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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 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Imaging how thermal capillary waves and anisotropic interfacial stiffness shape nanoparticle supracrystals

Abstract Development of the surface morphology and shape of crystalline nanostructures governs the functionality of various materials, ranging from phonon transport to biocompatibility. However, the kinetic pathways, following which such development occurs, have been largely unexplored due to the lack of real-space imaging at single particle resolution. Here, we use colloidal nanoparticles assembling into supracrystals as a model system, and pinpoint the key role of surface fluctuation in shaping supracrystals. Utilizing liquid-phase transmission electron microscopy, we map the spatiotemporal surface profiles of supracrystals, which follow a capillary wave theory. Based on this theory, we measure otherwise elusive interfacial properties such as interfacial stiffness and mobility, the former of which demonstrates a remarkable dependence on the exposed facet of the supracrystal. The facet of lower surface energy is favored, consistent with the Wulff construction rule. Our imaging–analysis framework can be applicable to other phenomena, such as electrodeposition, nucleation, and membrane deformation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Observation of nanoparticle coalescence during core-shell metallic nanowire growth in colloids via nanoscale imaging

The surface morphology and shape of crystalline nanowires significantly influence their functional properties, including phonon transport, electrocatalytic performance, to name but a few. However, the kinetic pathways driving these morphological changes remain underexplored due to challenges in real-space and real-time imaging at single-particle and atomic resolutions. This study investigates the dynamics of shell (Au, Pd, Pt, Fe, Cu, Ni) deposition on AuAg alloy seed nanowires during core-shell formation. By using chiral/non-chiral seed nanowires, advanced imaging techniques, including liquid-phase transmission electron microscopy (LPTEM), cryogenic TEM, and three-dimensional electron tomography, a three-step deposition process is revealed: heterogeneous nucleation, nanoparticle attachment, and coalescence. It is found that colloidal Ostwald ripening, metal reactivity, and deposition amount modulate nanoparticle size and surface roughness, shaping final morphologies. Noble metal nanoparticles (Au, Ag, Pd, Pt) coalesce with seed nanowire along the 〈111〉 direction, distinct from that of other metals. These findings are consistent across different metals, including Ru, Cu, Fe, and Ni, highlighting the hypothesis of these processes in nanowire formation. These findings enhance traditional crystallographic theories and provide a framework for designing nanowire morphology. Additionally, our imaging techniques may be applied to investigate phenomena like electrodeposition, dendrite growth in batteries, and membrane deformation.

Yang, Dahai↗
DOE OSTI2026

Lithium metal-mediated electrochemical reduction of per- and poly-fluoroalkyl substances

Per- and poly-fluoroalkyl substances (PFAS) have substantial environmental and health hazards. Unfortunately, current degradation routes require high temperatures or corrosive conditions and/or lead to incomplete defluorination and the generation of shorter alkyl chains. Inspired by the lithium-metal battery literature, here we develop an electrochemical degradation process that leverages reactive metals and highly reducing environments. Here, we show that electrodeposited lithium metal can enable 95% degradation and 94% defluorination of perfluorooctanoic acid to LiF without forming any shorter C 2 –C 6 PFAS as end products. Using computational simulations, we find that electron transfer from lithium to perfluorooctanoic acid leads to rapid C–F bond cleavage, fluoride formation and carbon chain fragmentation. We expand the scope to other PFAS compounds and demonstrate substantial degrees of degradation on over 22 different PFAS, plus complete mineralization to inorganic fluorides. Finally, we use the mineralized F − as a fluorine source for the synthesis of fluorinated non-PFAS compounds to complete a circular fluorine loop from waste to valuable product.

Sarkar, Bidushi [Univ. of Chicago, IL (United Stat↗
DOE OSTI2021

Corrosion of lithium metal anodes during calendar ageing and its microscopic origins

Rechargeable lithium (Li) metal batteries must have long cycle life and calendar life (retention of capacity during storage at open circuit). Particular emphasis has been placed on prolonging the cycle life of Li metal anodes, but calendar ageing is less understood. Here, we show that Li metal loses at least 2–3% of its capacity after only 24 hours of ageing, regardless of the electrolyte chemistry. These losses of capacity during calendar ageing also shorten the cycle life of Li metal batteries. Cryogenic transmission electron microscopy shows that chemical corrosion of Li and the continuous growth of the solid electrolyte interphase—a passivation film on Li—cause the loss of capacity. Electrolytes with long cycle life do not necessarily form a solid electrolyte interphase with more resistance to chemical corrosion, so functional electrolytes must simultaneously minimize the rate of solid electrolyte interphase growth and the surface area of electrodeposited Li metal.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Chirality-induced spin selectivity as a mechanism to control product selectivity during electrochemical CO 2 reduction

Electrocatalytic CO 2 reduction often suffers from competition with the hydrogen evolution reaction (HER), which lowers efficiency and limits product selectivity. Recent studies suggest that electron spin, when controlled at an electrode surface, can influence reaction pathways, but direct evidence linking spin effects to suppressed HER has been limited. Here, in this work, we show that helical chiral copper (Cu) electrodes reduce competing HER during CO 2 reduction, consistent with spin polarization induced via the chiral-induced spin selectivity effect. The helically structured Cu electrodes are fabricated by electrodeposition with a chiral templating reagent. Time-resolved Kerr ellipticity measurements, which track spin-polarized carriers generated by an ultrafast Seebeck current, confirm spin accumulation at the chiral Cu surface. This spin polarization disfavours H—H bond formation, thereby suppressing HER and enabling formate production alongside CO. These findings demonstrate that chirality-based spin control offers a strategy for steering selectivity in CO 2 reduction and other reactions where HER is an undesired competitor.

14 SOLAR ENERGY↗
DOE OSTI2019

Catalyst synthesis under CO 2 electroreduction favours faceting and promotes renewable fuels electrosynthesis

The electrosynthesis of C 2+ hydrocarbons from CO 2 has garnered recent attention in light of the relatively high market price per unit energy input. Today’s low selectivities and stabilities towards C 2+ products at high current densities curtail system energy efficiency, which limits their prospects for economic competitiveness. Here we present a materials processing strategy based on in situ electrodeposition of copper under CO 2 reduction conditions that preferentially expose and maintain Cu(100) facets, which favour the formation of C 2+ products. We observe capping of facets during catalyst synthesis and achieve control over faceting to obtain a 70% increase in the ratio of Cu(100) facets to total facet area. We report a 90% Faradaic efficiency for C 2+ products at a partial current density of 520 mA cm –2 and a full-cell C 2+ power conversion efficiency of 37%. We achieve nearly constant C2H4 selectivity over 65 h operation at 350 mA cm –2 in a membrane electrode assembly electrolyser.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Engineering medium-range order and polyamorphism in a nanostructured amorphous alloy

Like crystalline materials, the properties of amorphous materials can be tailored by tuning the local atomic-to-nanoscale structural configurations. Polyamorphism is evident by the coexistence of kinetically stabilized amorphous structures with tailorable short-to-medium-range orders, providing a viable means to engineer the degree of local order and heterogeneity. Here, we report experimental evidence of the coexistence of liquid-like and solid-like amorphous phases in a Ni82P18 amorphous alloy with enhanced thermal stability and plasticity prepared by pulsed electrodeposition. The two amorphous phases, of comparable volume fraction of ~50% each, have similar short-range order but are distinguished by packing at the medium-range length scale (>6 Å). Upon heating, a structure crossover at ~450 K was observed, where the liquid-like structure transforms to the solid-like structure, as evidenced by the enthalpy release and an anomalous contraction of atomic structure over the medium-range length scale, due to the metastable nature of the liquid-like structure.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Nanodomained Nickel Unite Nanocrystal Strength with Coarse-Grain Ductility

Conventional metals are routinely hardened by grain refinement or by cold working with the expense of their ductility. Recent nanostructuring strategies have attempted to evade this strength versus ductility trade-off, but the paradox persists. It has never been possible to combine the strength reachable in nanocrystalline metals with the large uniform tensile elongation characteristic of coarse-grained metals. Here a defect engineering strategy on the nanoscale is architected to approach this ultimate combination. For Nickel, spread-out nanoscale domains (average 7 nm in diameter) were produced during electrodeposition, occupying only ~2.4% of the total volume. Yet the resulting Ni achieves a yield strength approaching 1.3 GPa, on par with the strength for nanocrystalline Ni with uniform grains. Simultaneously, the material exhibits a uniform elongation as large as ~30%, at the same level of ductile face-centered-cubic metals. Electron microscopy observations and molecular dynamics simulations demonstrate that the nanoscale domains effectively block dislocations, akin to the role of precipitates for Orowan hardening. In the meantime, the abundant domain boundaries provide dislocation sources and trapping sites of running dislocations for dislocation multiplication and the ample space in the grain interior allows dislocation storage; a pronounced strain-hardening rate is therefore sustained to enable large uniform elongation.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Hybrid Li-air battery cathodes with sparse carbon nanotube arrays directly grown on carbon fiber papers

Sparsely populated, vertically aligned nitrogen doped carbon nanotube arrays (CNTAs) with dislocated-graphene stacking were grown directly on carbon fiber papers and investigated as hierarchical air cathodes in hybrid Li-air batteries with aqueous catholytes. The CNTAs were made with electrodeposited Ni nanocatalysts, followed by plasma-enhanced chemical vapor deposition. The thus obtained CNTAs can reach a population number density as low as similar to 10(7) per cm(2) on the carbon fibers, achieving an extremely high porosity of over 99% for the active layer in the cathode. The sparse CNTAs not only provide effective pathways for the reacting species, but also show a significantly high catalytic activity, which is found to be comparable to that of a supported Pt electrocatalyst. The high activity of the CNTAs is attributed to the rich graphene edges exposed on the CNT surface and nitrogen doping. Hybrid Li-air batteries with such cathodes have shown a consistent discharging capacity of 710 mA h g(-1) and a specific energy of 2057 W h kg(-1) at 0.5 mA cm(-2). Stable charge-discharge cycling at 0.5 mA cm(-2) showed an average potential difference of 1.35 V, indicative of a relatively small overpotential and high round trip efficiency (71%). Furthermore, the hybrid Li-air battery based on the hierarchical cathode can reach a power density as high as 10.4 mW cm(-2).

Li, YF↗
DOE OSTI2014

Discovering Ce-rich oxygen evolution catalysts, from high throughput screening to water electrolysis

In this paper, we report a new Ce-rich family of active oxygen evolution reaction (OER) catalysts composed of earth abundant elements, discovered using high-throughput methods. High resolution inkjet printing was used to produce 5456 discrete oxide compositions containing the elements nickel, iron, cobalt and cerium. The catalytic performance of each of these compositions was measured under conditions applicable to distributed solar fuels generation using a three-electrode scanning drop electrochemical cell. The catalytic activity and stability of representative compositions (Ni 0.5 Fe 0.3 Co 0.17 Ce 0.03 O x and Ni 0.3 Fe 0.07 Co 0.2 Ce 0.43 O x ) from 2 distinct regions were verified by resynthesizing these compositions on glassy carbon rods for electrochemical testing. The activity of the new Ce-rich catalysts was further verified using an unrelated synthetic method to electrodeposit a pseudo-ternary composition Ni 0.2 Co 0.3 Ce 0.5 O x , which produced a catalyst with 10 mA cm -2 oxygen evolution current at 310 mV overpotential. Finally, the unique Tafel behavior of these Ce-rich catalysts affords the opportunity for further improvement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

A review of cermet-based spectrally selective solar absorbers

Spectrally selective solar absorbers harvest solar energy in the form of heat. Solar absorbers using cermet-based coatings reflect a high absorptance of the solar spectrum and a low emittance in the infrared (IR) regime. Extensive work has been done to optimize cermet-based solar absorbers to achieve high performance by exploring different cermet (ceramic–metal composite) materials and film configurations through different preparation techniques such as electrodeposition, sputtering, pulsed laser deposition, and solution-based methods. Here in this work, we review the progress of cermet-based spectrally selective absorbers with high solar absorptance and low thermal emittance, such as Cr 2 O 3 , Al 2 O 3 , AlN, SiO 2 , and ZrO 2 based cermets as absorption layers. We also present an outlook for cermet-based spectrally selective absorbers with high thermal stability and high conversion efficiency from sunlight to heat.

14 SOLAR ENERGY↗
DOE OSTI2014

Electrophoretic deposition improves catalytic performance of Co 3 O 4 nanoparticles for oxygen reduction/oxygen evolution reactions

The effects of nanoparticle deposition on the catalytic activity of Co 3 O 4 nanoparticles for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are evaluated for two deposition methods: dropcasting and electrophoretic deposition (EPD). In this work it is found that the EPD catalyst films demonstrate better catalytic activity per unit mass than do the dropcast films, as defined by diffusion-limited current, by approximately 27% for ORR and 25% for OER. When accounting for different loading levels, the absolute activities of these catalysts are superior to those of other reported Co 3 O 4 colloidal nanoparticulate catalysts without conductive additives, showing that this material has excellent intrinsic activity for future optimization. Inspection of the electrode kinetics shows that EPD catalysts have more favorable characteristics as exhibited by their smaller Tafel slope (96 mV per decade for EPD versus 109 mV per decade for dropcast films). We analyze this enhancement by determining the metal oxide surface area for each catalyst film using a novel sequential metal deposition technique starting with electrodeposition of Ag followed by Pb underpotential deposition (UPD). Through UPD experiments we find, surprisingly, that EPD films have a smaller surface area than the dropcast films. We conclude that EPD films are more active per unit surface area. When accounting for surface area and mass, the EPD catalyst outperforms dropcast by a factor of 2.5 for ORR and 2.6 for OER. We anticipate that morphological differences in the EPD films relative to the dropcast ones, such as particle coverage and electrical conductivity, are responsible for this behavior. Such a result has important implications for future studies on the structure of EPD-manufactured nanoparticulate thin films and on the mechanisms for performance enhancement in such catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

New ionic liquids based on complexation of dipropylsulfide and AlCl3 for electrochodeposition of aluminum

A new kind of ionic liquid based on complexation of dipropyl sulfide (DPS) and AlCl 3 has been prepared. The equivalent concentration of AlCl3 in the ionic liquid is as high as 2.3 M. More importantly, it is highly fluidic and exhibits an ambient ionic conductivity of 1.25 x 10 -4 S cm -1 . This new ionic liquid can be successfully used as an electrolyte for electrodeposition of aluminum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Benchmarking nanoparticulate metal oxide electrocatalysts for the alkaline water oxidation reaction

Nanoparticulate metal-oxide catalysts are among the most prevalent systems for alkaline water oxidation. However, comparisons of the electrochemical performance of these materials have been challenging due to the different methods of attachment, catalyst loadings, and electrochemical test conditions reported in the literature. Here in this paper, we have leveraged a conventional drop-casting method that allows for the successful adhesion of a wide range of nanoparticulate catalysts to glassy-carbon electrode surfaces. We have applied this adhesion method to prepare catalyst films from 16 crystalline metal-oxide nanoparticles with a constant loading of 0.8 mg cm -2 , and evaluated the resulting nanoparticulate films for the oxygen evolution reaction under conditions relevant to an integrated solar fuels device. In general, the activities of the adhered nanoparticulate films are similar to those of thin-film catalysts prepared by electrodeposition or sputtering, achieving 10 mA cm -2 current densities per geometric area at overpotentials of ~0.35–0.5 V.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Revealing the semiconductor–catalyst interface in buried platinum black silicon photocathodes

Nanoporous 'black' silicon semiconductors interfaced with buried platinum nanoparticle catalysts have exhibited stable activity for photoelectrochemical hydrogen evolution even after months of exposure to ambient conditions. The mechanism behind this stability has not been explained in detail, but is thought to involve a Pt/Si interface free from SiOx layer that would adversely affect interfacial charge transfer kinetics. In this paper, we resolve the chemical composition and structure of buried Pt/Si interfaces in black silicon photocathodes from a micron to sub-nanometer level using aberration corrected analytical scanning transmission electron microscopy. Through a controlled electrodeposition of copper on samples aged for one month in ambient conditions, we demonstrate that the main active catalytic sites are the buried Pt nanoparticles located below the 400-800 nm thick nanoporous SiOx layer. Though hydrogen production performance degrades over 100 h under photoelectrochemical operating conditions, this burying strategy preserves an atomically clean catalyst/Si interface free of oxide or other phases under air exposure and provides an example of a potential method for stabilizing silicon photoelectrodes from oxidative degradation in photoelectrochemical applications.

14 SOLAR ENERGY↗
DOE OSTI2017

Design of template-stabilized active and earth-abundant oxygen evolution catalysts in acid

Oxygen evolution reaction (OER) catalysts that are earth-abundant and are active and stable in acid are unknown. Active catalysts derived from Co and Ni oxides dissolve at low pH, whereas acid stable systems such as Mn oxides (MnO x ) display poor OER activity. We now demonstrate a rational approach for the design of earth-abundant catalysts that are stable and active in acid by treating activity and stability as decoupled elements of mixed metal oxides. Manganese serves as a stabilizing structural element for catalytically active Co centers in CoMnO x films. In acidic solutions (pH 2.5), CoMnO x exhibits the OER activity of electrodeposited Co oxide (CoO x ) with a Tafel slope of 70–80 mV per decade while also retaining the long-term acid stability of MnO x films for OER at 0.1 mA cm -2 . Driving OER at greater current densities in this system is not viable because at high anodic potentials, Mn oxides convert to and dissolve as permanganate. However, by exploiting the decoupled design of the catalyst, the stabilizing structural element may be optimized independently of the Co active sites. By screening potential–pH diagrams, we replaced Mn with Pb to prepare CoFePbO x films that maintained the high OER activity of CoO x at pH 2.5 while exhibiting long-term acid stability at higher current densities (at 1 mA cm -2 for over 50 h at pH 2.0). Under these acidic conditions, CoFePbO x exhibits OER activity that approaches noble metal oxides, thus establishing the viability of decoupling functionality in mixed metal catalysts for designing active, acid-stable, and earth-abundant OER catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗