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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 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Water vapor oxidation behaviors of nuclear graphite IG-110 for a postulated accident scenario in high temperature gas-cooled reactors

Water leakage in accidental conditions of high temperature gas-cooled reactors is one of the most critical problems that can compromise the integrity of different nuclear components. In this study, oxidation behaviors of nuclear graphite IG-110 in water ingress accidental conditions were investigated. Mass loss and oxidation rates were evaluated after oxidation tests at temperatures up to 1400 °C in an Ar-20 vol% H 2 O mixed atmosphere. The activation energy decreased from 318.6 to 148.9 kJ/mol with temperature, indicating two different oxidation regimes. The cross-sections of the oxidized samples were systematically characterized. The corresponding logarithmic porosity profiles showed a temperature dependency. Pore formation moved toward near-surface regions with increasing temperature and preferential binder oxidation, with filler particle degradation. Furthermore, oxidant concentration profiles and oxidation depths were estimated using a theoretical model and compared with the experimental results. This work provides important benchmark data and safety analysis guidance for the accident scenario in high temperature gas-cooled reactors.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2023

Critical Contribution of Imbalanced Charge Loss to Performance Deterioration of Si-Based Lithium-Ion Cells during Calendar Aging

Increasing the energy density of lithium-ion batteries, and thereby reducing costs, is a major target for industry and academic research. One of the best opportunities is to replace the traditional graphite anode with a high-capacity anode material, such as silicon. However, Si-based lithium-ion batteries have been widely reported to suffer from a limited calendar life for automobile applications. Heretofore, there lacks a fundamental understanding of calendar aging for rationally developing mitigation strategies. Both open-circuit voltage and voltage-hold aging protocols were utilized to characterize the aging behavior of Si-based cells. Particularly, a high-precision leakage current measurement was applied to quantitatively measure the rate of parasitic reactions at the electrode/electrolyte interface. The rate of parasitic reactions at the Si anode was found 5 times and 15 times faster than those of LiNi 0.8 Mn 0.1 Co 0.1 O 2 and LiFePO 4 cathodes, respectively. Here, the imbalanced charge loss from parasitic reactions plays a critical role in exacerbating performance deterioration. In addition, a linear relationship between capacity loss and charge consumption from parasitic reactions provides fundamental support to assess calendar life through voltage-hold tests. These new findings imply that longer calendar life can be achieved by suppressing parasitic reactions at the Si anode to balance charge consumption during calendar aging.

25 ENERGY STORAGE↗
DOE OSTI2015

Coating Strategies to Improve Lithium-ion Battery Safety

This work investigated the effects of Al 2 O 3 ALD coatings on the performance and thermal abuse tolerance of graphite based anodes and Li(NixMnyCoz)O 2 (NMC) based cathodes. It was found that 5 cycles of Al 2 O 3 ALD on the graphite anode increased the onset temperature of thermal runaway by approximately 20 °C and drastically reduced the anode’s contribution to the overall amount of heat released during thermal runaway. Although Al 2 O 3 ALD improves the cycling stability of NMC based cathodes, the thermal abuse tolerance was not greatly improved. A series of conductive aluminum oxide/carbon composites were created and characterized as potential thicker protective coatings for use on NMC based cathode materials. A series of electrodes were coated with manganese monoxide ALD to test the efficacy of an oxygen scavenging coating on NMC based cathodes.

25 ENERGY STORAGE↗
DOE OSTI2011

Investigation of Path Dependence in Commercial Li-ion Cells Chosen for PHEV Duty Cycle Protocols (paper)

Path dependence is emerging as a premier issue of how electrochemical cells age in conditions that are diverse and variable in the time domain. For example, lithium-ion cells in a vehicle configuration will experience a variable combination of usage and rest periods over a range of temperature and state of charge (SOC). This is complicated by the fact that some aging can actually become worse (or better) when a lithium-ion cell is idle for extended periods under calendar-life (calL) aging, as opposed to cycle-life (cycL) conditions where the cell is used within a predictable schedule. The purpose of this study is to bridge the gap between highly idealized and controlled laboratory test conditions and actual field conditions regarding PHEV applications, so that field-type aging mechanisms can be mimicked and quantified in a repeatable laboratory setting. The main parameters are the magnitude and frequency of the thermal cycling, looking at isothermal, mild, and severe scenarios. To date, little is known about Li-ion aging effects caused by thermal cycling superimposed onto electrochemical cycling, and related path dependence. This scenario is representative of what Li-ion batteries will experience in vehicle service, where upon the typical start of a HEV/PHEV, the batteries will be cool or cold, will gradually warm up to normal temperature and operate there for a time, then will cool down after the vehicle is turned off. Such thermal cycling will occur thousands of times during the projected life of a HEV/PHEV battery pack. We propose to quantify the effects of thermal cycling on Li-ion batteries using a representative chemistry that is commercially available. The secondary Li-ion cells used in this study are of the 18650 configuration, have a nominal capacity rating of 1.9 Ah, and consist of a {LiMn2O4 + LiMn(1/3)Ni(1/3)Co(1/3)O2} cathode and a graphite anode. Electrochemical cycling is based on PHEV-relevant cycle-life protocols that are a combination of charge depleting (CD) and charge sustaining (CS) modes discussed in the Battery Test Manual for Plug-in Hybrid Electric Vehicles (INL, March 2008, rev0). A realistic duty cycle will involve both CD and CS modes, the proportion of each defined by the severity of the power demands. We assume that the cells will start each cycling day at 90% SOC, and that they will not be allowed to go below 35% SOC, with operation around 70% SOC being a nominal condition. The 35, 70, and 90% SOC conditions are also being used to define critical aspects of the related reference performance test (RPT) for this investigation. There are three primary components to the RPT, all assessed at room temperature: (A) static and residual capacity (SRC) over a matrix of current, (B) kinetics and pulse performance testing (PPT) over current for SOCs of interest, and (C) EIS for SOCs of interest. The RPT is performed on all cells every 30 day test interval, as well as a pulse-per-day to provide a quick diagnostic snapshot. Where feasible, we utilize various elements of Diagnostic Testing (DT) to characterize performance of the cells and to gain mechanistic-level knowledge regarding both performance features and limitations. We will present the rationale behind the experimental design, early data, and discuss the fundamental tools used to elucidate performance degradation mechanisms.

25 ENERGY STORAGE↗
DOE OSTI2024

Monitoring SEIRAS on a Graphitic Electrode for Surface-Sensitive Electrochemistry: Real-Time Electrografting

The ubiquity of graphitic materials in electrochemistry makes it highly desirable to probe their interfacial behavior under electrochemical control. Probing the dynamics of molecules at the electrode/electrolyte interface is possible through spectroelectrochemical approaches involving surface-enhanced infrared absorption spectroscopy (SEIRAS). Usually, this technique can only be done on plasmonic metals such as gold or carbon nanoribbons, but a more convenient substrate for carbon electrochemical studies is needed. Here, we expanded the scope of SEIRAS by introducing a robust hybrid graphene-on-gold substrate, where we monitored electrografting processes occurring at the graphene/electrolyte interface. These electrodes consist of graphene deposited onto a roughened gold-sputtered internal reflection element (IRE) for attenuated total reflectance (ATR) SEIRAS. The capabilities of the graphene-gold IRE were demonstrated by successfully monitoring the electrografting of 4-amino-2,2,6,6-tetramethyl-1-piperidine N -oxyl (4-amino-TEMPO) and 4-nitrobenzene diazonium (4-NBD) in real time. These grafts were characterized using cyclic voltammetry and ATR-SEIRAS, clearly showing the 1520 and 1350 cm –1 NO 2 stretches for 4-NBD and the 1240 cm –1 C–C, C–C–H, and N–Ȯ stretch for 4-amino-TEMPO. Successful grafts on graphene did not show the SEIRAS effect, while grafting on gold was not stable for TEMPO and had poorer resolution than on graphene-gold for 4-NBD, highlighting the uniqueness of our approach. The graphene-gold IRE is proficient at resolving the spectral responses of redox transformations, unambiguously demonstrating the real-time detection of surface processes on a graphitic electrode. This work provides ample future directions for real-time spectroelectrochemical investigations of carbon electrodes used for sensing, energy storage, electrocatalysis, and environmental applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

On the densification of cubic ZrO{sub 2} nanocondensates by capillarity force and turbostratic C–Si–H multiple shell

A turbostratic C–Si–H lamellar phase with 0.35–0.39 nm interspacing and ZrO{sub 2} condensates having cubic (c), tetragonal and monoclinic structures stabilized by increasing particle size were synthesized by pulsed laser ablation on Zr plate in TEOS and characterized by X-ray/electron diffraction and optical spectroscopy. The c-ZrO{sub 2} phase ca. 10% denser than the ambient lattice was stabilized as 3–10 nm sized cubo-octahedral nanoparticles but as abnormal large-sized (up to 30 nm) ones when encapsulated by the C{sub 1−x}Si{sub x}:H multiple shell with defective graphite-like structure units to exert an effective compressive stress. The potential application of such core–shell nanostructure with enhanced binding of Zr and O ions and implication for natural dynamic occurrence of the C{sub 1−x}Si{sub x}:H phase are addressed. - Graphical abstract: Lattice image of a typical cubic-ZrO{sub 2} particle densified by the turbostratic Si{sub x}C{sub 1−x}:H shell. Highlights: ► Turbostratic C–Si–H lamellar phase and ZrO{sub 2} condensates were synthesized by PLA. ► The c-ZrO{sub 2} phase ca. 10% denser than the ambient lattice was stabilized as 3–10 nm. ► The c-ZrO{sub 2} particles up to 30 nm were densified when encapsulated by the C{sub 1−x}Si{sub x}:H multiple shell. ► Tight ion binding of the c-ZrO{sub 2} due to capillarity force and turbostratic shell.

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

Optical Spectroscopy and Scanning Tunneling Microscopy Studies of Molecular Adsorbates and Anisotropic Ultrathin Films

The goal of the research under this project was to develop sufficient fundamental understanding to allowthe controlled preparation of nano-, and meso-structured surfaces with novel optical propertiesand chemical reactivity. The research placed an emphasis on the synthesis of, sometimes complex, surface structures under conditions that allow for detailed control and understanding of the composition and structure and the subsequent relationship to properties and chemical reactivity. In this research we utilized a combination of optical probes (Polarization and angle dependent laser reflectivity and Laser Raman Scattering) with modern surface imaging experiments (electron microscopy (SEM, TEM), and variable temperature ultra high vacuum scanning tunneling microscopy (STM)). These experiments were combined with conventional methods of UHV surface science (High Resolution Electron Energy Loss Vibrational Spectroscopy (HREELS), Auger electron spectroscopy (AES), x-ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS)). The conventional surface probes provide well-tested methods for the preparation and characterization of substrates. The optical probes used provided powerful methods for the characterization of the structure dependent optical properties of novel molecular and nanometer scale, and mesoscale surface structures as well as molecular identification and quantification of adsorbates in monolayers and ultrathin films. A combination of STM and SEM/TEM were utilized to study the growth of mesoscopically ordered nanometer sized metal and metal oxide structures on well-defined substrates such as highly ordered pyrolytic graphite (HOPG). We developed methods (e.g.photoelectrochemical deposition) to decorate nanometer scale metal oxide structures with transition metal nanoparticles generating Nanoparticles on Nanoscale substrate materials (NpNs). The electronic structure and chemical properties of these new structures were studied and contrasted with those of the more conventional nanoparticles on macroscopic substrate materials.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Nitrogen-Doping Enables Covalent-Like pi-pi Bonding between Graphenes

The neighboring layers in bi-layer (and few-layer) graphenes of both AA and AB stacking motifs are known to be separated at a distance corresponding to van der Waals (vdW) interactions. In this Letter, we present for the first time a new aspect of graphene chemistry in terms of a special chemical bonding between the giant graphene molecules . Through rigorous theoretical calculations, we demonstrate that the N-doped graphenes (NGPs) with various doping levels can form an unusual two-dimensional (2D) pi pi bonding in bi-layer NGPs bringing the neighboring NGPs to significantly reduced interlayer separations. The interlayer binding energies can be enhanced by up to 50% compared to the pristine graphene bi-layers that are characterized by only vdW interactions. Such an unusual chemical bonding arises from the pi pi overlap across the vdW gap while the individual layers maintain their in-plane pi-conjugation and are accordingly planar. The existence of the resulting interlayer covalent-like bonding is corroborated by electronic structure calculations and crystal orbital overlap population (COOP) analyses. In NGP-based graphite with the optimal doping level, the NGP layers are uniformly stacked and the 3D bulk exhibits metallic characteristics both in the in-plane and along the stacking directions.

Tian, Yong-Hui↗
DOE OSTI2019

Three-Dimensional Resistivity vs. Depth Profiling for Advanced Characterization of the Lithium-Ion Battery Solid Electrolyte Interphase

In this work, we investigate the evolution of SEI formed from a standard electrolyte (1.2 M LiPF6 in EC:EMC (3:7 wt%)) through various points in cycling on several model Si surfaces. We also examine the solubility of SEI by resting the anode in the cell at varied temperatures then characterizing the residual SEI. Evolution of the SEI surface is also analyzed with atomic force microscopy (AFM) measurements. AFM and SSRM-derived results are presented in combination with chemical characterization, including time-of-flight secondary ion mass spectrometry (TOF-SIMS).

25 ENERGY STORAGE↗
DOE OSTI2016

Fabrication of electrocatalytic Ta nanoparticles by reactive sputtering and ion soft landing

About 40 years ago, it was shown that tungsten carbide exhibits similar catalytic behavior to Pt for certain commercially relevant reactions, thereby suggesting the possibility of cheaper and earth-abundant substitutes for costly and rare precious metal catalysts. In this work, reactive magnetron sputtering of Ta in the presence of three model hydrocarbons (2-butanol, heptane, and m-xylene) combined with gas aggregation and ion soft landing was employed to prepare organic-inorganic hybrid nanoparticles (NPs) on surfaces for evaluation of catalytic activity and durability. The electro-catalytic behavior of the NPs supported on glassy carbon was evaluated in acidic aqueous solution by cyclic voltammetry. The Ta-heptane and Ta-xylene NPs were revealed to be active and robust toward promotion of the oxygen reduction reaction, an important process occurring at the cathode in fuel cells. In comparison, pure Ta and Ta-butanol NPs were essentially unreactive. Characterization techniques including atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) were applied to probe how different sputtering conditions such as the flow rates of gases, sputtering current, and aggregation length affect the properties of the NPs. AFM images reveal the focused size of the NPs as well as their preferential binding along the step edges of graphite surfaces. In comparison, TEM images of the same NPs on carbon grids show that they bind randomly to the surface with some agglomeration but little coalescence. The TEM images also reveal morphologies with crystalline cores surrounded by amorphous regions for NPs formed in the presence of 2-butanol and heptane. In contrast, NPs formed in the presence of m-xylene are amorphous throughout. XPS spectra indicate that while the percentage of Ta, C, and O in the NPs varies depending on the sputtering conditions and hydrocarbon employed, the electron binding energies of the elements are similar for all of the NPs. Here, the difference in reactivity between the NPs is attributed to their Ta/C ratios. Collectively, the findings presented herein indicate that reactive magnetron sputtering and gas aggregation combined with ion soft landing offer a promising physical approach for the synthesis of organic-inorganic hybrid NPs that have potential as low-cost durable substitutes for precious metals in catalysis

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

Lattice chain theories for dynamics of acoustic flexural phonons in nonpolar nanomaterials

Knowledge of lattice dynamics of acoustic flexural phonons is critically important in understanding the mechanical, electrical, and thermal properties of nanomaterials. However, the general nature of acoustic flexural phonons for the span of possible nanomaterials and the dependence of these on microscopic material properties remain unclear. Therefore, we develop general lattice chain theories to understand acoustic flexural vibrations in covalent and van der Waals lattices. Furthermore, the analytic theories suggest that the flexure branch has quadratic dispersion for low dimensional lattices in the long-wavelength limit, quite different from linear branches in bulk van der Waals bonded lattices like graphite. Surprisingly, interlayer van der Waals interactions in multilayer lattices do not determine the behavior of the flexural dispersion. The bonds of covalent interactions in multilayer and buckled monolayer lattices play different roles in determining the flexural dispersion with those in flat monolayer lattices, e.g., graphene. Further, based on the correspondence between microscopic and continuum dynamics, we provide a universal and effective approach to characterize the intrinsic bending rigidity of low dimensional nanomaterials using dispersion data.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2012

Effect of e-beam irradiation on graphene layer grown by chemical vapor deposition

We have grown graphene by chemical vapor deposition (CVD) and transferred it onto Si/SiO{sub 2} substrates to make tens of micron scale devices for Raman spectroscopy study. The effect of electron beam (e-beam) irradiation of various doses (600 to 12 000 {mu}C/cm{sup 2}) on CVD grown graphene has been examined by using Raman spectroscopy. It is found that the radiation exposures result in the appearance of the strong disorder D band attributed the damage to the lattice. The evolution of peak frequencies, intensities, and widths of the main Raman bands of CVD graphene is analyzed as a function of defect created by e-beam irradiation. Especially, the D and G peak evolution with increasing radiation dose follows the amorphization trajectory, which suggests transformation of graphene to the nanocrystalline and then to amorphous form. We have also estimated the strain induced by e-beam irradiation in CVD graphene. These results obtained for CVD graphene are in line with previous findings reported for the mechanically exfoliated graphene [D. Teweldebrhan and A. A. Balandin, Appl. Phys. Lett. 94, 013101 (2009)]. The results have important implications for CVD graphene characterization and device fabrication, which rely on the electron microscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Nitrogen Doping Enables Covalent-Like π–π Bonding between Graphenes

In neighboring layers of bilayer (and few-layer) graphenes, both AA and AB stacking motifs are known to be separated at a distance corresponding to van der Waals (vdW) interactions. In this Letter, we present for the first time a new aspect of graphene chemistry in terms of a special chemical bonding between the giant graphene "molecules". Through rigorous theoretical calculations, we demonstrate that the N-doped graphenes (NGPs) with various doping levels can form an unusual two-dimensional (2D) pi-pi bonding in bilayer NGPs bringing the neighboring NGPs to significantly reduced interlayer separations. The interlayer binding energies can be enhanced by up to 50% compared to the pristine graphene bilayers that are characterized by only vdW interactions. Such an unusual chemical bonding arises from the pi-pi overlap across the vdW gap while the individual layers maintain their in-plane pi-conjugation and are accordingly planar. Moreover, the existence of the resulting interlayer covalent-like bonding is corroborated by electronic structure calculations and crystal orbital overlap population (COOP) analyses. In NGP-based graphite with the optimal doping level, the NGP layers are uniformly stacked and the 3D bulk exhibits metallic characteristics both in the in-plane and along the stacking directions.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Controlling N speciation in solution synthesis of N-doped carbon materials

Carbon-based materials, such as graphite and its functionalized/doped derivatives, are promising lightweight layered materials for hydrogen activation and storage. Their propensity to control the thermodynamics of hydrogen binding and the kinetics of hydrogen mobility strongly depends on the speciation and the arrangement of dopants. In this study, we demonstrate precise control over dopant speciation and clustering in nitrogen-containing layered carbon materials during hydrothermal synthesis. Through extensive spectroscopic characterization and first principles simulations, we demonstrate that the formation of N-motifs can be controlled by the choice of precursor and synthesis temperature. The distinct three-dimensional architecture and porosity in graphene oxide and carbon nitride-derived materials furnish a synthetic pathway for precise control over the local and global structure of nitrogen-doped carbon materials and their activity toward the activation of molecular hydrogen.

Byun, Mi Yeon [Pacific Northwest National Laborato↗
DOE OSTI2019

Multiple parameter dynamic photoresponse microscopy for data-intensive optoelectronic measurements of van der Waals heterostructures

Quantum devices made from van der Waals (vdW) heterostructures of two dimensional (2D) materials may herald a new frontier in designer materials that exhibit novel electronic properties and unusual electronic phases. However, due to the complexity of layered atomic structures and the physics that emerges, experimental realization of devices with tailored physical properties will require comprehensive measurements across a large domain of material and device parameters. Such multi-parameter measurements require new strategies that combine data-intensive techniques—often applied in astronomy and high energy physics—with the experimental tools of solid state physics and materials science. We discuss the challenges of comprehensive experimental science and present a technique, called Multi-Parameter Dynamic Photoresponse Microscopy (MPDPM), which utilizes ultrafast lasers, diffraction limited scanning beam optics, and hardware automation to characterize the photoresponse of 2D heterostructures in a time efficient manner. Using comprehensive methods on vdW heterostructures results in large and complicated data sets; in the case of MPDPM, we measure a large set of images requiring advanced image analysis to extract the underlying physics. We discuss how to approach such data sets in general and in the specific case of a graphene–boron nitride–graphite heterostructure photocell.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Circumventing thermodynamic limitations in converting carbon dioxide into carbon nanotubes via tandem catalysis

Carbon nanotubes (CNTs) are important materials for electronics and structural composites, but their production still relies on hydrocarbon-based chemical vapor deposition, an energy-intensive and fossil-dependent process, limited by rapid catalyst deactivation. Using CO2 as a carbon feedstock offers a sustainable route for CNT synthesis, yet direct CO2 conversion to CNTs is thermodynamically unfavorable and existing CO2-to-carbon pathways mainly yield amorphous or weakly graphitized solids. Here, we demonstrate a tandem electrochemical–thermochemical (EC-TC) strategy that overcomes these limitations. CO2 is first electrochemically reduced to a tunable mixture of C2H4 and CO, which is directly fed into a thermochemical reactor and converted into CNTs with controllable morphology and high CNT-to-metal mass ratios (~200) over NiFe catalysts at 750 °C. In situ synchrotron-based characterization and density functional theory calculations reveal that CO dissociation and C2H4 decomposition on NiFe alloys cooperatively promote CNT nucleation and sustained growth. This EC-TC strategy establishes a modular route for converting CO2 into value-added carbon nanomaterials.

03 NATURAL GAS↗
NASA NTRS1974

Advances in the analysis and design of adhesive-bonded joints in composite aerospace structures

Several aspects of adhesive-bonded joint analysis and design are presented from the reference of size of structure or load intensity. This integrates the individual characterizations of double-lap, single-lap, stepped-lap, tapered-lap and scarf joints. The paper includes an overview of bonded joint selection from the standpoints of design, fabrication, and processing, each bearing in mind the influence of such considerations on the strength of the joint. A case study is presented of the optimization of a specific relatively thick titanium-to-graphite epoxy stepped-lap joint, using the digital computer analysis program A4EG. The factors accounted for are adhesive plasticity, adherend stiffness imbalance, adherend thermal mismatch, and change of material properties within the range of temperature environment and with load direction. The strength increases obtainable by refining the initial design are demonstrated.

Hart-Smith, L. J.↗