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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Dynamic Monkey Bar Mechanism of Superionic Li‐ion Transport in LiTaCl 6

Abstract The LiTaCl 6 solid electrolyte has the lowest activation energy of ionic conduction at ambient conditions (0.165 eV), with a record high ionic conductivity for a ternary compound (11 mS cm −1 ). However, the mechanism has been unclear. We train machine‐learning force fields (MLFF) on ab initio molecular dynamics (AIMD) data on‐the‐fly and perform MLFF MD simulations of AIMD quality up to the nanosecond scale at the experimental temperatures, which allows us to predict accurate activation energy for Li‐ion diffusion (at 0.164 eV). Detailed analyses of trajectories and vibrational density of states show that the large‐amplitude vibrations of Cl − ions in TaCl 6 − enable the fast Li‐ion transport by allowing dynamic breaking and reforming of Li−Cl bonds across the space in between the TaCl 6 − octahedra. We term this process the dynamic‐monkey‐bar mechanism of superionic Li + transport which could aid the development of new solid electrolytes for all‐solid‐state lithium batteries.

Lei, Ming↗
DOE OSTI2023

Dynamic Monkey Bar Mechanism of Superionic Li–ion Transport in LiTaCl 6

Here, the LiTaCl 6 solid electrolyte has the lowest activation energy of ionic conduction at ambient conditions (0.165 eV), with a record high ionic conductivity for a ternary compound (11 mS cm –1 ). However, the mechanism has been unclear. We train machine-learning force fields (MLFF) on ab initio molecular dynamics (AIMD) data on-the-fly and perform MLFF MD simulations of AIMD quality up to the nanosecond scale at the experimental temperatures, which allows us to predict accurate activation energy for Li-ion diffusion (at 0.164 eV). Detailed analyses of trajectories and vibrational density of states show that the large-amplitude vibrations of Cl – ions in TaCl 6 – enable the fast Li-ion transport by allowing dynamic breaking and reforming of Li–Cl bonds across the space in between the TaCl 6 – octahedra. We term this process the dynamic-monkey-bar mechanism of superionic Li + transport which could aid the development of new solid electrolytes for all-solid-state lithium batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Hydrogen and Solid Carbon Products from Natural Gas: A Review of Process Requirements, Current Technologies, Market Analysis, and Preliminary Techno Economic Assessment

In this paper, we review relevant technologies—primarily thermochemical and plasma conversion processes—that use natural gas to produce solid carbon and hydrogen, and recent research progress and commercial activities. Technical challenges include the high energetic requirements necessary for methane activation and, for some catalytic processes, the separation of solid carbon product from the spent catalyst. We assess current and new carbon product markets that could be served given technological advances, and we discuss technical barriers and potential areas of research to address these needs. We provide preliminary economic analysis where it was concluded that the cost of pyrolytically produced CO2-free hydrogen can be potentially reduced to <$4/kg target levels with the co-production and sale of sufficiently high-value carbon products.

Dagle, Robert A.↗
DOE OSTI2020

$t_1$-Noise eliminated dipolar heteronuclear multiple-quantum coherence solid-state NMR spectroscopy

Heteronuclear correlation (HETCOR) spectroscopy is one of the key tools in the arsenal of the solid-state NMR spectroscopist to probe chemical and spatial proximities between two different nuclei and enhance spectral resolution. Dipolar heteronuclear multiple-quantum coherence (D-HMQC) is a powerful technique that can be potentially utilized to obtain 1 H detected 2D HETCOR solid-state NMR spectra of any NMR active nucleus. A long-standing problem in 1 H detected D-HMQC solid-state NMR experiments is the presence of t 1 -noise which reduces sensitivity and impedes spectral interpretation. In this contribution, we describe novel pulse sequences, termed t 1 -noise eliminated (TONE) D-HMQC, that minimize t 1 -noise and can provide higher sensitivity and resolution than conventional D-HMQC. Monte-Carlo and numerical simulations confirm that t 1 -noise in conventional D-HMQC primarily occurs because random MAS frequency fluctuations cause variations in the NMR signal amplitude from scan to scan, leading to imperfect cancellation of uncorrelated signals by phase cycling. The TONE D-HMQC sequence uses 1 H π-pulses to refocus the evolution of 1 H CSA across each SR4 2 1 recoupling block, improving the stability of the pulse sequence to random MAS frequency fluctuations. The 1 H refocusing pulses also restore the orthogonality of in-phase and anti-phase magnetization for all crystallite orientations at the end of each recoupling block, enabling the use of 90° flip-back or LG spin-lock trim pulses to reduce the intensity of uncorrelated signals. We demonstrate the application of these methods to acquire 1 H detected 2D 1 H{ 35 Cl} and 1 H{ 13 C} HETCOR spectra of histidine·HCl·H 2 O with reduced t 1 -noise. To show generality, we also apply these methods to obtain 2D 1 H{ 17 O} spectra of 20%- 17 O fmoc-alanine and for the first time at natural abundance, 2D 1 H{ 25 Mg} HETCOR spectra of magnesium hydroxide. The TONE D-HMQC sequences are also used to probe 1 H– 25 Mg and 1 H– 27 Al proximities in Mg–Al layered double hydroxides and confirm the even mixing of Mg and Al in these materials.

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

The Role of Cooperative Interactions Among Surfaces, Solvents, and Reactive Intermediates on Catalysis at Liquid–Solid Interfaces (Final Report DE-SC0020224)

This project established quantitative links between inner‑sphere chemistry (active metal identity, coordination, and zeolite topology) and outer‑sphere organization (solvent identity, hydrogen‑bond networks, and pore condensation) that govern rates, activation barriers, and selectivities for alkene epoxidation and epoxide ring‑opening at solid–liquid and quasi‑liquid–solid interfaces. We deconvoluted contributions from covalent interactions at active sites and noncovalent, solvent‑mediated interactions within pores by pairing well‑defined metal substituted zeolites with controlled solvent environments. We then mapped those contributions onto measurable kinetics (ΔH‡, ΔS‡), adsorption thermodynamics (ITC), and in situ spectroscopy. The transferrable outcomes include a set of design rules that include the following understandings. First, tune silanol ((SiOH)x) density and pore topology to organize solvent networks that selectively stabilize transition states. Second, exploit activity‑coefficient‑normalized rates and adsorption– barrier correlations to diagnose when solvent reorganization rather than surface chemistry limits performance. Third, use partial pore condensation (e.g., acetonitrile, water but also generalizable to other solvents) to elicit liquid‑like stabilization effects even in nominally vapor‑phase reactors. Collectively, these results provide strategies to increase epoxidation rates, improve oxidant utilization (i.e., selectivities), and steer regioselectivity in zeolite‑based catalytic processes relevant to sustainable oxidation chemistry. These outcomes should be transferable to other classes of reactions that proceed in microporous materials and under confinement provided by organized solvents (e.g., electrochemical double layers).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Plastic deformation of single crystals of the equiatomic Cr-Mn-Fe-Co-Ni high-entropy alloy in tension and compression from 10 K to 1273 K

In this report the plastic deformation behavior of single crystals of the quinary, equiatomic Cr-Mn-Fe-Co-Ni high-entropy alloy (HEA) with the face-centered cubic structure has been investigated in tension and compression as a function of crystal orientation and temperature from 10 K to 1373 K. The critical resolved shear stress (CRSS) for {111}<110> slip at room temperature is 42-45 MPa. It does not depend much on crystal orientation (i.e., the Schmid law holds true) and the sense (tension vs. compression) of the applied load. The CRSS for {111}<110> slip increases with the decrease in temperature, without showing any significant inertia effects at cryogenic temperatures below 77 K. Extrapolation from the measured yield stresses down to 10 K yields a CRSS value at 0 K of 168 MPa. At cryogenic temperatures, the measured strain-rate sensitivity of flow stress is consistent with a very small activation volume. The concept of stress equivalence holds true both for the temperature dependence of CRSS and the stress dependence of activation volume, indicating that solid-solution hardening is the major strengthening mechanism. Deformation twinning occurs at 77 K but not at room temperature, resulting in higher tensile elongation to failure at 77 K than at room temperature. Deformation twinning at 77 K occurs at a shear stress of 378 MPa on conjugate ($\bar1\bar11$) planes in the form of Lüders deformation after large plastic strain (about 85%) achieved by the stage I (easy glide) and stage II (linear work-hardening) deformation.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Direct regeneration of degraded LiFePO4 cathodes via a separator-enabled prelithiation strategy

A persistent challenge in lithium-ion batteries is the loss of active lithium due to the solid electrolyte interphase (SEI) formation and associated side reactions. While prelithiation employing lithium replenishment separator (LRS) has been proven effective in compensating for lithium loss, previous studies have largely been accompanied by gas evolution or solid residue formation during the prelithiation process. To surmount this challenge, we present a LRS based on 4-fluoro-1,2-dihydroxybenzene lithium salt (LiDF), capable of mitigating lithium loss while producing decomposition products that integrate directly into the electrolyte as functional additives which can assist with the stability of the SEI, free from gas or solid formation, thus establishing a sustainable and environmentally benign strategy for lithium compensation. Incorporation of the LRS enables the pristine LiFePO4||graphite (Gr) full cell to achieve 10.8% higher capacity than the cell with a polypropylene separator (PPS) after 200 cycles at 0.5C. Remarkably, the degraded LiFePO4 (D-LFP)||Gr full cell with the LRS exhibits a 135.8% capacity improvement over the PPS-based cell after 500 cycles. These findings establish the LRS as a powerful approach for both boosting high-performance lithium-ion batteries and recovering the capacity of degraded batteries.

Tao, Fujun↗
DOE OSTI2024

Operando NMR characterization of cycled and calendar aged nanoparticulate silicon anodes for Li-ion batteries

Replacing graphite anodes with Si anodes can greatly increase the energy of current Li-ion batteries. Detailed characterization of Si lithiation reactions, SEI formation, and reversibility are therefore active areas of research. Solid-state 7 Li nuclear magnetic resonance (NMR) spectroscopy is useful for characterizing different lithium local environments within Si anodes. Here, we developed an operando NMR methodology to characterize aging of carbon-coated nanoparticulate Si anodes in pouch cells paired with Ni-rich cathodes. We observed a new lithiation mechanism in the Si nanoparticles: direct formation of over-lithiated Li 15+x Si 4 (x<0.6) phase. Furthermore, our novel operando cells maintained good performance with long-term cycle and calendar aging. Here we identified trapped lithium silicides as a major contributor to capacity fade with aging. Finally, we determined that the addition of Mg (TFSI) 2 to the electrolyte decreased the amount of trapped lithium silicides and therefore increased the capacity and capacity retention for the nanoparticulate Si used.

25 ENERGY STORAGE↗
DOE OSTI2022

Comparative uptake, translocation, and plant mediated transport of Tc-99, Cs-133, Np-237, and U-238 in Savannah River Site soil columns for the grass species Andropogon virginicus

Here, this study examines the ability of the grass species Andropogon virginicus to alter the subsurface transport and redistribution of a suite of radionuclides ( 99 Tc, 133 Cs (stable analog for 135 Cs and 137 Cs), 237 Np, 238 U) with varying chemical behaviors in a Savannah River Site soil via the use of vegetated and unvegetated soil columns. After an acclimation period, a small volume of solution containing all radionuclides was introduced into the columns via Rhizon© pore water sampling tubes. Plants were grown for an additional 4 weeks before shoots were harvested, and columns were prepared for sampling. Plant presence led to decreased radionuclide release from the columns, mainly due to radionuclide specific combinations of system hydrology differences resulting from plant transpiration as well as plant uptake. For the most mobile radionuclides, 99 Tc followed by 237 Np, plant presence resulted in significantly different soil concentration profiles between vegetated and unvegetated columns, including notable upward migration for 237 Np in columns with plants. Additionally, plant uptake of 99 Tc was the greatest of all the radionuclides, with plant tissues containing an average of 44 % of the 99 Tc, while plant uptake only accounted for <2 % of 237 Np and <0.5 % of 133 Cs and 238 U in the system. Although overall plant uptake of 133 Cs and 238 U were similar, the majority of 133 Cs taken up by plants was associated with 133 Cs already available in the aqueous phase while 238 U uptake was mainly associated with the solid phase, meaning that plant activity resulted in a fraction of the native 238 U being mobilized and thus, made available for plant uptake. Overall, this study quantified the influence of several plant-mediated physical and biogeochemical factors that have significant influence on radionuclide mobility and transport in this complex system which can be further utilized in future system or site-specific environmental transport and risk assessment models.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Unraveling the influence of non-fullerene acceptor molecular packing on photovoltaic performance of organic solar cells

In non-fullerene organic solar cells, the long-range structure ordering induced by end-group π–π stacking of fused-ring non-fullerene acceptors is considered as the critical factor in realizing efficient charge transport and high power conversion efficiency. Here, we demonstrate that side-chain engineering of non-fullerene acceptors could drive the fused-ring backbone assembly from a π–π stacking mode to an intermixed packing mode, and to a non-stacking mode to refine its solid-state properties. Different from the above-mentioned understanding, we find that close atom contacts in a non-stacking mode can form efficient charge transport pathway through close side atom interactions. The intermixed solid-state packing motif in active layers could enable organic solar cells with superior efficiency and reduced non-radiative recombination loss compared with devices based on molecules with the classic end-group π–π stacking mode. Our observations open a new avenue in material design that endows better photovoltaic performance.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Thermal activation of low-density Ga implanted in Ge

The nuclear spins of low-density implanted Ga atoms in Ge are interesting candidates for solid state-based qubits. To date, activation studies of implanted Ga in Ge have focused on high densities. Here, we extend activation studies into the low-density regime. We use spreading resistance profiling and secondary ion mass spectrometry to derive electrical activation of Ga ions implanted into Ge as a function of the rapid thermal anneal temperature and implant density. We show that for our implant conditions, the activation is best for anneal temperatures between 400 and 650 °C with a maximum activation of 69% at the highest fluence. Below 400 °C, remaining implant damage results in defects that act as superfluous carriers, and above 650 °C, surface roughening and loss of Ga ions are observed. The activation increased monotonically from 10% to 69% as the implant fluence increased from 6×1010 to 6×1012 cm−2. The results provide thermal anneal conditions to be used for initial studies of using low-density Ga atoms in Ge as nuclear spin qubits.

Foster, Natalie D. (ORCID:0000000235712054)↗
DOE OSTI2025

Investigation of the Cyanothece nitrogenase cluster in Synechocystis : a blueprint for engineering nitrogen-fixing photoautotrophs

ABSTRACT The nitrogenase gene cluster of unicellular diazotrophic cyanobacteria, such asCyanothece, is frequently selected by nature for nitrogen-fixing partnerships with eukaryotic phototrophs. The essential cluster components that confer an advantage in such partnerships remain underexplored. To use this cluster for the development of synthetic, phototrophic nitrogen-fixing systems, a thorough and systematic analysis of its constituent genes is necessary. An initial effort to assess the possibility of engineering this cluster into non-diazotrophic phototrophs led to the generation of aSynechocystis6803 strain with significant nitrogenase activity. In the current study, a refactoring approach was taken to determine the dispensability of the non-structural genes in the cluster and define a minimal gene set for constructing a functional nitrogenase for phototrophs. Using a bottom-up strategy, thenifgenes fromCyanothece51142 were re-organized to form new operons. The genes were then seamlessly removed to determine their essentiality in the nitrogen fixation process. We demonstrate that besides the structural genesnifHDK,nifBSUENPVZTXW, as well ashesAB, are important for optimal nitrogenase function in a phototroph. We also show that optimal expression of these genes is crucial for efficient nitrogenase activity. Our findings provide a solid foundation for generating synthetic systems that will facilitate solar-powered conversion of atmospheric nitrogen into nitrogen-rich compounds, a stride toward a greener world. IMPORTANCE Integrating nitrogen fixation genes into various photosynthetic organisms is an exciting strategy for converting atmospheric nitrogen into nitrogen-rich products in a green and energy-efficient way. In order to facilitate this process, it is essential that we understand the fundamentals of the functioning of a prokaryotic nitrogen-fixing machinery in a non-diazotrophic, photoautotrophic cell. This study examines a nitrogenase gene cluster that has been naturally selected on multiple occasions for a nitrogen-fixing partnership by eukaryotic photoautotrophs and provides a basic blueprint for designing a photosynthetic organism with nitrogen-fixing ability.

Microbiology↗
DOE OSTI2020

Seismology on Venus with infrasound observations from balloon and orbit

The study of Venus' evolution is inexorably linked with studying its interior properties, which can be investigated by performing seismic studies on the planet. However, seismology on Venus has long eluded planetary scientists due to technological challenges presented by high surface temperature and pressure, which limit lifetimes of surface-based instrumentation. In this white paper, we present two complementary techniques for performing seismology on Venus by measuring the low-frequency acoustic signature (infrasound) produced by seismic activity through coupling between the solid planet and the atmosphere. These techniques may be implemented with technology available today, without the use of high-temperature electronics.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

Lithium–Divertor Interactions and Helium/Hydrogen Trapping in Lithiated Metals (Final Technical Report)

The goal of this project was to develop a fundamental understanding of helium and hydrogen behavior in lithium, both in bulk and at interfaces with tungsten, in order to inform the design of lithium based plasma facing components for fusion devices. Over the course of the award, the project produced the first comprehensive, peer reviewed dataset describing helium energetics, migration behaviors, and defect interactions in lithium. The research demonstrated that helium behaves in ways not previously observed in any other body centered cubic (BCC) metal: its interstitial configurations are more stable than substitutional ones, and its migration barriers are extraordinarily low, in some cases more than an order of magnitude below those in tungsten or iron. These discoveries reveal that helium in lithium diffuses so rapidly that its transport may be dominated by translational motion rather than the vibrationally activated mechanisms that underpin conventional solid state diffusion. This work lays a scientific foundation for understanding gas retention, bubble formation, and wall evolution in lithium based fusion environments and provides new computational tools, most notably a newly developed Li–He interatomic potential, for advancing future modeling efforts.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Metaproteomics reveals enzymatic strategies deployed by anaerobic microbiomes to maintain lignocellulose deconstruction at high solids

Economically viable production of cellulosic biofuels requires operation at high solids loadings—on the order of 15 wt%. To this end we characterize Nature’s ability to deconstruct and utilize mid-season switchgrass at increasing solid loadings using an anaerobic methanogenic microbiome. This community exhibits undiminished fractional carbohydrate solubilization at loadings ranging from 30 g/L to 150 g/L. Metaproteomic interrogation reveals marked increases in the abundance of specific carbohydrate-active enzyme classes. Significant enrichment of auxiliary activity family 6 enzymes at higher solids suggests a role for Fenton chemistry. Stress-response proteins accompanying these reactions are similarly upregulated at higher solids, as are β-glucosidases, xylosidases, carbohydrate-debranching, and pectin-acting enzymes—all of which indicate that removal of deconstruction inhibitors is important for observed undiminished solubilization. Our work provides insights into the mechanisms by which natural microbiomes effectively deconstruct and utilize lignocellulose at high solids loadings, informing the future development of defined cultures for efficient bioconversion.

09 BIOMASS FUELS↗
DOE OSTI2026

A Prodrug Strategy to Conditionally Trap Therapeutic Payloads for Improved Tumor Retention

Altered extracellular proteolysis has been exploited to selectively activate therapeutics in diseases such as cancer; however, once activated, extracellular drugs can diffuse away, limiting efficacy. We address this challenge by coupling proteolytic activation with membrane tethering to retain drugs within diseased tissue. To accomplish this, we developed “restricted interaction peptides” (RIPs), a delivery platform that leverages elevated proteolytic activity to activate membrane-interacting peptides, localizing cargos near the site of proteolysis. We demonstrate that RIPs can deliver diverse therapeutic cargos, including cytotoxins and radioisotopes. As proof of concept, we engineered “FRIP,” a RIP designed for cleavage by fibroblast activation protein (FAP), an endoprotease upregulated in solid tumors and fibrosis. Efficient P4–P4’ substrate sequences were identified and incorporated into FRIPs. Cell-based studies showed that, upon activation, the peptide adhered to membranes rapidly internalized and successfully delivered therapeutic cargos. Consistent with this, FRIPs delivering MMAE inhibited proliferation in an FAP-dependent manner. Imaging studies confirmed tumor targeting with minimal uptake in normal tissues. Finally, FRIPs delivering MMAE or Cu-67 exhibited potent antitumor effects. These findings establish membrane tethering as a strategy to enhance drug retention.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Electrical Analysis of Pulsed Laser Annealed Poly-Si: Ga/SiOx Passivating Contacts

In this contribution, we examine Ga hyper-doped poly-Si/SiOx contacts realized by pulsed laser melting (PLM). Here, we use Ga as a novel p-type dopant and B as a conventional dopant to induce non-equilibrium doping using an excimer laser. We perform simulations to visualize the maximum melt depth profiles within the poly-Si, with a goal of distributing dopants close to the tunneling oxide, but at the same time preserving the passivation. Hall measurements show that sheet resistance for B is lower than Ga due to its higher solid solubility limit in Si. After comparing the Hall active dopant concentration with the chemical concentration obtained by SIMS measurement, we show nearly 100% activation B activation reaching 10^21 cm-3, while only ~20% activation for Ga. Nevertheless, we achieve active doping concentrations of Ga in poly-Si six times higher than its solid solubility limit in Si (~10^19 cm-3). We compare our Hall mobilities with values in the literature for c-Si and show that B mobilities in laser-treated poly-Si are close to that of the literature value for B, while Ga mobilities are lower, possibly due to additional scattering channels within grain boundaries and deformed lattice. We also compare our results on PLM samples with conventional furnace annealed samples, and we show much higher percent activation and mobilities. Previously, we showed a low contact resistivity of 35.5 +/- 2.4 m..omega..cm2. Here, we further confirm this result by scanning spreading resistance microscopy and Kelvin force nanoprobe microscopy. We demonstrate that our poly-Si: Ga/nCz contact exhibits large drift and diffusion currents under normal cell operating voltage, which widens the laser processing window for a good metal/poly-Si/c-Si contact.

high-efficiency solar cells↗
DOE OSTI2023

Structure–transport correlations in Na 11 Sn 2 SbSe 12 and its sulfide solid solutions

We report a new ion conductor—Na 11 Sn 2 SbSe 12 —as a possible candidate for a solid catholyte in composite cathodes for all-solid state Na-batteries, which exhibits a room temperature ionic conductivity of 0.15 ± 0.03 mS cm −1 and an activation energy of 0.39 ± 0.02 eV. The sulfide solid solutions of Na 11 Sn 2 SbSe 12 , namely, Na 11 Sn 2 SbS 12−x Se x (x = 1 and 6), were also investigated through a combination of Rietveld refinement against powder x-ray diffraction data and electrochemical impedance spectroscopy to reveal the complex structure–property relationships governing ion transport in this class of materials. Meanwhile, broadening of the Na-ion diffusion pathways in Na 11 Sn 2 SbSe 12 is expected to facilitate Na-ion transport compared to the sulfide-rich member of the solid solution, the opposite holds: increasing the Se fraction in Na 11 Sn 2 SbS 12−x Se x leads to a little change in the activation energy but a reduction in the ionic conductivity. We ascribe this to the lowering of the prefactor, σ 0 , in the Arrhenius relationship with increasing lattice “softening” as a function of higher Se content.

Ramos, Erika P.↗