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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 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Genesis of Nanogalvanic Corrosion Revealed in Pearlitic Steel

Nanoscale, localized corrosion underpins billions of dollars in damage and material costs each year; however, the processes responsible have remained elusive due to the complexity of studying degradative material behavior at nanoscale liquid–solid interfaces. Recent improvements to liquid cell scanning/transmission electron microscopy and associated techniques enable this first look at the nanogalvanic corrosion processes underlying this widespread damage. Nanogalvanic corrosion is observed to initiate at the near-surface ferrite/cementite phase interfaces that typify carbon steel. In minutes, the corrosion front delves deeper into the material, claiming a thin layer of ferrite around all exposed phase boundaries before progressing laterally, converting the ferrite to corrosion product normal to each buried cementite grain. Over the following few minutes, the corrosion product that lines each cementite grain undergoes a volumetric expansion, creating a lateral wedging force that mechanically ejects the cementite grains from their grooves and leaves behind percolation channels into the steel substructure.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Resolving Current-Dependent Regimes of Electroplating Mechanisms for Fast Charging Lithium Metal Anodes

Poor fast-charge capabilities limit the usage of rechargeable Li metal anodes. Understanding the connection between charging rate, electroplating mechanism, and Li morphology could enable fast-charging solutions. In this report we develop a combined electroanalytical and nanoscale characterization approach to resolve the current-dependent regimes of Li plating mechanisms and morphology. Measurement of Li + transport through the solid electrolyte interphase (SEI) shows that low currents induce plating at buried Li||SEI interfaces, but high currents initiate SEI-breakdown and plating at fresh Li||electrolyte interfaces. The latter pathway can induce uniform growth of {110}-faceted Li at extremely high currents, suggesting ion-transport limitations alone are insufficient to predict Li morphology. At battery relevant fast-charging rates, SEI-breakdown above a critical current density produces detrimental morphology and poor cyclability. Thus, prevention of both SEI-breakdown and slow ion-transport in the electrolyte is essential. This mechanistic insight can inform further electrolyte engineering and customization of fast-charging protocols for Li metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Picosecond Ultrasonics in Magnetic Topological Insulator MnBi 2 Te 4

MnBi 2 Te 4 is a magnetic topological insulator with layered A-type antiferromagnetic order. It exhibits a rich layer- and magnetic-state dependent topological phase diagram; however, much about the coupling between spin, charge, and lattice remains to be explored. Here, in this work, we report that MnBi 2 Te 4 is an excellent acoustic phonon cavity by realizing phonon frequency combs using picosecond ultrasonics. With the generated acoustic phonon wavepackets, we demonstrate that the timing and phase of acoustic echoes can be used to detect the presence of stacking faults between van der Waals layers buried deep within the crystal. Furthermore, by implementing this nondestructive ultrafast optical measurement in conjunction with time-resolved magneto-optical Kerr effect experiments, we uncover that out-of-plane vibrations in MnBi 2 Te 4 do not couple to the magnetic order, i.e. there is no appreciable magnetostriction. Our work points out how a well-developed technique can probe the structural defects and phonon pulse engineering in layered topological insulators.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Nanoscale Ferroelectric Programming of van der Waals Heterostructures

We demonstrate an approach to creating nanoscale potentials in van der Waals layers integrated with a buried programmable ferroelectric layer. Using ultra-low-voltage electron beam lithography (ULV-EBL), we can program the ferroelectric polarization in Al 1–x B x N (AlBN) thin films, generating structures with sizes as small as 35 nm. We demonstrate the ferroelectric field effect with a graphene/vdW stack on AlBN by creating a p–n junction. This resist-free, high-resolution, contactless patterning method offers a new pathway to integrate ferroelectric films with a wide range of two-dimensional layers including transition-metal dichalcogenides (TMD), enabling arbitrary programming and top-down creation of multifunctional devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Steric Mapping, Ligand Dynamics, and Cycloisomerization Catalysis with Redox Robust Mn I/0/-I Dicarbenes

Manganese is perhaps the most electronically versatile element, yet the redox properties, reactivity, and catalytic applications of low-valent Mn 0 /Mn −I complexes remain underexplored due to the propensity for Mn 0 to dimerize, quenching highenergy metalloradicals. We report a series of redox-active monometallic Mn I , Mn 0 and Mn −I complexes containing a BH 2 - bridged dicarbene, characterized using a suite of experimental and cutting-edge computational (DFT) methods. Slow electron transfer kinetics at Mn I/0 are observed, with computations and electrochemical simulations in excellent agreement with experimental values. Despite the lack of steric bulk at the BH 2 -bridged Mn 0 , the t Bu groups at the dicarbene provide adequate steric protection to prevent dimerization, with percent buried volume (% V bur ) serving as a valuable steric ranking tool. We also show that a %V bur > 83% prevents dimerization for a diverse array of Mn 0 complexes from the literature. Ligand sterics of BPh 2 -and BH 2 -bridged complexes dictate reaction outcomes when Mn I and Mn −I are exposed to nucleophiles and electrophiles, respectively, while Mn0 facilitates the radical cycloisomerization catalysis of 6-iodo-1- hexene at room temperature. Furthermore, this work underscores the importance of ligand sterics in rationalizing reactivity patterns at Mn and provides valuable insights for designing chelating ligands that can selectively leverage Mn I/0/‑I states in redox-mediated catalytic reactions.

Ligands↗
DOE OSTI2020

Hydrogen-Bond-Driven Chemical Separations: Elucidating the Interfacial Steps of Self-Assembly in Solvent Extraction

Chemical separations, particularly liquid extractions, are pervasive in academic and industrial laboratories, yet a mechanistic understanding of the events governing their function are obscured by interfacial phenomena that are notoriously difficult to measure. In this work, we investigate the fundamental steps of ligand self-assembly as driven by changes in the interfacial H-bonding network using vibrational sum frequency generation. Our results show how the bulk pH modulates the interfacial structure of extractants at the buried oil/aqueous interface via the formation of unique H-bonding networks that order and bridge ligands to produce self-assembled aggregates. These extended H-bonded structures are key to the subsequent extraction of Co2+ from the aqueous phase in promoting micelle formation and subsequent ejection of the said micelle into the oil phase. The combination of static and time-resolved measurements reveals the events underlying complexities of liquid extractions at high [Co2+]:[ligand] ratios by showing an evolution of interfacially assembled structures that are readily tuned on a chemical basis by altering the compositions of the aqueous phase. The results of this work point to new principles to design-applied separations through the manipulation of surface charge, electrostatic screening, and the associated H-bonding networks that arise at the interface to facilitate organization and subsequent extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Operando Depth-Resolved Measurement of Solvation Entropy, Interfacial Transport, and Charge-Transfer Kinetics in Lithium-Ion Batteries

Understanding and improving the performance and longevity of lithium-ion batteries critically depends on insight into the dynamic processes occurring at buried electrode-electrolyte interfaces. However, direct, depth-resolved, and operando diagnosis of these interfaces remains a longstanding challenge due to their inaccessibility beneath bulk materials, the limitations of conventional surface- and bulk-sensitive characterization tools, and the difficulty of maintaining realistic cell environments during measurement. These challenges have made it nearly impossible to uniquely resolve important interfacial properties such as charge transfer resistance, SEI (solid electrolyte interphase) resistance, and solvation entropy at the individual electrode interfaces within a working cell, information that is essential for mechanistic insight and accelerated battery design. Here, in this study, we report the development of multiharmonic electro-thermal spectroscopy (METS), an operando technique that enables depth-resolved measurement of solvation entropy, interfacial transport resistance, charge-transfer resistance, and SEI resistance at individual electrode-electrolyte interfaces within practical lithium-ion batteries. By leveraging frequency-dependent, thermal-wave sensing and interface-specific modeling, METS uniquely attributes interfacial properties to specific electrodes, as validated by comparison with traditional electrochemical impedance spectroscopy (EIS). The ability to spatially and temporally resolve interfacial processes in real time provides new diagnostic capabilities that are crucial for mechanistic studies of battery degradation and for the rapid development of next-generation energy storage systems.

Chalise, Divya [University of California, Berkeley↗
DOE OSTI2025

Chemistry and Interfacial Structure Promoting Quasi-van der Waals Epitaxial Growth of WS 2 Nanosheets on Sapphire for Prospective Application in Field-Effect Transistors

How do chemical and structural modifications to the supporting crystal surface affect the subsequent van der Waals (vdW) or quasi(Q)-vdW epitaxial growth of 2D nanocrystals? Developing an atomic-scale picture of such an interfacial system is crucial for understanding its impact on the physical and chemical properties of the supported 2D materials. The elucidation of the interfacial structure and chemistry needed to promote the Q-vdW epitaxial growth of 2D tungsten disulfide (WS 2 ) nanocrystals contributes to the growth mechanism understanding, thus pushing forward the integration of such atomically thin semiconductors toward real field-effect transistor applications. In addition to an atomic-force microscopy top view, we showcase a combination of X-ray techniques for a top-to-bottom investigation of the complexities of the buried interface structures. Furthermore, this approach uses X-ray photoelectron spectroscopy, X-ray standing wave excited X-ray fluorescence, and crystal truncation rod scattering to produce a highly resolved chemical-state-specific 3D atomic map for the extended interface structure of WS 2 /α-Al 2 O 3 (001). Employing these detailed analysis methods, along with density functional theory to further refine the picoscale structure, we demonstrate how two different types of interface engineering during the pregrowth stage lead to significant differences in the chemical and structural modifications to the terminal surface of c-face sapphire, which in turn leads to substantial differences in the submonolayer growth of supported WS 2 2D nanocrystals in terms of lateral domain sizes, epitaxial registry, vdW gaps, and stability.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Surface Sn(IV) Hydrolysis Improves Inorganic Sn–Pb Perovskite Solar Cells

Cesium tin-lead (Sn-Pb) perovskites are exceptional for their combined capabilities in unlocking ideal bandgaps for solar cells and mitigating the stability issue faced by their hybrid organic-inorganic counterparts. But the development of high-performance solar cells using these materials is retarded by their inherent high density of detrimental Sn(IV) defects. Herein, we demonstrate a sequential surface treatment method, which entails a Sn(II) halide treatment to displace the buried Sn(IV) ions underneath the film surface, followed by a H 2 O treatment to hydrolyze the displaced Sn(IV) ions. The surface treatment induces chemical and microstructural reconstructions that significantly improve the optoelectronic properties and stability of perovskites. As a result, a power conversion efficiency of 16.79% and a T 90 stability of 958 h are achieved, topping all previously reported performance parameters for inorganic Sn-Pb PSCs. This achievement further shortens the performance gap between all-inorganic and hybrid organic- inorganic Sn-Pb PSCs with sub-1.4 eV bandgaps.

14 SOLAR ENERGY↗
DOE OSTI2020

Challenges in Lithium Metal Anodes for Solid-State Batteries

In this Perspective, we highlight recent progress and challenges related to the integration of lithium metal anodes in solid-state batteries. While prior reports have suggested that solid electrolytes may be impermeable to lithium metal, this hypothesis has been disproven under a variety of electrolyte compositions and cycling conditions. Herein, we describe the mechanistic origins and importance of lithium filament growth and interphase formation in inorganic and organic solid electrolytes. Multimodal techniques that combine real and reciprocal space imaging and modeling will be necessary to fully understand nonequilibrium dynamics at these buried interfaces. Currently, most studies on lithium electrode kinetics at solid electrolyte interfaces are completed in symmetric Li–Li configurations. To fully understand the challenges and opportunities afforded by Li-metal anodes, full-cell experiments are necessary. Lastly, the impacts of operating conditions on solid-state batteries are largely unknown with respect to pressure, geometry, and break-in protocols. Given the rapid growth of this community and the diverse portfolio of solid electrolytes, we highlight the need for detailed reporting of experimental conditions and standardization of protocols across the community.

25 ENERGY STORAGE↗
DOE OSTI2024

Resolving the Electron Plume within a Scanning Electron Microscope

Scanning electron microscopy (SEM), a century-old technique, is today a ubiquitous method of imaging the surface of nanostructures. However, most SEM detectors simply count the number of secondary electrons from a material of interest, and thereby overlook the rich material information contained within them. Here, by simple modifications to a standard SEM tool, we resolve the momentum and energy information on secondary electrons by directly imaging the electron plume generated by the electron beam of the SEM. Leveraging these spectroscopic imaging capabilities, our technique is able to image lateral electric fields across a prototypical silicon p–n junctions and to distinguish differently doped regions, even when buried beyond depths typically accessible by SEM. Intriguingly, the subsurface sensitivity of this technique reveals unexpectedly strong surface band bending within nominally passivated semiconductor structures, providing useful insights for complex layered component designs, in which interfacial dynamics dictate device operation. Further, these capabilities for noninvasive, multimodal probing of complicated electronic components are crucial in today’s electronic manufacturing but is largely inaccessible even with sophisticated techniques. These results show that seemingly simple SEM can be extended to probe complex and useful material properties.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Uniform Diffusion of Cooper Pairing Mediated by Hole Carriers in Topological Sb 2 Te 3 /Nb

Spin-helical Dirac Fermions at a doped topological insulator’s boundaries can support Majorana quasiparticles when coupled with s-wave superconductors, but in n-doped systems, the requisite induced Cooper pairing in topological states is often buried at heterointerfaces or complicated by degenerate coupling with bulk conduction carriers. Rarely probed are p-doped topological structures with nondegenerate Dirac and bulk valence bands at the Fermi level, which may foster long-range superconductivity without sacrificing Majorana physics. Using ultrahigh-resolution photoemission, we report proximity pairing with a large decay length in p-doped topological Sb 2 Te 3 on superconducting Nb. Despite no momentum-space degeneracy, the topological and bulk states of Sb 2 Te 3 /Nb exhibit the same isotropic superconducting gaps at low temperatures. Furthermore, our results unify principles for realizing accessible pairing in Dirac Fermions relevant to topological superconductivity.

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

Diffractive Imaging of Conical Intersections Amplified by Resonant Infrared Fields

The fate of virtually all photochemical reactions is determined by conical intersections. These are energetically degenerate regions of molecular potential energy surfaces that strongly couple electronic states, thereby enabling fast relaxation channels. Their direct spectroscopic detection relies on weak features that are often buried beneath stronger, less interesting contributions. For azobenzene photoisomerization, a textbook photochemical reaction, we demonstrate how a resonant infrared field can be employed during the conical intersection passage to significantly enhance its coherence signatures in time-resolved Xray diffraction while leaving the product yield intact. Furthermore, this transition-state amplification holds promise to bring signals of conical intersections above the detection threshold.

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

Identification and Catalysis of the Potential-Limiting Step in Lithium-Sulfur Batteries

The Li-S chemistry is thermodynamically promising for high-density energy storage but kinetically challenging. Over the past few years, many catalyst materials have been developed to improve the performance of Li-S batteries and their catalytic role has been increasingly accepted. However, the classic catalytic behavior, i.e., reduction of reaction barrier, has not been clearly observed. Crucial mechanistic questions, including what specific step is limiting the reaction rate, whether/how it can be catalyzed, and how the catalysis is sustained after the catalyst surface is covered by solid products, remain unanswered. Herein, we report the first identification of the potential-limiting step of Li-S batteries operating under lean electrolyte conditions and its catalysis that conforms to classic catalysis principles, where the catalyst lowers the kinetic barrier of the potential-limiting step and accelerates the reaction without affecting the product composition. After carefully examining the electrochemistry under lean electrolyte conditions, we update the pathway of the Li-S battery reaction: S 8 solid is first reduced to Li 2 S 8 and Li 2 S 4 molecular species sequentially; the following reduction of Li 2 S 4 to a Li 2 S 2 -Li 2 S solid with an almost constant ratio of 1:4 is the potential-limiting step; the previously believed Li 2 S 2 -to-Li 2 S solid-solid conversion does not occur; the recharging reaction is relatively fast. We further demonstrate that supported cobalt phthalocyanine molecules can effectively catalyze the potential-limiting step. After Li 2 S 2 /Li 2 S buries the active sites, it can self-catalyze the reaction and continue driving the discharging process.

25 ENERGY STORAGE↗
DOE OSTI2024

Tailoring Interfaces for Enhanced Methanol Production from Photoelectrochemical CO 2 Reduction

Efficient and stable photoelectrochemical reduction of CO 2 into highly reduced liquid fuels remains a formidable challenge, which requires an innovative semiconductor/catalyst interface to tackle. In this study, we introduce a strategy involving the fabrication of a silicon micropillar array structure coated with a superhydrophobic fluorinated carbon layer for the photoelectrochemical conversion of CO 2 into methanol. The pillars increase the electrode surface area, improve catalyst loading and adhesion without compromising light absorption, and help confine gaseous intermediates near the catalyst surface. The superhydrophobic coating passivates parasitic side reactions and further enhances local accumulation of reaction intermediates. Upon one-electron reduction of the molecular catalyst, the semiconductor–catalyst interface changes from adaptive to buried junctions, providing a sufficient thermodynamic driving force for CO 2 reduction. These structures together create a unique microenvironment for effective reduction of CO 2 to methanol, leading to a remarkable Faradaic efficiency reaching 20% together with a partial current density of 3.4 mA cm –2 , surpassing the previous record based on planar silicon photoelectrodes by a notable factor of 17. Furthermore, this work demonstrates a new pathway for enhancing photoelectrocatalytic CO 2 reduction through meticulous interface and microenvironment tailoring and sets a benchmark for both Faradaic efficiency and current density in solar liquid fuel production.

14 SOLAR ENERGY↗
DOE OSTI2024

Ethylene Polymerizations Catalyzed by Fluorinated “Sandwich” Diimine-Nickel and Palladium Complexes

Nickel and palladium complexes bearing “sandwich” diimine ligands with perfluorinated aryl caps have been synthesized, characterized, and explored in ethylene polymerization reactions. The X-ray crystallographic analysis of the precatalysts 16 and 6b show differences from their non-fluorinated analogues 17 and 19, with the perfluorinated aryl caps centered precisely over the nickel and palladium centers which results in higher buried volumes of the metal centers relative to the non-fluorinated analogs. The sandwich diimine palladium complexes 5a and 5b containing perfluorinated aryl caps polymerize ethylene in a controlled fashion with activities that are substantially increased compared with their non-fluorinated analogues. Migratory insertion rates in relevant methyl ethylene complexes agree with activities exhibited in bulk polymerization experiments. DFT studies suggest that facility of ethylene rotation from its preferred orientation perpendicular to the Pd-alkyl bond into a parallel in-plane conformation contributes to the higher polymerization activity for 5b relative to 18a. For these palladium systems polymer molecular weights can be controlled via hydrogen addition (hydrogenolysis) which is unusual for late transition metal-catalyzed olefin polymerizations with no catalyst deactivation occurring. Sandwich diimine nickel complexes 6a and 6b with perfluorinated aryl caps show ethylene polymerization activities that are about half that of classical tetraisopropyl-substituted catalyst 2 but again are more active than the analogous nonfluorinated sandwich complexes. Ethylene polymerizations exhibit living behavior and branched ultra-high molecular weight polyethylenes (UHMWPEs) with very low molecular weight distributions (less than 1.1) are obtained. The activated nickel catalysts are stable in the absence of monomer and show good long-term stability at 25 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Pt Particles on a Dynamic TiO 2 Support in Near-Ambient Conditions−Disentangling Size, Pressure, and Support Effects

Platinum particles on reducible oxides are known to form complex and highly dynamic catalyst systems at elevated pressures and temperatures, often adopting active structures that differ from those found at room temperature and under ultrahigh vacuum (UHV). Here, we study the oxidation and structural evolution of subnanometer Pt clusters and nanoparticles supported on rutile TiO 2 (110) across an oxygen pressure range from UHV to 0.1 mbar, using near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), scanning tunneling microscopy (STM) under UHV and NAP conditions, and low-energy ion scattering (LEIS). Our results reveal distinct differences in oxidation behavior and thermal stability between Pt nanoparticles and clusters, which are further modulated by the support stoichiometry and oxygen pressure. Small Pt clusters become oxidized even at room temperature but are susceptible to accelerated sintering in 0.1 mbar O 2 at elevated temperatures. In contrast, well-crystallized Pt nanoparticles on near-stoichiometric TiO 2 show weaker oxidation. On a reduced, defective TiO 2 support, Pt instead quickly becomes deeply buried by new titania layers, which are formed during support reoxidation. This process appears to result primarily from interactions of the support with the gas phase, unlike the classical, selflimited encapsulation that is induced by the strong metal−support interaction (SMSI). Finally, we address the full complexity of real catalysts in a direct side-by-side comparison of the single-crystalline model system with a Pt-loaded TiO 2 powder catalyst (P25). We conclude that the stoichiometry of the model supports must be carefully chosen and controlled to accurately reproduce the expected state of powder supports during redox reactions.

metal nanoparticles↗
DOE OSTI2020

Using Ambient Noise Seismic Interferometry and Local and Teleseismic Earthquakes to Determine Crustal Thickness and Moho Structure of the Northwestern Gulf of Mexico Margin

Abstract The northwestern part of the Gulf of Mexico has undergone two episodes of continental rifting and collision and produced structural artifacts that are now buried under many kilometers of sediments, complicating investigations of the region. The deep sedimentary package precludes outcrops and points to a need for the application of seismic techniques, but low rates of seismicity in the region and sparse seismic monitoring limit the utility of traditional seismic methods. We therefore use diverse data to perform two‐dimensional seismic tomography across the dry land portion of the margin. Data are gleaned from teleseismic and regional earthquakes, postcritical SsPmp arrivals, and direct P wave energy identified with seismic interferometry that were recorded by a broadband, three‐component array and partially overlapping short‐period, vertical‐component array. The Pn and postcritical SsPmp phase help constrain the Moho discontinuity, which a previous receiver function study suggested was absent beneath the seaward portion of this transect. A high‐velocity body is observed in the crust at the same location as the Houston Magnetic Anomaly, possibly marking rocks from the Alleghenian continental assembly. The crust thins from NW to SE, indicating that extension occurred mostly to the south of the Ouachita orogeny. Our model indicates that the margin's sediment package reaches a maximum thickness of ~15 km at the coast and becomes unresolvably thin near the Llano Uplift.

58 GEOSCIENCES↗