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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 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

New challenges in oxygen reduction catalysis: a consortium retrospective to inform future research

In this perspective, we highlight results of a research consortium devoted to advancing understanding of oxygen reduction reaction (ORR) catalysis as a means to inform fuel cell science. We demonstrate how targeted collaborations between different institutions from academic, national lab, and industry backgrounds and different scientific disciplines like theory, experiment, and characterization can yield unique insights into fuel cell catalysts. We comment on such insights into material designs for platinum-group-metal alloys, transition metal oxides, and non-traditional materials including metal–organic frameworks; systems that have served as the foundational building blocks for our consortium. We also motivate a renewed focus on catalyst durability in light of emerging technological requirements and paths forward in understanding in situ and operando electrochemical stability. Lastly, we describe new frontiers ORR research can take and how emerging artificial intelligence tools can assist researchers in capturing data, selecting new experiments, and guiding characterization to accelerate the design and discovery of fuel cell catalysts. A main goal of sharing this perspective is to discuss the rationale for our future research plans based on our consortium work. However, we also hope to illustrate both the potential impact of a collaborative strategy with the hopes of inspiring a higher degree of Industry-Academia-National Laboratory collaboration and encourage other centers and consortiums to distill and share their findings in a similar perspective-type article. Together we hope to enable the fuel cell research community to engage in a discussion of strategies for research and accelerated development of catalysts with improved activity and stability.

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

Mesoporous Textured Fe-N-C Electrocatalysts as Highly Efficient Cathodes for Proton Exchange Membrane Fuel Cells

A new platinum group metal (PGM)-free proton exchange membrane fuel cell (PEMFC) cathode catalyst materials, synthesized using the VariPore™ method by Pajarito Powder, LLC, are characterized for their structure and activity. The physico-chemical analysis of the iron-nitrogen-carbon (Fe-N-C) electrocatalysts show mesoporous carbon material effectively doped with iron and nitrogen. The materials have an average pore size of 7-8 nm and high specific surface area. The Fe-N-C catalysts exhibit good oxygen reduction reaction (ORR) activity in 0.5 M H2SO4 electrolyte with high half-wave potential and sustainable electrochemical stability over 10,000 repeated potential cycles with insignificant losses in their activities. As cathode catalysts in a PEMFC, the Fe-N-C materials deliver remarkably good fuel cell performance at low overpotential approaching that of the commercial Pt catalyst. The high ORR electrocatalytic activity of these Fe-N-C catalysts is credited to the synergy between nitrogen-moieties, specifically pyrrolic-N, pyridinic-N, and graphitic-N, and iron in addition to the high mesoporosity that facilitate an effective reaction path in boosting the electrocatalytic activity and stability.

DIRECT ENERGY CONVERSION↗
DOE OSTI2021

Nomenclatural issues concerning cultured yeasts and other fungi: why it is important to avoid unneeded name changes

The unambiguous application of fungal names is important to communicate scientific findings. Names are critical for (clinical) diagnostics, legal compliance, and regulatory controls, such as biosafety, food security, quarantine regulations, and industrial applications. Consequently, the stability of the taxonomic system and the traceability of nomenclatural changes is crucial for a broad range of users and taxonomists. The unambiguous application of names is assured by the preservation of nomenclatural history and the physical organisms representing a name. Fungi are extremely diverse in terms of ecology, lifestyle, and methods of study. Predominantly unicellular fungi known as yeasts are usually investigated as living cultures. Methods to characterize yeasts include physiological (growth) tests and experiments to induce a sexual morph; both methods require viable cultures. Thus, the preservation and availability of viable reference cultures are important, and cultures representing reference material are cited in species descriptions. Historical surveys revealed drawbacks and inconsistencies between past practices and modern requirements as stated in the International Code of Nomenclature for Algae, Fungi, and Plants (ICNafp). Improper typification of yeasts is a common problem, resulting in a large number invalid yeast species names. With this opinion letter, we address the problem that culturable microorganisms, notably some fungi and algae, require specific provisions under the ICNafp. We use yeasts as a prominent example of fungi known from cultures. But viable type material is important not only for yeasts, but also for other cultivable Fungi that are characterized by particular morphological structures (a specific type of spores), growth properties, and secondary metabolites. We summarize potential proposals which, in our opinion, will improve the stability of fungal names, in particular by protecting those names for which the reference material can be traced back to the original isolate.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Combinatorial Synthesis and High-Throughput Characterization of Microstructure and Phase Transformation in Ni–Ti–Cu–V Quaternary Thin-Film Library

Ni–Ti–based shape memory alloys (SMAs) have found widespread use in the last 70 years, but improving their functional stability remains a key quest for more robust and advanced applications. Named for their ability to retain their processed shape as a result of a reversible martensitic transformation, SMAs are highly sensitive to compositional variations. Alloying with ternary and quaternary elements to fine-tune the lattice parameters and the thermal hysteresis of an SMA, therefore, becomes a challenge in materials exploration. Combinatorial materials science allows streamlining of the synthesis process and data management from multiple characterization techniques. In this study, a composition spread of Ni–Ti–Cu–V thin-film library was synthesized by magnetron co-sputtering on a thermally oxidized Si wafer. Composition-dependent phase transformation temperature and microstructure were investigated and determined using high-throughput wavelength dispersive spectroscopy, synchrotron X-ray diffraction, and temperature-dependent resistance measurements. Of the 177 compositions in the materials library, 32 were observed to have shape memory effect, of which five had zero or near-zero thermal hysteresis. These compositions provide flexibility in the operating temperature regimes that they can be used in. A phase map for the quaternary system and correlations of functional properties are discussed with respect to the local microstructure and composition of the thin-film library.

42 ENGINEERING↗
DOE OSTI2025

Harnessing metastability for grain size control in multiprincipal element alloys during additive manufacturing

Abstract Controlling microstructure in fusion-based metal additive manufacturing (AM) remains a significant challenge due to the many parameters that directly impact solidification condition. Multiprincipal element alloys (MPEAs), also known as high entropy alloys, offer a vast compositional space to design for microstructural engineering due to their chemical complexity and exceptional properties. Here, we use the FeMnCoCr system as a model platform for exploring alloy design in MPEAs for AM. By exploiting the decreasing stability of the face-centered cubic phase with increasing Mn content, we achieve notable grain refinement and breakdown of epitaxial columnar grain growth. We employ a multifaceted approach encompassing thermodynamic modeling, operando synchrotron X-ray diffraction, multiscale microstructural characterization, and mechanical testing to gain insight into the solidification physics and its ramifications on the resulting microstructure of FeMnCoCr MPEAs. This work aims toward tailoring desirable grain sizes and morphology through targeted manipulation of phase stability, thereby advancing microstructure control in AM applications.

Wakai, Akane↗
DOE OSTI2020

The Neighboring Subunit Is Engaged to Stabilize the Substrate in the Active Site of Plant Arginases

Arginine acts as a precursor of polyamines in plants in two known pathways, agmatine and ornithine routes. It is decarboxylated to agmatine by arginine decarboxylase, and then transformed to putrescine by the consecutive action of agmatine iminohydrolase and N-carbamoylputrescine amidohydrolase. Alternatively, it can be hydrolyzed to ornithine by arginase and then decarboxylated by ornithine decarboxylase to putrescine. Some plants lack a functional ornithine pathway, but all have one or two arginases that can have dual cellular localization, in mitochondria and plastids. It was recently shown that arginases from Arabidopsis thaliana and soybean act also as agmatinases, thus they can produce putrescine directly from agmatine. Therefore, arginase (together with arginine decarboxylase) can complement putrescine production in plastids, providing a third polyamine biosynthesis pathway in plants. Phylogenetic analysis suggests that arginases, highly conserved in the plant kingdom, create the only group of enzymes recognized in the family of ureohydrolases in plants. Arginases are metalloenzymes with binuclear manganese cluster in the active site. In this work, two arginases from A. thaliana and Medicago truncatula are structurally characterized and their binding properties are discussed. Crystal structures with bound ornithine show that plant hexameric arginases engage a long loop from the neighboring subunit to stabilize α-amino and carboxyl groups of the ligand. This unique ligand binding mode is unobserved in arginases from other domains of life. Structural analysis shows that substrate binding by residues from two neighboring subunits might also characterize some prokaryotic agmatinases. This feature of plant arginases is most likely the determinant of their ability to recognize not only arginine but also agmatine as their substrates, thus, to act as arginase and agmatinase.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Synergetic Effect of Aluminum Oxide and Organic Halide Salts on Two‐Dimensional Perovskite Layer Formation and Stability Enhancement of Perovskite Solar Cells

Long-chain organic halide salts are widely used in perovskite-based optoelectronic devices for surface passivation owing to their capability to interact with the surface defects of perovskites. Here, aluminum oxide (AlO x ) is introduced via atomic layer deposition onto octylammonium iodide (OAI) to exploit the benefits of organic halide salts without generating undesired defects. The devices incorporating AlO x on OAI-treated perovskite (OAI/AlO x ) show enhancement in both device performance and photo-stability compared to those with only treatment. A diffusion of aluminum from AlO x into the perovskite through surface characterization contributes to a uniform photo-generated carrier transport in both the surface and the bulk of the perovskite absorber. In addition, it is revealed that light-induced two-dimensional perovskite formation on OAI/AlO x . This may be ascribed to preventing the loss of OA cations due to the presence of AlO x , leading to a decrease in the number of iodine anions which suppresses the light-induced degradation of corresponding devices. Consequently, the devices show over 24% efficiency and retain their efficiency over 1000 hours under continuous light illumination.

14 SOLAR ENERGY↗
DOE OSTI2024

Identifying point defects and ordering in the high-entropy layered oxide Li 1.5 MO 3-δ (M=Mn, Al, Fe, Co, Ni) for energy storage applications

High-entropy layered oxides (HELOs) represent a very promising class of next-generation battery cathodes, combining the well-studied properties of layered cathode materials such as LiCoO 2 with the chemical tunability and stability of high-entropy materials. HELO materials often form particles with complex defects and domain structures, complicating accurate characterization of structure and cation mixing. Understanding disorder and order in HELO materials is necessary for understanding their performance and utility as cathodes. Here we demonstrate the characterization of the HELO Li 1.5 MO 3-δ (M = Mn, Al, Fe, Co, Ni), wherein X-ray powder diffraction, transmission electron microscopy imaging, and electron diffraction patterns are analyzed to reveal the presence of ordering in the HELO, with imaging and diffraction simulation employed to compare experimental results to atomic modeling. Finally, without rigorous characterization at the atomic scale, important features such as defect ordering can be easily overlooked and therefore remain unconsidered when interpreting experimental results.

36 MATERIALS SCIENCE↗
DOE OSTI2022

A Superior Carbonate Electrolyte for Stable Cycling Li Metal Batteries Using High Ni Cathode

Li metal batteries pairing Li metal anode with high-nickel layer structured oxide cathode are a promising energy storage technology to achieve high energy density. To obtain long cycling life for Li metal batteries, the electrolyte plays a pivotal role in stabilizing both the Li metal anode and the high-nickel cathode upon electrochemical cycling. Herein, we report a carbonate electrolyte that enables a Li||LiNi 0.8 Mn 0.1 Co 0.1 O 2 pouch cell to achieve a high gravimetric energy density of 366 Wh/kg and unprecedented cycling stability with 80% capacity retention after 335 cycles. Here, the 19 F quantitative nuclear magnetic resonance spectroscopy and interface characterization demonstrate that FEC and LiDFOB can reduce the consumption rate of each other and the electrolyte, form a robust LiF-rich SEI on Li metal anode, and improve the microstructure integrity of the high-nickel cathode.

25 ENERGY STORAGE↗
DOE OSTI2022

Stable CsPbBr 3 Nanoclusters Feature a Disk-like Shape and a Distorted Orthorhombic Structure

CsPbBr 3 nanoclusters have been synthesized by several groups and mostly employed as single-source precursors for the synthesis of anisotropic perovskite nanostructures or perovskite-based heterostructures. Yet, a detailed characterization of such clusters is still lacking due to their high instability. In this work, we were able to stabilize CsPbBr 3 nanoclusters by carefully selecting ad hoc ligands (benzoic acid together with oleylamine) to passivate their surface. The clusters have a narrow absorption peak at 400 nm, a band-edge emission peaked at 410 nm at room temperature, and their composition is identified as CsPbBr 2.3 . Synchrotron X-ray pair distribution function measurements indicate that the clusters exhibit a disk-like shape with a thickness smaller than 2 nm and a diameter of 13 nm, and their crystal structure is a highly distorted orthorhombic CsPbBr 3 . Based on small- and wide-angle X-ray scattering analyses, the clusters tend to form a two-dimensional (2D) hexagonal packing with a short-range order and a lamellar packing with a long-range order.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Peroxide-Selective Reduction of O 2 at Redox-Inactive Rare-Earth(III) Triflates Generates an Ambiphilic Peroxide

Metal peroxides are key species involved in a range of critical biological and synthetic processes. Rare-earth (group III and the lanthanides; Sc, Y, La–Lu) peroxides have been implicated as reactive intermediates in catalysis; however, reactivity studies of isolated, structurally characterized rare-earth peroxides have been limited. Herein, we report the peroxide-selective (93–99% O22-) reduction of dioxygen (O 2 ) at redox-inactive rare-earth triflates in methanol using a mild metallocene reductant, decamethylferrocene (Fc*). The first molecular praseodymium peroxide ([Pr III 2( O 2 2- )(18C6) 2 (EG)2][OTf]4; 18C6 = 18-crown-6, EG = ethylene glycol, - OTf = - O 3 SCF 3 ; 2-Pr) was isolated and characterized by single-crystal X-ray diffraction, Raman spectroscopy, and NMR spectroscopy. 2-Pr displays high thermal stability (120 °C, 50 mTorr), is protonated by mild organic acids [pK a1 (MeOH) = 5.09 ± 0.23], and engages in electrophilic (e.g., oxygen atom transfer) and nucleophilic (e.g., phosphate-ester cleavage) reactivity. Our mechanistic studies reveal that the rate of oxygen reduction is dictated by metal-ion accessibility, rather than Lewis acidity, and suggest new opportunities for differentiated reactivity of redox-inactive metal ions by leveraging weak metal–ligand binding events preceding electron transfer.

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

Photoinduced correlations in stochastic dynamics of a solid-state ionic conductor

Photoexcitation by ultrashort laser pulses plays a crucial role in controlling reaction pathways, creating nonequilibrium material properties, and probing complex molecular dynamics. The photoresponse following a laser pulse is generally nonidentical between exposures due to spatiotemporal fluctuations or the stochastic nature of dynamical pathways. However, most ultrafast pump-probe experiments struggle to distinguish intrinsic sample fluctuations from extrinsic apparatus noise, often missing deviations from the averaged response. Leveraging the stability and high photon flux of time-resolved X-ray micro-diffraction at a synchrotron, we characterized stochastic photoinduced dynamics in a solid-state ionic conductor. By analyzing temporal evolutions of the lattice parameter of a single grain, we found that shot-to-shot fluctuations are not independent. Instead, correlations exist between nonequilibrium lattice trajectories following adjacent shots, with a characteristic correlation length of approximately 1500 shots, corresponding to an energy barrier of 0.4 ± 0.1 eV, close to the activation energy of lithium-ion diffusion.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Synthetic-domain computing and neural networks using lithium niobate integrated nonlinear phononics

Analogue computing uses the physical behaviours of devices to provide energy-efficient arithmetic operations. However, scaling up analogue computing platforms by simply increasing the number of devices leads to challenges such as device-to-device variation. Here, in this study, we report scalable analogue computing and neural networks in the synthetic frequency domain using an integrated nonlinear phononic platform on lithium niobate. This synthetic-domain computing is robust to device variations, as vectors and matrices are concurrently encoded at different frequencies within a single device, achieving a high throughput per area. Leveraging inherent nonlinearities, our device-aware neural network can perform a four-class classification task with an accuracy of 98.2%. The nonlinear phononic computing hardware also maintains consistent performance over a wide operational temperature range (characterized up to 192 °C). Our synthetic-domain computing combines single-device parallelism, inherent nonlinearity and environmental stability, and could be of use in edge computing applications in which power efficiency and environmental resilience are crucial.

Ji, Jun [Virginia Polytechnic Inst. and State Univ↗
DOE OSTI2020

A highly substituted pyrazinophane generated from a quinoidal system via a cascade reaction

Here the generation of a highly-substituted [2.2](2,5)pyrazinophane via a cascade reaction is presented. The pyrazinophane product is formed via the dimerization of a member of the para-azaquinodimethane (p-AQM) family of conjugated quinoidal compounds—reactivity that sheds light on the nature of stability in p-AQMs. Additionally, the electronic and structural nature of this highly-strained ring system are characterized.

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

Colonization of Naive Roots from Populus tremula × alba Involves Successive Waves of Fungi and Bacteria with Different Trophic Abilities

ABSTRACT Through their roots, trees interact with a highly complex community of microorganisms belonging to various trophic guilds and contributing to tree nutrition, development, and protection against stresses. Tree roots select for specific microbial species from the bulk soil communities. The root microbiome formation is a dynamic process, but little is known on how the different microorganisms colonize the roots and how the selection occurs. To decipher whether the final composition of the root microbiome is the product of several waves of colonization by different guilds of microorganisms, we planted sterile rooted cuttings of gray poplar obtained from plantlets propagated in axenic conditions in natural poplar stand soil. We analyzed the root microbiome at different time points between 2 and 50 days of culture by combining high-throughput Illumina MiSeq sequencing of the fungal ribosomal DNA internal transcribed spacer and bacterial 16S rRNA amplicons with confocal laser scanning microscopy observations. The microbial colonization of poplar roots took place in three stages, but bacteria and fungi had different dynamics. Root bacterial communities were clearly different from those in the soil after 2 days of culture. In contrast, if fungi were also already colonizing roots after 2 days, the initial communities were very close to that in the soil and were dominated by saprotrophs. They were slowly replaced by endophytes and ectomycorhizal fungi. The replacement of the most abundant fungal and bacterial community members observed in poplar roots over time suggest potential competition effect between microorganisms and/or a selection by the host. IMPORTANCE The tree root microbiome is composed of a very diverse set of bacterial and fungal communities. These microorganisms have a profound impact on tree growth, development, and protection against different types of stress. They mainly originate from the bulk soil and colonize the root system, which provides a unique nutrient-rich environment for a diverse assemblage of microbial communities. In order to better understand how the tree root microbiome is shaped over time, we observed the composition of root-associated microbial communities of naive plantlets of poplar transferred in natural soil. The composition of the final root microbiome relies on a series of colonization stages characterized by the dominance of different fungal guilds and bacterial community members over time. Our observations suggest an early stabilization of bacterial communities, whereas fungal communities are established following a more gradual pattern.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

High-speed phase contrast imaging of spray breakup of jet fuels under combusting conditions

X-ray phase contrast imaging is conducted at 90,517 Hz on a fuel spray to characterize the breakup of the bulk fuel into ligaments and individual droplets in a single-sector, swirl-stabilized combustor under reacting conditions. Phase contrast imaging is used to qualitatively assess spray breakup for two fuels: Jet-A, which represents a normal viscosity fuel, and a blend of JP-5 (64%) and farnesane (36% by volume), which represents a high-viscosity fuel, at three fuel-flow rates and two air inlet temperatures. Time-series images of the fuels show that atomization occurs much more rapidly at higher fuel pressure with thinner ligaments being rapidly shredded. The high-viscosity fuel is qualitatively observed to have markedly longer, thicker ligaments and larger droplet diameters after the primary breakup than the normal viscosity fuel. Using an image processing and droplet quantification strategy, the mean droplet velocity magnitudes were found to decrease with decreasing fuel pressure and fuel-flow rate. The increase in preheat temperature from 323 to 370 K results in an increase in the mean droplet velocity magnitude and a decrease in numerical average and Sauter mean diameter, indicating improved atomization. The high-viscosity fuel was found to have larger average droplet diameters at each condition than the normal viscosity fuel. The increased preheat is found to enhance the combustion efficiency, which is hypothesized to couple with the improved atomization due to the higher combustion temperatures. This indicates the importance of examining spray atomization and breakup under realistic combusting conditions for relevant fuels as the heat release directly couples with the atomization process.

42 ENGINEERING↗
DOE OSTI2022

Understanding Solid-Electrolyte Interphase Formation at the Lithium Metal Anode of Lithium-Sulfur Batteries

Lithium-sulfur (Li-S) batteries are one of the most promising chemistries for the next generation of energy storage devices. In a standard Li-S cell, the metallic lithium anode is an essential component of the battery due to its low density, extremely high theoretical specific capacity, and very low negative electrochemical potential. However, several challenges related to the use of Li metal have prevented this battery technology from becoming commercially available. For instance, Li-anodes are highly reactive, which results in the continuous decomposition of the electrolyte and the formation of the solid-electrolyte interphase (SEI) layer. This, combined with the non-uniform deposition of Liions during plating at the anode surface, can seriously affect the performance, cycling, and safety of the battery. In addition, it has been suggested that a controlled SEI formation at the metallic Li anode can yield enhanced battery performance. Hence, a comprehensive understanding of how the SEI layer is formed can help elucidate improvements in this battery technology. In this work, the formation of the SEI layer in Li-S batteries is investigated using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. The stability of liquid organic-based electrolyte components, salt concentration, electron-rich environments, and the use of inorganic solid-state electrolyte (SSE) materials are explored in order to provide molecular-level fundamental insights into how the nature and composition of the electrolyte can alter the initial stages of the SEI formation. The products of electrolyte decomposition and electro-/chemical reaction pathways of liquid electrolyte component such as solvent and salts are predicted from AIMD simulations of electrolyte-anode interfaces. Energetics of reactions from DFT ground-state optimizations are also presented to confirm the decomposition mechanisms. Some significant differences are then drawn regarding the use of low and high salt concentrations. Simulations under electron-rich environments show additional multielectron electrochemical reactions of solvent and salt decomposition taking place due to the excess of electrons and the presence of radical anions in the solution. Finally, the initial stages of formation, stability, and main constituents of interfaces between Li-metal and Sbased electrodes with sulfide-based SSEs are characterized in detail.

25 ENERGY STORAGE↗
DOE OSTI2021

Boosting the cycling stability of Ni-rich layered oxide cathode by dry coating of ultrastable Li 3 V 2 (PO 4 ) 3 nanoparticles

Nickel (Ni)-rich layered oxides such as LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) represent one of the most promising candidates for next-generation high-energy lithium-ion batteries (LIBs). However, the pristine Ni-rich cathode materials usually suffer from poor structural stability during cycling. In this work, we demonstrate a simple but effective approach to improve the cycling stability of the NCM622 cathode by dry coating of ultrastable Li 3 V 2 (PO 4 ) 3 -carbon (LVP-C) nanoparticles, which leads to a robust composite cathode (NCM622/LVP-C) without sacrificing the specific energy density compared with pristine NCM622. The optimal NCM622/LVP-C composite presents a high specific capacity of 162 mA h g -1 at 0.5 C and excellent cycling performance with 85.0% capacity retention after 200 cycles at 2 C, higher than that of the pristine NCM622 (67.6%). Systematic characterization confirms that the LVP-C protective layer can effectively reduce the side reactions, restrict the cation mixing of NCM622 and improve its structural stability. Moreover, the NCM622/LVP-C||graphite full cells also show a commercial-level capacity of 3.2 mA h cm -2 and much improved cycling stability compared with NCM622/LVP-C||graphite full cells, indicating the great promise for low-cost, high-capacity and long-life LIBs.

36 MATERIALS SCIENCE↗