surface Photovoltage Spectra (VK-SPV) via its 1.2–1.4 eV photovoltage onset. Here, it suggests that the surface Ta( IV ) ions contribute empty d-states 0.5–0.7 eV below the BaTaO 2 N conduction band edge. These findings highlight how the energetics and concentrations of Ta( IV ) defects influence the photoelectrochemical water oxidation ability of BaTaO 2 N. Additionally, the work establishes ammonolysis with diluted NH 3 as a new tool to minimize defects in BaTaO 2 N and to raise its solar energy conversion efficiency toward its theoretical limit. Because of its simplicity, the reduced ammonia pressure strategy will likely be applicable to other oxynitrides, which generally suffer from overreduction problems during ammonolysis.

Salmanion, Mahya [University of California, Davis,

Novel PtNi single-atom–nanocluster (SA–NC) ensembles promote Tafel kinetics and ampere-class AEM hydrogen evolution

The development of efficient, durable, and low-PGM electrocatalysts for the hydrogen evolution reaction (HER) in alkaline media is critical for next-generation electrolysis technologies. We report a facile two-step synthesis of highly dispersed PtNi and PtNi-nitride nanoclusters (NCs) (~2.3 nm) with ultralow Pt content (0.5 at.%) anchored on N-doped Vulcan carbon. Structural and compositional characterization via XAS, XPS, HAADF-STEM, HRTEM, and EDS mapping established key structure–activity relationships across varying Pt/Ni ratios and pyrolysis temperatures. The Pt0.5Ni0.5/C-750 catalyst, an ensemble of PtNi M-N-C type single-atom (SA) moieties with neighboring PtNi nanoclusters (NC), exhibited superior HER performance in alkaline media, achieving overpotentials of 30, 115, and 210 mV at 10, 100, and 500 mA cm−2, respectively. Despite at a lower Pt content, this novel SA–NC ensemble outperformed commercial Pt/C by ~36%. A standardized literature comparison with contemporary Pt- and Ru-doped analogues reveals the as-prepared Pt0.5Ni0.5/C-750 to sit at the apex of Tafel-limited kinetics and low overpotential at 100 mA cm−2. Tafel-limited Tafel slopes in both alkaline and acidic regimes confirm favorable proton recombination kinetics. Mass activities at 200 mV reached 13.8 and 18.84 A mgPt−1 in alkaline and acidic media, respectively. However, excessive nitridation (e.g., at 650 °C) adversely altered Pt electronic structure and HER kinetics. While Ni enhanced alkaline HER, acidic HER favored Ni-free analogues. Pt0.5Ni0.5/C-750 also demonstrated robust temperature responsiveness and 300-h operational stability at high current densities (0.5–1.0 A cm−2) in MEA tests. This work presents a scalable strategy for designing thermally responsive, durable, and compositionally tunable NC catalysts with neighboring SA moieties for alkaline electrolysis.

AEMWE

Complex-Concentrated Anion Doping Enables Ultra-Stable Lattice Oxygen and Structural Integrity in Lithium-Rich Layered Oxide Cathodes

Lithium- and manganese-rich layered oxides (LMR) stand out as next-generation lithium-ion cathode chemistries, which harness both transition-metal and lattice-oxygen redox processes to deliver exceptional capacity and energy density. However, their full potential is hindered by intrinsic oxygen instability and structural degradation, resulting in pronounced voltage fade and capacity decay. Here, we present a complex-concentrated anion-doping paradigm in which multiple anions, F, Br, and S, are incorporated into the oxygen sublattice to enhance oxygen-redox and structural stability. X-ray absorption spectroscopy and aberration-corrected scanning transmission electron microscopy confirm ultra-stable local oxygen coordination environments during long-term cycling, with detrimental phase transformations and oxygen-loss-induced cavitation dramatically inhibited. Notably, we show that the characteristic LiTM6 transition metal (TM) honeycomb ordering is preserved even after electrochemical cycling. Concurrently, this strategy yields an unprecedented volume change of only 0.63% upon charging to 4.8 V vs. Li+/Li, achieving the first zero-strain LMR cathode. The resulting LMR cathode delivers ultralow voltage fade (1 mV per cycle during the first 100 cycles and becomes negligible in subsequent cycles) and outstanding energy retention (93% after 200 cycles) in a pouch cell configuration. Our complex-concentrated anion-doping concept establishes a broadly applicable strategy for resolving chemo-mechanical failure mechanisms in ceramic intercalation electrodes for next-generation energy storage.

Li-ion batteries

Effect of Fe on Co-Based SiO2Al2O3 Mixed Support Catalyst for Fischer–Tropsch Synthesis in 3D-Printed SS Microchannel Microreactor

This research explores the effect of a composite support of SiO2 and Al2O3 with Fe and Co incorporated as catalysts for Fischer–Tropsch synthesis (FTS) using a 3D-printed stainless steel (SS) microchannel microreactor. Two mesoporous catalysts, FeCo/SiO2Al2O3 and Co/SiO2Al2O3, were synthesized via a one-pot (OP) method and extensively characterized using N2 physisorption, XRD, SEM, TEM, H2-TPR, TGA-DSC, FTIR, and XPS. H2-TPR results revealed that the synthesis method significantly affected the reducibility of metal oxides, thereby influencing the formation of active FTS sites. SEM-EDS and TEM further revealed a well-defined hexagonal matrix with a porous surface morphology and uniform metal ion distribution. FTS reactions, carried out in the 200–350 °C temperature range at 20 bar with a H2/CO molar ratio of 2:1, exhibited the highest activity for FeCo/SiO2Al2O3, with up to 80% CO conversion. Long-term stability was evaluated by monitoring the catalyst performance for 30 h on stream at 320 °C under identical reaction conditions. The catalyst was initially active for the methanation reaction for up to 15 h, after which the selectivity for CH4 declined. Correspondingly, the C4+ selectivity increased after 15 h of time-on-stream, indicating a shift in the product distribution toward longer-chain hydrocarbons. This trend suggests that the catalyst undergoes gradual activation or restructuring under reaction conditions, which enhances chain growth over time. The increase in C4+ products may be attributed to the stabilization of the active sites and suppression of methane or light hydrocarbon formation.

Biochemistry & Molecular Biology

Simulating the Lunar Thermal Environment for the Surface-Deployed LEMS Artemis III TVAC Test

The Lunar Environment Monitoring Station (LEMS) is an autonomous, survive-the lunar-night seismic suite to be deployed on the Lunar surface by the Artemis III crew and designed to operate continuously for two years. It will see the extremes of the Lunar south pole thermal environment where surface temperatures range from -200°C to +20°C and where nighttime duration is at least 354 hours. Given power and mass constraints, the thermal system is limited to 2.5 Watts of heat during the lunar night. Presented is the system thermal vacuum test plan and configuration to validate the thermal control system performance in a flight-like environment. The test will measure the nighttime heat leaks for the bus and 18 seismometers to ensure lunar night survival and operability.

Thermal

Simulating the Lunar Thermal Environment for the Surface-Deployed LEMS Artemis III TVAC Test

The Lunar Environment Monitoring Station (LEMS) is an autonomous, survive-the lunar-night seismic suite to be deployed on the Lunar surface by the Artemis III crew and designed to operate continuously for two years. It will see the extremes of the Lunar south pole thermal environment where surface temperatures range from -200°C to +20°C and where nighttime duration is at least 354 hours. Given power and mass constraints, the thermal system is limited to 2.5 Watts of heat during the lunar night. Presented is the system thermal vacuum test plan and configuration to validate the thermal control system performance in a flight-like environment. The test will measure the nighttime heat leaks for the bus and 18 seismometers to ensure lunar night survival and operability.

Thermal

Simulating the Lunar Thermal Environment for the Surface-Deployed LEMS Artemis III TVAC Test

The Lunar Environment Monitoring Station (LEMS) is an autonomous, survive-the lunar-night seismic suite to be deployed on the Lunar surface by the Artemis III crew and designed to operate continuously for two years. It will see the extremes of the Lunar south pole thermal environment where surface temperatures range from -200°C to +20°C and where nighttime duration is at least 354 hours. Given power and mass constraints, the thermal system is limited to 2.5 Watts of heat during the lunar night. Presented is the system thermal vacuum test plan and configuration to validate the thermal control system performance in a flight-like environment. The test will measure the nighttime heat leaks for the bus and 18 seismometers to ensure lunar night survival and operability.

TVAC

Gas permeation properties of amorphous zeolitic imidazolate framework membranes made by atomic/molecular layer deposition

Amorphous metal-organic framework (MOF) membranes are desirable because they may retain some of the molecular sieving properties of their crystalline counterparts while being free of grain boundary defects, which often hinder the consistent achievement of high membrane performance. However, current methods, like melting and compression, for fabricating amorphous MOF membranes involve multi-step processes that require the formation of a crystalline membrane first, that is then amorphized, and therefore, could be challenging to scale. Here, we utilize atomic/molecular layer deposition (ALD/MLD) of diethylzinc (DEZ) and 2-methylimidazole (2mIm) to directly synthesize ultrathin amorphous zeolitic imidazolate framework (aZIF) deposits on γ-alumina-coated α-alumina supports. As the number of ALD/MLD cycles increased from 10 to 300, gas permeances decreased while ideal selectivities increased. Mixture separation factors for C3H6/C3H8, CO2/N2, and H2/C3H8 as high as 4, 37, and 194, respectively, were obtained. At 200 °C and 2.5 bar equimolar feed of H2 and C3H8, a H2/C3H8 mixture separation factor of 185 is obtained with an H2 permeance of ca. 4.15x10-8 mol/m2-s-Pa (124 GPU). Additionally, the membrane achieves a CO2/N2 mixture separation factor of 37 at 25 °C and 1 bar with a CO2 permeance of ca. 3.96x10-8 mol/m2-s-Pa (118 GPU). Considering the vast array of compositionally distinct aZIFs that can be potentially deposited by this approach, an enormously large parameter space for membrane design is emerging to be explored.

36 MATERIALS SCIENCE

Technology & Design Innovations to Maximize the Reduction Effect on DCFC Unit Cost Economics (Max‐REDUCE)

With the high cost and reliability issues of DCFC infrastructure the project specifically addressed the needs of innovating on the AC to DC power conversion. We proved the integration of a new power module into existing charger units, and that theoretical educational work on single stage energy conversion is commercially viable, and a reduced cost compared to existing methods. Our A sample shown 3 PH 480VAC 60hz to 350VDC 8.5kW power transfer, and our software and simulation proved efficiency greater than 97% from 20kW to > 60kW, over the DC output voltage range 200 – 1200V. The project was stopped before we could implement B sample and execute full power testing, validation and integration into a demonstration charger (budget period 3).

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI

High Temperature - Thin Film Strain Gages Based on Alloys of Indium Tin Oxide

A stable, high temperature strain gage based on reactively sputtered indium tin oxide (ITO) was demonstrated at temperatures up to 1050 C. These strain sensors exhibited relatively large, negative gage factors at room temperature and their piezoresistive response was both linear and reproducible when strained up to 700 micro-in/in. When cycled between compression and tension, these sensors also showed very little hysteresis, indicating excellent mechanical stability. Thin film strain gages based on selected ITO alloys withstood more than 50,000 strain cycles of +/- 500 micro-in/in during 180 hours of testing in air at 1000 C, with minimal drift at temperature. Drift rates as low as 0.0009%/hr at 1000 C were observed for ITO films that were annealed in nitrogen at 700 C prior to strain testing. These results compare favorably with state of the art 10 micro-m thick PdCr films deposited by NASA, where drift rates of 0.047%/hr at 1050 C were observed. Nitrogen annealing not only produced the lowest drift rates to date, but also produce the largest dynamic gage factors (G = 23.5). These wide bandgap, semiconductor strain sensors also exhibited moderately low temperature coefficients of resistance (TCR) at temperatures up to 1100 C, when tested in a nitrogen ambient. A TCR of +230 ppm/C over the temperature range 200 C < T < 500 C and a TCR of -469 ppm/C over the temperature range 600 C < T < 1100 C was observed for the films tested in nitrogen. However, the resistivity behavior changed considerably when the same films were tested in oxygen ambients. A TCR of -1560 ppm/C was obtained over the temperature range of 200 C < T < 1100 C. When similar films were protected with an overcoat or when ITO films were prepared with higher oxygen contents in the plasma, two distinct TCR's were observed. At T < 800 C, a linear TCR of -210 ppm/C was observed and at T > 800 C, a linear TCR of -2170 DDm/C was observed. The combination of a moderately low TCR and a relatively large gage factor make these semiconducting oxide films promising candidates for the active strain elements in high temperature thin film strain gages, particularly in applications where static strain measurement is desired.

Otto J Gregory

Harness Thermal Heat Loss Measurement for a Lunar Surface-Deployed LEMS Artemis III Payload

The Lunar Environment Monitoring Station (LEMS) is an autonomous, survive-the-lunar-night seismic suite to be deployed on the Lunar surface by the Artemis III crew and designed to operate continuously for two years. It will see the extremes of the Lunar south pole thermal environment where surface temperatures range from -200°C to +20°C and where nighttime duration is at least 354 hours. Given power and mass constraints, the thermal system is limited to 2.5 Watts of heat during the lunar night. The electrical harnessing named the Signal and Power Passthrough (SAPP) was designed to minimize heat loss while meeting power and signal integrity requirements. To mitigate risk due to uncertainty associated with the harnessing materials, routing, and tie-downs, a flight-like thermal conductance test was performed to measure the heat loss. The test methodology, results, and model correlation are presented.

TVAC

Harness Thermal Heat Loss Measurement for A Lunar Surface-Deployed LEMS Artemis III Payload

The Lunar Environment Monitoring Station (LEMS) is an autonomous, survive-the-lunar-night seismic suite to be deployed on the Lunar surface by the Artemis III crew and designed to operate continuously for two years. It will see the extremes of the Lunar south pole thermal environment where surface temperatures range from -200°C to +20°C and where nighttime duration is at least 354 hours. Given power and mass constraints, the thermal system is limited to 2.5 Watts of heat during the lunar night. The electrical harnessing named the Signal and Power Passthrough (SAPP) was designed to minimize heat loss while meeting power and signal integrity requirements. To mitigate risk due to uncertainty associated with the harnessing materials, routing, and tie-downs, a flight-like thermal conductance test was performed to measure the heat loss. The test methodology, results, and model correlation are presented.

Thermal

Harness Thermal Heat Loss Measurement for A Lunar Surface-Deployed LEMS Artemis III Payload

The Lunar Environment Monitoring Station (LEMS) is an autonomous, survive-the-lunar-night seismic suite to be deployed on the Lunar surface by the Artemis III crew and designed to operate continuously for two years. It will see the extremes of the Lunar south pole thermal environment where surface temperatures range from -200°C to +20°C and where nighttime duration is at least 354 hours. Given power and mass constraints, the thermal system is limited to 2.5 Watts of heat during the lunar night. The electrical harnessing named the Signal and Power Passthrough (SAPP) was designed to minimize heat loss while meeting power and signal integrity requirements. To mitigate risk due to uncertainty associated with the harnessing materials, routing, and tie-downs, a flight-like thermal conductance test was performed to measure the heat loss. The test methodology, results, and model correlation are presented.

TVAC

Safe, High Power/Voltage Battery Module Design Challenges

NASA seeks to demonstrate a path for achieving safe, high power, and high performing Li-ion battery designs for the purpose of establishing design guidelines for our aeronautic and spacecraft applications. Safe means passively resistant to thermal runaway propagation of any single cell catastrophic thermal runaway. High power means capable of 3C continuous discharge without overheating. High performing means achieving > 160 Wh/kg, 200 Wh/L. The biggest challenge has been balancing a high flux light weight path for cell heat dissipation during the high rate discharge that minimizes thermal gradients between cells and also protects adjacent cells from the heat load of thermal runaway cell. Our solution includes an oscillating heat pipe spine that contacts every 18650 cell in the pack and careful cell design selection to maximize the range of initial temperatures conditions where the battery can safely complete the 3C discharge.

Thermal runaway

Formation and Shape Changing of Conductive Helical Ribbons via Deposition of Highly Stressed Films on Mechanically Responsive Substrates

Abstract This work demonstrates that the electrodeposition of highly stressed films on compliant ribbons is a robust process to obtain helical structures with excellent mechanical stability and potentially high thermal and electrical conductance. Electrodeposition on end‐tethered ribbons alters their axial and bending stiffness while imparting mechanical stress to drive the formation of a helix with a microscale diameter and pitch in a controlled and scalable manner. The process generates helices with diameters and pitches between 80 and 200 µm and lengths as large as several millimeters. The approach is amenable to parallel processing a large number of 3D structures on any substrate, including large‐area semiconductor wafers. This phenomenon is explained in terms of the change of stress gradients as material is added. Applications of the fabricated helices include antennas, metamaterials, and slow‐wave structures in frequency ranges not previously attainable.

Chemistry

Block copolymer self-assembly derived mesoporous magnetic materials with three-dimensionally (3D) co-continuous gyroid nanostructure

Magnetic nanomaterials are gaining interest for their many applications in technological areas from information science and computing to next-generation quantum energy materials. While magnetic materials have historically been nanostructured through techniques such as lithography and molecular beam epitaxy, there has recently been growing interest in using soft matter self-assembly. In this work, a triblock terpolymer, poly(isoprene-block-styrene-block-ethylene oxide) (ISO), is used as a structure directing agent for aluminosilicate sol nanoparticles and magnetic material precursors to generate organic–inorganic bulk hybrid films with co-continuous morphology. After thermal processing into mesoporous materials, results from a combination of small angle X-ray scattering (SAXS) and scanning electron microscopy (SEM) are consistent with the double gyroid morphology. Nitrogen sorption measurements reveal a type IV isotherm with H1 hysteresis, and yield a specific surface area of around 200 m 2 g −1 and an average pore size of 23 nm. The magnetization of the mesostructured material as a function of applied field shows magnetic hysteresis and coercivity at 300 K and 10 K. Comparison of magnetic measurements between the mesoporous gyroid and an unstructured bulk magnetic material, derived from the identical inorganic precursors, reveals the structured material exhibits a coercivity of 250 Oe, opposed to 148 Oe for the unstructured at 10 K, and presence of remnant magnetic moment not conventionally found in bulk hematite; both of these properties are attributed to the mesostructure. This scalable route to mesoporous magnetic materials with co-continuous morphologies from block copolymer self-assembly may provide a pathway to advanced magnetic nanomaterials with a range of potential applications.

Chemistry