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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 37 records · Page 2

Engineering metal-oxide interface by depositing ZrO 2 overcoating on Ni/Al 2 O 3 for dry reforming of methane

Zirconium oxide (ZrO 2 ) was deposited onto Ni/Al 2 O 3 catalyst as overcoating by atomic layer deposition (ALD) for dry reforming of methane (DRM). High-temperature heating during H-2-reduction could transform the ALD-prepared ZrO 2 thin film to tetragonal phase and crack the encapsulating layer on Ni sites, which constructed a beneficial Ni-ZrO x interface. Here, interfacial surface oxygen vacancies on ZrO 2 overcoating were induced by the partial reduction of ZrO 2 surface during high-temperature H 2 reduction, with the assistance of Ni. During DRM, the interfacial oxygen vacancies enhanced CO 2 activation by dissociating CO 2 and releasing active O, thereby limiting carbon formation. For DRM at 700 °C and 800 °C, Ni/Al 2 O 3 with 5 cycles of ZrO 2 ALD overcoating enhanced both activity and stability significantly. For a 100-h DRM test at 600 °C, no deactivation was observed for the Ni/Al 2 O 3 catalyst with 10 cycles of ZrO 2 ALD overcoating, as compared to 59% relative activity loss of Ni/Al 2 O 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Blended conventional and high oxygen permeability ionomers as a fuel cell electrode binder

Ionomer strongly influences the performance of proton exchange membrane fuel cells (PEMFCs), affecting catalyst activity and reactant transport within the electrodes. While recent work on high oxygen permeability ionomers (HOPI) has demonstrated improved performance compared to conventional perfluorosulfonic acid (PFSA) ionomers such as Nafion™, there have also been reports of increased cracking in fabricated electrodes. We investigated the effects of blending HOPI with Nafion™ ionomer dispersions when fabricating cathode catalyst layers (CCLs). Small-angle x-ray scattering suggests that the ionomers mix well, and adsorption measurements indicate that HOPI adsorbs less strongly to the carbon-supported platinum (Pt) catalyst, and in blends, the Nafion™ ionomer exhibits a greater degree of adsorption. Imaging CCLs revealed a decrease in crack formation in blended samples as HOPI content decreased, with 14% HOPI having the lowest crack density. In a membrane electrode assembly (MEA) using a high surface area carbon support, the 14% HOPI blend exhibited similar performance to 100% HOPI. However, similar performance enhancements were not achieved with a medium surface area carbon support. These findings suggest a path for low-crack CCLs with enhanced oxygen transport, while highlighting a need for further investigation of ionomer blending towards efficient and durable PEMFCs.

25 ENERGY STORAGE↗

AGR TRISO Fuel Performance Modeling in FY-25

This report summarizes the activities performed in FY-25 to support fuel performance modeling for the Advanced Gas Reactor (AGR) Fuel Development and Qualification Program. This includes implementation of a new uranium oxycarbide (UCO) kernel swelling rate model, inner pyrolytic carbon (IPyC) cracking behavior and failure predictions, development of new UCO and silicon carbide (SiC) cesium diffusion parameters, and the thermomechanical behavior of particle layers using experimental data from micro-tensile strength testing.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

In–Depth Analysis of the Degradation Mechanisms of High–Nickel, Low/No–Cobalt Layered Oxide Cathodes for Lithium–Ion Batteries

A rational compositional design of high-nickel, cobalt-free layered oxide materials for high-energy and low-cost lithium-ion batteries would be expected to further propel the widespread adoption of electric vehicles (EVs), yet a composition with satisfactory electrochemical properties has yet to emerge. The previous work has demonstrated a promising LiNi 0.883 Mn 0.056 Al 0.061 O 2 (NMA-89) composition that outperformed high-nickel, cobalt-containing analogs in cycling stability and maintained a comparable rate performance and thermal stability. Herein, the capacity fading mechanism of NMA-89 in a pouch full cell with a 4.2 V cutoff is compared to that of its cobalt-containing analogs. The results reveal that particle cracking in LiNi 0.89 Mn 0.055 Co 0.055 O 2 (NMC-89) and LiNi 0.883 Co 0.053 Al 0.064 O 2 (NCA-89) leads to a loss of active material and an increase in surface area, thereby exacerbating structural and surface instabilities, accelerating impedance and polarization growth, and ultimately reducing their capacity retentions. LiNi 0.89 Mn 0.044 Co 0.042 Al 0.013 Mg 0.011 O 2 (NMCAM-89) and NMA-89 experience subdued surface reactions and maintain spherical particle structures, both of which are conducive to their capacity retentions during long-term cycling. Furthermore, this investigation offers insights into how specific transition-metal ions dictate the electrochemical stability of high-Ni layered oxide cathode materials, highlights the benefit of Mn-Al combination in NMA-89, and presents potential strategies to further enhance the performance of this novel class of cathode materials.

degradation mechanisms↗

Coupling Redox Compensation and Interfacial Stabilization in Low-Ni O3-Type Sodium Layered Oxide Cathodes

Low-Ni O3-type sodium layered oxides are attractive cathodes for cost-robust sodium-ion batteries, yet high-voltage cycling is often limited by Fe-driven degradation, including cation migration/dissolution, irreversible slab gliding with large strain, particle cracking, and accelerated interfacial parasitic reactions. Here, in this study, we introduce a redox-interface codesign strategy using stoichiometric, charge-balanced Cu 2+ /Ti 4+ cosubstitution while preserving full Na stoichiometry, transitioning from NaNi 1/4 Fe 1/2 Mn 1/4 O 2 to NaNi 1/4 Fe 1/5 Mn 1/4 Cu 3/20 Ti 3/20 O 2 . With the cosubstitution, Cu and Ti suppress Fe migration and dissolution and facilitate sustained Fe oxidation at high voltage. Meanwhile, Cu is also shown to be redox-active, providing reversible cationic charge compensation that mitigates the capacity penalty typically associated with reducing Fe participation. Operando diffraction and spectroscopy collectively indicate a more reversible high-voltage structural evolution with suppressed Fe-related irreversibility. Particularly, spontaneous Ti enrichment at surface/grain-boundary regions stabilizes the cathode−electrolyte interface and promotes a more NaF-rich interphase signature. This work establishes a generalizable route to reconcile stability and capacity in low-Ni, Fe-containing O3 sodium layered oxide cathodes via compositionally encoded bulk-interfacial coupling.

25 ENERGY STORAGE↗

Sequentially regular polymer acceptors featuring flexible spacers for high-performance and mechanically robust all-polymer solar cells

Developing high-performance and mechanically robust polymer solar cells (PSCs) is crucial for realizing wearable power sources. While efficient all-polymer solar cells (all-PSCs) can be fabricated from polymerized small-molecule acceptors (PSMAs) with high optical absorption and electron mobilities, they still show limited mechanical robustness. Here, we achieve highly efficient and mechanically robust all-PSCs by designing a PSMA (PYFS-Reg) containing sequence-regular flexible spacers (FSs). The regular incorporation of the FS units into PSMAs is essential in simultaneously improving the electrical and mechanical properties of blend films. As a result, all-PSCs featuring PYFS-Reg achieve a high power conversion efficiency (PCE = 16.1%) and stretchability (crack onset strain (COS) = 22.4%), outperforming PSMAs without FSs (i.e., PYBDT, PCE = 12.6% and COS = 11.7%) or with randomly distributed FSs (i.e., PYFS-Ran, PCE = 12.2% and COS = 18.1%). Importantly, these all-PSCs are fabricated by an environmentally benign, non-halogenated solvent process. To further demonstrate their feasible applications in wearable devices, we construct intrinsically stretchable (IS) all-PSCs by using PYFS-Reg-based active layers, which exhibit a high PCE (10.6%) and excellent device stretchability (strain at PCE 80% = 36.7%).

14 SOLAR ENERGY↗

High‐Loading Lithium‐Sulfur Batteries with Solvent‐Free Dry‐Electrode Processing

Abstract Lithium‐sulfur (Li‐S) batteries, with their high energy density, nontoxicity, and the natural abundance of sulfur, hold immense potential as the next‐generation energy storage technology. To maximize the actual energy density of the Li‐S batteries for practical applications, it is crucial to escalate the areal capacity of the sulfur cathode by fabricating an electrode with high sulfur loading. Herein, ultra‐high sulfur loading (up to 12 mg cm −2 ) cathodes are fabricated through an industrially viable and sustainable solvent‐free dry‐processing method that utilizes a polytetrafluoroethylene binder fibrillation. Due to its low porosity cathode architecture formed by the binder fibrillation process, the dry‐processed electrodes exhibit a relatively lower initial capacity compared to the slurry‐processed electrode. However, its mechanical stability is well maintained throughout the cycling without the formation of electrode cracking, demonstrating significantly superior cycling stability. Additionally, through the optimization of the dry‐processing, a single‐layer pouch cell with a loading of 9 mg cm −2 and a novel multi‐layer pouch cell that uses an aluminum mesh as its current collector with a total loading of 14 mg cm −2 are introduced. To address the reduced initial capacity of dry‐processed electrodes, strategies such as incorporating electrocatalysts or employing prelithiated active materials are suggested.

Chemistry↗

Deconstructing the High Voltage Degradation Mechanisms in Na 2/3 Ni 1/3 Mn 2/3 O 2 with Single Crystals and Advanced Electrolyte

Abstract Sodium layered oxide cathodes can uniquely benefit from the existing lithium‐ion battery industry as sodium‐ion batteries gain traction as a potential low‐cost, drop‐in replacement. However, achieving relevant energy density with a suitable cycle life remains a challenge for sodium layered oxides. At high operating potentials, several competing degradation mechanisms prevent P2‐type Na 2/3 Ni 1/3 Mn 2/3 O 2 (≈550 Wh kg −1 ) from achieving meaningful cycle life—with bulk structural instability and surface reactivity being the primary retractors. Herein, the issue of particle cracking is addressed through detailed synthesis methods of “single‐crystal” materials. By comparison to a polycrystalline baseline, the single‐crystal materials quantify the capacity loss due to isolation of active material caused by intergranular particle cracking. The single crystal materials are then employed in cells with an advanced, “localized saturated electrolyte” (LSE) to demonstrate the magnitude of capacity loss due to electrolyte decomposition at the cathode surface. Mitigation of the surface reactivity through the LSE electrolyte effectively demonstrates the elevated importance of surface reactivity at high voltages despite the onset of egregious particle cracking. This work aims to guide future research into understanding molten‐salt assisted syntheses and advance the debate on surface versus bulk degradation.

Darga, Joe↗

Establishing Co‐Continuous Network of Conjugated Polymers and Elastomers for High‐Performance Polymer Solar Cells with Extreme Stretchability

High power conversion efficiency (PCE) and mechanical robustness are prerequisites for wearable applications of organic solar cells (OSCs). However, stretchability of present active systems (i.e., crack-onset strain (COS) < 30%) should be improved. While introducing elastomers into active systems is considered a simple method for improving stretchability, the inclusion of elastomers typically results in a decrease in PCE of the OSC with a limited enhancement in the stretchability due to lack of interconnected electrical and mechanical pathways. In this study, it is developed efficient and intrinsically stretchable (IS)-OSCs with exceptional mechanical robustness, by constructing co-continuous networks of conjugated polymers (D18) and elastomers (SEBS) within active layers. It is demonstrated that the blend film with a specific ratio (40:60 w/w) of D18:SEBS is crucial for forming co-continuous structures, establishing well-connected mechanical and electrical channels. Consequently, D18 0.4 :SEBS 0.6 /L8-BO OSCs achieve 16-times higher stretchability (COS = 126%) than the OSCs based on D18/L8-BO (COS = 8%), while achieving 4-times higher PCE (12.13%) compared to the OSCs based on SEBS-rich active layers (D18 0.2 :SEBS 0.8 /L8-BO, PCE = 3.15%). Furthermore, D18 0.4 :SEBS 0.6 -based IS-OSCs preserve 86 and 90% of original PCEs at 50% strain and after 200 stretching/releasing cycles with 15% strain, respectively, demonstrating the highest mechanical robustness among reported IS-OSCs.

14 SOLAR ENERGY↗

Stress rupture of SiC/SiC composite tubes under high-temperature steam

SiC-fiber–reinforced SiC matrix composite cladding for light water reactor fuel elements must withstand high-temperature steam oxidation in a loss-of-coolant accident scenario (LOCA). Current composite designs include an outer monolithic SiC layer, in part, to increase steam oxidation resistance. However, it is not clear how such a structure would behave under high-temperature steam in the case when the monolithic layer cracks and carbon interphases and SiC fibers are exposed to the environment. To fill this knowledge gap, stress-rupture tests of prototypic SiC composite cladding at 1000°C under steam and inert environments were conducted. The applied stress was ~120 MPa, which was beyond the initial cracking stress. The failure lifetime under steam was 400–1300 s, while 75% of the composite specimens did not fail after 3 h of total exposure under inert gases. Microstructural observations suggest that steam oxidation activated slow crack growth in the fibers, which led to failure of the composite. The results from this study suggest that stress rupture in steam environments could be a limiting factor of the cladding under reactor LOCA conditions.

36 MATERIALS SCIENCE↗

Growth of Matrix Cracks During Intermediate Temperature Stress Rupture of a SiC/SiC Composite in Air

The crack density of woven Hi-Nicalon(sup TM) (Nippon Carbon, Japan) fiber, BN interphase, melt-infiltrated SiC matrix composites was determined for specimens subjected to tensile stress rupture at 815 C. A significant amount of matrix cracking occurs due to the growth of fiber-bridged microcracks even at stresses below the run-out condition. This increased cracking corresponded to time dependent strain accumulation and acoustic emission activity during the constant load test. However, the portion of the rupture specimens subjected to cooler temperatures (< 600 C than the hot section had significantly lower crack densities compared to the hotter regions. From the acoustic emission and time dependent strain data it can be inferred that most of the matrix crack growth occurred within the first few hours of the tensile rupture experiment. The crack growth was attributed to an interphase recession mechanism that is enhanced by the presence of a thin carbon layer between the fiber and the matrix as a result of the composite fabrication process. One important consequence of matrix crack growth at the lower stresses is poor retained strength at room temperature for specimens that did not fail.

Morscher, Gregory N.↗

Curvilinear crack layer propagation

An account is given of an experiment designed to allow observation of the effect of damage orientation on the direction of crack growth in the case of crack layer propagation, using polystyrene as the model material. The direction of crack advance under a given loading condition is noted to be determined by a competition between the tendency of the crack to maintain its current direction and the tendency to follow the orientation of the crazes at its tip. The orientation of the crazes is, on the other hand, determined by the stress field due to the interaction of the crack, the crazes, and the hole. The changes in craze rotation relative to the crack define the active zone rotation.

Chudnovsky, Alexander↗

Advancement of Entry System Modeling to Support Exploration of Giant Planets

This paper describes NASA’s efforts to advance entry system modeling and simulation capabilities to support future exploration of Giant planets. The Giant planets are key destinations of interest to the planetary science community for their potential to provide insight into the formation and evolution of our Solar System, as well as extrasolar planetary systems. To date, the Galileo atmospheric probe is the only purpose-built entry probe to a Giant planet. Post-flight analysis of Galileo’s performance showed that there was significant recession of the thermal protection system (TPS), well beyond what was anticipated on the flank, and this was due in part to insufficiently accurate capability for estimating the flight environment and TPS response. While Galileo ultimately survived its flight, the example serves to highlight the great challenge of designing successful missions for environments that are poorly understood or where models have not yet been validated. An important means to reduce mission risks is the incorporation of physics-based modeling with well-quantified uncertainties. The emphasis on physics-based modeling – in contrast to empirically-driven models – is motivated by the fact that it is impossible to completely replicate entry environments through ground tests and, therefore, extrapolation to the flight environment is required. Basing analysis in fundamental physics removes the bias of ground test limitations, though one must then be careful to properly characterize model inputs, simplifying assumptions, and the limits wherein the model is valid. NASA’s Entry Systems Modeling (ESM) Project is tasked with investigating such considerations for planetary science missions across the Solar System, and in recent years has begun to do so for Giant planets. The most distinctive features of the Giant planets, from an entry system perspective, are the atmospheres composed primarily of hydrogen and helium. The entry velocities of proposed missions are generally very large and can therefore be expected to result in significant convective and radiative heating generated by the vehicle’s shock layer. Yet thermochemical behavior of the hydrogen-helium system is not well understood under such conditions. The ESM project is leading efforts to develop accurate thermochemical databases based on state-of-the-art measurements in the Electric Arc Shock Tube and detailed computational chemistry. The large heat fluxes anticipated by missions has driven interest in new TPS materials, in particular woven materials, which may be enabling but have never been flown before. Consequently, multiscale models are in development to describe properties and performance of the materials from micro- to system-scale. The goal is to not only provide accurate thermal response but also to inform thermostructural reliability predictions for extreme entries. Additionally, new computational models have been developed to evaluate performance of non-destructive evaluation techniques which are vital to establishing acceptance of systems to be free of manufacturing faults like material cracking, voids, and debonding. Finally, in the area of guidance and control, aerocapture has been shown conceptually to provide a number of mission benefits, including reducing transit time and increasing payload fraction. The ESM project is building a launch-to-landing trajectory simulation capability to enable detailed studies of aerocapture maneuvers in the context of Giant planets missions. The final presentation and paper will describe each of these topics in detail, including discussion of specific gaps and the technical approach to solving them. In addition, the final paper will briefly discuss ongoing coordination between ESM project work and an ESA-funded technology development activity comprised of validation testing in the Oxford T6, IRS PWK and IST ESTHER tunnels, as well as state-to-state modeling of the shock layer to better represent non-Boltzmann energy distributions leading to non-equilibrium radiation.

Entry systems↗

Reactive boride infusion stabilizes Ni-rich cathodes for lithium-ion batteries

Engineered polycrystalline electrodes are critical to the cycling stability and safety of lithium-ion batteries, yet it is challenging to construct high-quality coatings at both the primary- and secondary-particle levels. Here, we present a room-temperature synthesis route to achieve full surface coverage of secondary particles and facile infusion into grain boundaries, thus offering a complete “coating-plus-infusion” strategy. Cobalt boride metallic glass is successfully applied to Ni-rich layered cathode LiNi 0.8 Co 0.1 Mn 0.1 O 2 . Here, it dramatically improves the rate capability and cycling stability, including under high-discharge-rate and elevated-temperature conditions and in pouch full cells. The superior performance originates from simultaneous suppression of microstructural degradation of intergranular cracking and side reactions with electrolyte. Atomistic simulations identified the critical role of strong selective interfacial bonding, which offers not only a large chemical driving force to ensure uniform reactive wetting and facile infusion but also lowered the surface/interface oxygen activity, contributing to the exceptional mechanical and electrochemical stabilities of the infused electrode.

25 ENERGY STORAGE↗

BISON Simulation Development for ALD Coated Particles (Progress Report, FY21)

Argonne has on ongoing effort to perform atomic layer deposition coatings on micron-scale fuel particles. Initial results showed cracking of the coating layer above a specific coating thickness, which motived the development of a BISON model for the coated particle system to help explain the behavior. This report describes the initial development of the BISON model, the materials models used, and the conditions used in the simulation. A 2D model has been developed, with sensitivity studies performed on several key parameters. Based on the 2D model results, and 3D model was also developed, with results from all calculations described. First principles calculations were also performed on the fuel/coating interface to help describe the observed behavior. Potential future activities are also described.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Directed energy deposition of functionally graded V-4Cr-4Ti to Fe-9Cr transition for fusion power systems

This study proposes a graded structure via additive manufacturing for divertor and first wall blanket applications in fusion reactors. Materials were selected based on thermodynamic calculations to operate from 1100 °C at the plasma-facing level to 550 °C at the structural steel level. Conventional joining methods often lead to failures due to discrete reaction layers with significant mechanical property differences. Using laser beam-directed energy deposition (LB-DED), this study demonstrates the fabrication of a VCrTi-Gr91 steel functionally graded component through a novel process parameter optimization framework. A systematic approach included powder characterization, single-track depositions, and construction of printability maps. Near full-density specimens of each interlayer were additively manufactured, and a transition from V-based alloys to reduced activation ferritic martensitic steels was achieved. Computational material selection of interlayer alloys and thermodynamic/diffusion kinetics simulations prevented most interface incompatibilities. A brittle intermetallic formed at one interface, causing cracking, which was not predicted by current thermodynamic models. Transition alloy design approach was updated with a more recent database and a mitigation strategy has been proposed to eliminate the formation of deleterious intermetallic phases. Ultimately, LB-DED has proven effective for producing multi-material graded systems for fusion applications, with the demonstrated process parameter optimization framework applicable to various materials.

Additive manufacturing↗

Liquid water and active resurfacing on Europa

Arguments for recent resurfacing of Europa by H2O from a liquid layer are presented, based on new interpretations of recent spacecraft and earth-based observations and revised theoretical calculations. The heat flow in the core and shell due to tidal forces is discussed, and considerations of viscosity and convection in the interior are found to imply water retention in the outer 60 km or so of the silicates, forming a layer of water/ice many tens of km thick. The outer ice crust is considered to be too thin to support heat transport rates sufficient to freeze the underlying water. Observational evidence for the calculations would consist of an insulating layer of frosts derived from water boiling up between cracks in the surface crust. Evidence for the existence of such a frost layer, including the photometric function of Europa and the deposits of sulfur on the trailing hemisphere, is discussed.

Squyres, S. W.↗

Hierarchical Defect Engineering for LiCoO 2 through Low-Solubility Trace Element Doping

Real-world industry-relevant battery composite electrodes are hierarchically structured. Their structural and chemical complexity is featured by ubiquitous multi-scale porosity and cracks, solid-solid and solid-liquid interfaces, compositional and redox heterogeneity, as well as lattice disordering and deformation. In particular for the active cathode particles, which are the fundamental building blocks for the energy reservoir, it is a consensus that these structural and chemical defects could have a profound impact on the battery performance. An in-depth understanding of the underlying mechanisms could critically inform the cathode material engineering, which would have a tremendous potential but remains a daunting challenge at present. In this work, we tackle this question by studying LiCoO 2 (LCO) with trace doping of Ti, which exhibits a low solubility in the LCO layered lattice. Additionally, we observed the spontaneous and heterogeneous segregation of the dopant (Ti) across a wide range of length scales. In addition to the modification of the particle surface and the buried grain boundaries within the particle, we reveal that the Ti doping has induced a significant amount of lattice distortions, which, in turn, promotes the robustness of the LCO lattice at high state of charge (above 4.5V). Our result formulates a multi-scale defect engineering strategy that could be applicable to the synthesis of a broad range of energy materials for applications in batteries and beyond.

36 MATERIALS SCIENCE↗