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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 OSTI2024

Solvent-Mediated, Reversible Ternary Graphite Intercalation Compounds for Extreme-Condition Li-Ion Batteries

Traditional Li-ion intercalation chemistry into graphite anode exclusively utilizes the co-intercalation-free or co-intercalation mechanism. The latter mechanism is based on ternary graphite intercalation compounds (t-GICs), where glyme solvents were explored and proved to deliver unsatisfied cyclability in LIBs. Herein, we report a novel intercalation mechanism, that is, in-situ synthesis of t-THF-GICs in the tetrahydrofuran (THF) electrolyte via a spontaneous, controllable reaction between binary-GICs and free THF molecules during initial graphite lithiation. The spontaneous transformation from b-GIC to t-GIC, which is different from conventional co-intercalation chemistry, is characterized and quantified via operando synchrotron X-ray and electrochemical analyses. The resulting t-GIC chemistry obviates the necessity for complete Li-ion desolvation, facilitating rapid kinetics and synchronous charge/discharge of graphite particles even under high current densities. Consequently, the graphite anode demonstrates unprecedented fast charging (1 min), dendrite-free low-temperature performance, and ultralong lifetimes exceeding 10,000 cycles. Full cells coupled with layered cathode, display remarkable cycling stability upon a 15-min charging and excellent rate capability even at -40 °C. Furthermore, our chemical strategies are shown to extend beyond Li-ion batteries to encompass Na-ion and K-ion batteries, underscoring their broad applicability. Our work contributes to the advancement of graphite intercalation chemistry and presents a low-cost, adaptable approach to achieving fast-charging and low-temperature batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Disorder and hydrogenation in graphene nanopowder revealed by complementary X-ray and neutron scattering

Functionalization of graphene's two-dimensional sheets can be used to modify the physical properties of graphene, such as changing its conductivity or inducing ferromagnetism, which is of broad interest for a myriad of applications. However, functionalized graphene can possess significant structural disorder that is often overlooked and is difficult to characterize quantitatively. Here we investigate hydrogenated graphene nanopowder (H-Gr) produced by Birch reduction of graphene oxide. By combining complementary x-ray and neutron diffraction, we show how to quantitatively characterize the H-Gr nanostructure, including the hydrogen content. Further, we show that the majority of the H-Gr consists of highly disordered molecular-scale carbon while a small portion of the sample contains few-layered graphene having an expanded interlayer spacing. Modeling the coherent diffuse scattering for both x-ray and neutron diffraction, and comparing it with the incoherent neutron scattering, the hydrogen to carbon ratio was measured and it was determined that most of the hydrogen resides within the disordered carbon rather than in the graphene. Evidence is presented for hydrogen clustering as well as for hydrogen bonded perpendicular to the plane of molecular-carbon bonds. Our quantitative approach to characterizing carbon nanopowders has broad relevance to understanding disorder and bonding of hydrogen in graphitic carbons and other nanomaterials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Extending carbon chemistry at high-pressure by synthesis of CaC 2 and Ca 3 C 7 with deprotonated polyacene- and para-poly(indenoindene)-like nanoribbons

Metal carbides are known to contain small carbon units similar to those found in the molecules of methane, acetylene, and allene. However, for numerous binary systems ab initio calculations predict the formation of unusual metal carbides with exotic polycarbon units, [C 6 ] rings, and graphitic carbon sheets at high pressure (HP). Here we report the synthesis and structural characterization of a HP-CaC 2 polymorph and a Ca 3 C7 compound featuring deprotonated polyacene-like and para-poly(indenoindene)-like nanoribbons, respectively. We also demonstrate that carbides with infinite chains of fused [C6] rings can exist even at conditions of deep planetary interiors (~140 GPa and ~3300 K). Hydrolysis of high-pressure carbides may provide a possible abiotic route to polycyclic aromatic hydrocarbons in Universe.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Elucidating the Origins of High Capacity in Iron-Based Conversion Materials: Benefit of Complementary Advanced Characterization toward Mechanistic Understanding

Lithium-ion batteries are recognized as an important electrochemical energy storage technology due to their superior volumetric and gravimetric energy densities. Graphite is widely used as the negative electrode, and its adoption enabled much of the modern portable electronics technology landscape. However, developing markets, such as electric vehicles and grid-scale storage, have increased demands, including higher energy content and a diverse materials supply chain. Alternatives that provide the opportunity to increase capacity and address supply chain concerns are of interest. Understanding the fundamental mechanisms that govern battery function is crucial to driving further improvements in the field. Advanced characterization techniques, such as those enabled by synchrotron light sources and high-resolution electron microscopes, that can uncover these mechanisms have become a necessity for elucidating structural evolution upon electrochemical conversion at the nano- to mesoscales. Performing these experiments with relevant electrochemistry using in situ and operando experiments imparts the ability to identify critical reaction pathways and capture intermediate (dis)charge products not discernible by traditional experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Enhanced Performance of Pt Nanoparticles on Ni-N Co-Doped Graphitized Carbon for Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells

Since the reaction rate and cost for cathodic catalyst in polymer electrolyte membrane fuel cells are obstacles for commercialization, the high-performance catalyst for oxygen reduction reaction is necessary. The Ni encapsulated with N-doped graphitic carbon (Ni@NGC) prepared with ethylenediamine and carbon black is employed as an efficient support for the oxygen reduction reaction. Characterizations show that the Ni@NGC has a large surface area and mesoporous structure that is suitable to the support for the Pt catalyst. The catalyst structure is identified and the size of Pt nanoparticles distributed in the narrow range of 2–3 nm. Four different nitrogen species are doped properly into graphitic carbon structure. The Pt/Ni@NGC shows higher performance than the commercial Pt/C catalyst in an acidic electrolyte. The mass activity of the Pt/Ni@NGC in fuel cell tests exhibits over 1.5 times higher than that of commercial Pt/C catalyst. The Pt/Ni@NGC catalyst at low Pt loading exhibits 47% higher maximum power density than the Pt/C catalyst under H2-air atmosphere. These results indicate that the Ni@NGC as a support is significantly beneficial to improving activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Antimicrobial mechanisms of g‐C 3 N 4 @ ZnO against oomycetes Phytophthora capsici: from its metabolism, membrane structures and growth

Abstract BACKGROUND Phytophthora capsici , a refractory and model oomycete plant pathogen, especially threatens multiple vegetable crops. A limited number of chemical pesticides play a vital role in controlling oomycete plant diseases. However, this approach often leads to excessive use of chemical agent, exacerbates environmental issues and more and more drug‐resistant strains of oomycete. Therefore, it is imperative to devise innovative solutions that can effectively address the infection of oomycete while maintaining high levels of environmental sustainability and low toxicity. RESULTS In this study, g‐C 3 N 4 @ZnO heterostructure was synthesized and characterized. The g‐C 3 N 4 @ZnO showed higher toxicity on Phytophthora capsici than graphitic carbon nitride (g‐C 3 N 4 ) nanosheets and zinc oxide (ZnO) nanoparticles in vitro and in vivo . Except the hyphal growth of Phytophthora capsici , their germination rate of spores, sporangium formation and number of spores were all suppressed by g‐C 3 N 4 @ZnO heterostructure. Furthermore, we found that this g‐C 3 N 4 @ZnO heterostructure has higher photocatalytic activity under visible light, which potentially enhanced the reactive oxygen species (ROS) mediated stress on Phytophthora capsici . Ultrastructural morphology, global changes of gene expression and weighted gene co‐expression network analysis all supported that the anti‐oomycete activity of g‐C 3 N 4 @ZnO was manifested in the destruction of membrane system and inhibition of multiple metabolisms of Phytophthora capsici under visible irradiation, which also could be attributed to the ROS and zinc ion (Zn 2+ ) mediated stress. CONCLUSION This works offers a novel oomycete disease management strategy by using g‐C 3 N 4 @ZnO, which were attributed to the ROS stress, destruction of membrane system and inhibition of multiple metabolisms. © 2023 Society of Chemical Industry.

Cai, Lin↗
DOE OSTI2021

Stamping Nanoparticles onto the Electrode for Rapid Electrochemical Analysis in Microfluidics

Electrochemical analysis is an efficient way to study various materials. However, nanoparticles are challenging due to the difficulty in fabricating a uniform electrode containing nanoparticles. We developed novel approaches to incorporate nanoparticles as a working electrode (WE) in a three-electrode microfluidic electrochemical cell. Specifically, conductive epoxy was used as a medium for direct application of nanoparticles onto the electrode surface. Three approaches in this work were illustrated, including sequence stamping, mix stamping, and droplet stamping. Shadow masking was used to form the conductive structure in the WE surface on a thin silicon nitride (SiN) membrane. Two types of nanomaterials, namely cerium oxide (CeO2) and graphite, were chosen as representative nanoparticles. The as-fabricated electrodes with attached particles were characterized using atomic force microscopy (AFM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Electrochemical analysis was performed to verify the feasibility of these nanoparticles as electrodes. Nanomaterials can be quickly assessed for their electrochemical properties using these new electrode fabrication methods in a microfluidic cell, offering a passport for rapid nanomaterial electrochemical analysis in the future.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Development of Electrochemical Detectors for Elemental Characterization of Actinides - 20563

The characterization of the actinides contained in radioactive waste involves complex and expensive separation processes. Electrochemical methods allow identifying and quantifying quickly and accurately the elementary concentration of actinides such as Th, U, Pu, Am, and Cm in liquid waste. The objective of this research proposal is to build a low-cost portable miniaturized electrochemical detector, which can be an alternative for an initial characterization of actinides in liquid waste. Therefore, this work proposes the use of an electrochemical graphite detector modified with phthalocyanine, to detect and quantify actinides in aqueous media. The electrochemical response of the modified graphite electrodes was performed by cyclic voltammetry, and so the detection and quantification limits for U and Th were determined. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Characterization of Annealing-Induced Phase Segregation in Composite Silicon Anodes for Li-ion Batteries

Silicon (Si) anodes present a promising alternative to graphite anodes for lithium-ion batteries (LIBs), as Si has a greater specific capacity. However, one major constraint is the volumetric change of Si during lithiation that results in an unstable solid-electrolyte interphase (SEI), so Si-containing electrodes require the use of various strategies to mitigate these effects and improve performance. One such solution is the use of Si nanoparticles (NPs) that maximize the surface area to volume ratio. Here, we discuss electrodes made with Si NPs treated with polyethylene oxide (PEO) (for improving dispersion during processing), conductive carbon NPs, and P84 polyimide binder which shows significant impacts of annealing treatment on improvements of active material utilization, first cycle efficiency, and capacity retention with extensive cycling . We used air-free argon ion polishing to create electrode cross sections and imaged through the electrode thickness using atomic force microscopy (AFM)-based nano-electrical characterization of scanning spreading resistance microscopy (SSRM), nano-mechanical characterizations of contact resonance and force volume (CR-FV), and scanning electron microscopy-based energy dispersive x-ray spectroscopy (SEM-EDS). Results show that the Si and conductive carbon segregate into phases with a distinctive carbon-rich banded morphology that surrounds the Si-rich phase during annealing. In pristine electrodes, the carbon- and SEI-rich bands exhibit a higher electronic conductivity and a lower elastic modulus than the Si active material phase. These structures, as well as distinct electronic and mechanical properties, remain during cycling, suggesting an improvement of electrical conduction pathways and a mechanical strain buffer for active Si material expansion during cycling. This phase separation may be a major factor in the improvement seen in electrochemical performance due to annealing. Additionally, our nm-scale and multi-mode characterizations provide a novel route for understanding and improving energy storage devices, which is advantageous due to the highly inhomogeneous of composite electrodes in nm-mm scales.

ENERGY STORAGE↗
DOE OSTI2020

Three-Dimensional Mapping of Resistivity and Microstructure of Composite Electrodes for Lithium-Ion Batteries

Nanoparticle silicon–graphite composite electrodes are a viable way to advance the cycle life and energy density of lithium-ion batteries. However, characterization of composite electrode architectures is complicated by the heterogeneous mixture of electrode components and nanoscale diameter of particles, which falls beneath the lateral and depth resolution of most laboratory-based instruments. In this work, we report an original laboratory-based scanning probe microscopy approach to investigate composite electrode microstructures with nanometer-scale resolution via contrast in the electronic properties of electrode components. Applying this technique to silicon-based composite anodes demonstrates that graphite, SiOx nanoparticles, carbon black, and LiPAA binder are all readily distinguished by their intrinsic electronic properties, with measured electronic resistivity closely matching their known material properties. Resolution is demonstrated by identification of individual nanoparticles as small as ~20 nm. Our technique presents future utility in multiscale characterization to better understand particle dispersion, localized lithiation, and degradation processes in composite electrodes for lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Overcoming Variability: A Reproducible Approach to SERS Detection of Nanodiamonds

Detonation nanodiamonds (DNDs) are formed at specific pressures and temperatures during explosions. Different explosives produce varied yields of DNDs within their detonation soot, with Composition B producing the highest yield. Raman spectroscopy (RS) is often used for the characterization of sp 2 - and sp 3 -hybridized carbon allotropes in carbonaceous materials because of distinct disorder and graphitic bands. Bulk diamond also gives a distinct Raman peak at 1332 cm –1 . Furthermore, as bulk diamond decreases in size to nanometer-sized species, the peak red-shifts and broadens, becoming increasingly difficult to detect with RS using visible excitations. Therefore, surface-enhanced Raman spectroscopy (SERS) was used to enhance the diamond peak of DNDs, enabling better detection and faster examination of DNDs within detonation soot. Previous literature of the SERS of DNDs delivered inconsistent results in spectral signatures and SERS substrates. Herein, refining of the methodology for the acquisition of SERS spectra of DNDs was achieved. Before any SERS experiments, the DNDs were first characterized with normal Raman (NR) and scanning electron microscopy. Two routes for SERS enhancement were evaluated: colloidal noble metal nanoparticles and evaporated silver films. Silver films produced the best signal enhancement of DNDs with the best signal-to-noise and peak enhancements observed at 20–30 nm thick silver films at 5% (∼300 μW) laser power. Consistent, reproducible SERS spectra were acquired of small aggregates of DNDs down to ∼500 nm. NR and SERS mapping analysis of DNDs before and after evaporation of silver films revealed the improvements in the detection capabilities of SERS compared with NR.

Carbon↗
DOE OSTI2025

Characterizing Hazardous Gases from NMC811 Materials and Coin Cells with TGA and Tube-Furnace FTIR-MS Evolved-Gas-Analysis

Abuse testing is useful for informing the risks of different battery chemistries but has been limited to larger formats. This paper conducted thermal abuse tests at the smaller coin cell level to determine its relevance in specifying vent gas flammability and toxicity. A nitrogen purge carried the evolved gases into a parallel Fourier-transform infrared spectrometer (FTIR) and a mass spectrometer (MS) downstream of the tube furnace. The experimental system was validated by comparing evolved gas data for single components between the tube furnace system and a thermogravimetric analysis (TGA) instrument. Multiple samples were tested during validation, including CaCO3, electrolyte, delithiated NMC 811 cathode, and lithiated graphite anode. Temperature-resolved gas evolution of HF, CO2, CO, H2, and hydrocarbons from isolated components helped to characterize the emission sources. A previously unreported H2 generation mechanism was found. It was shown that the reduced NMC cathode acts as a catalyst to crack polypropylene-decomposed hydrocarbons into H2 at around 450 degrees C. It was also shown, while studying LiPF6 thermal decomposition, that using the tube furnace with a coin cell casing as the sample holder has some advantages for evolved-gas analysis of environmentally sensitive samples relative to testing in TGA instruments. After validation with single components, a fully charged NMC 811 coin cell was failed in the tube furnace. The measured evolved gases were found to be a combination of the species measured from the single component tests. H2 formation related to the reduced cathode was found to have greater abundance than H2 formed from the anode. Hydrogen fluoride emission factors and diethyl carbonate conversion emission factors assist in understanding the gaseous hazards for larger format cells.

25 ENERGY STORAGE↗
DOE OSTI2021

Characterization of zirconium carbide microspheres synthesized via internal gelation

Microspheres of zirconium carbide with grain size 40-320 nm were synthesized using internal gelation techniques and characterized by scanning electron microscopy, synchrotron X-ray diffraction, and neutron total scattering. Compared with a polycrystalline benchmark ZrC sample prepared by plasma vapor phase deposition, the microspheres display lower variance in grain size and considerably lower microstrain representative of a more homogenous internal microstructure. However, excess carbon was present in the microspheres, evident in both the X-ray and neutron diffraction data as well as a corresponding hypostoichiometric ZrC phase. Furthermore, the excess carbon phase is assumed to be pockets of carbon that remained unreacted through the combined internal gelation and subsequent carbothermic reduction synthesis process. Atomic-scale structural characterization with neutron PDF analysis confirmed the presence of localized nano-sized domains of graphite-like carbon material.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Estimating the Diffusion Coefficient of Lithium in Graphite: Extremely Fast Charging and a Comparison of Data Analysis Techniques

Galvanostatic intermittent titration experiments were performed in three-electrode cells to characterize the effect of C/2, 2-C and 4-C charge rates on the observed lithium diffusion coefficient. As part of the data analysis process, we compared the classic Weppner-Huggins analysis of polarization data with a newer (Wang et al.) analysis method for depolarization data. At low values of x in Li x C 6 , both analysis methods showed the same general trend in the apparent lithium diffusion coefficient, 4-C > 2-C > C/2. The two techniques differed in the magnitude of the estimated diffusion coefficient by about a factor of 100. The observed increase in diffusion coefficient does not last over a large compositional range. Since the estimates from the method of Weppner and Huggins may contain artifacts due to the use of particulate electrodes and high charge rates, the method of Wang et al. may produce better values.

25 ENERGY STORAGE↗
DOE OSTI2026

Quantitative measurement of pebble fuel anisotropy using generalized ellipsometry

The renewed development of high-temperature gas-cooled reactors has created a need to modernize pebble fuel quality control methods. One important specification in these methods is the coefficient of thermal expansion (CTE) anisotropy, which reflects graphite grain alignment and affects fuel performance. This study investigates the feasibility of using two-modulator generalized ellipsometry microscopy (2-MGEM) as a potential surrogate metric for CTE anisotropy. Graphite matrix compacts with controlled levels of anisotropy were fabricated by varying pre-pressures during forming and were subsequently characterized using both optical dilatometry and 2-MGEM. Measured responses were compared to an isotropic reference pebble produced using an industrial manufacturing process to provide a practical baseline. The resulting measurements revealed a strong quantitative correlation between the CTE anisotropy ratio and the corresponding diattenuation ratio. However, propagated measurement uncertainties in the optical method were found to limit definitive pass/fail discrimination, highlighting the need for improved precision before qualification as a quality control tool. Still, the results establish a quantitative relationship between optical and CTE anisotropy and support further development of 2-MGEM as a potential surrogate method for evaluating graphite matrix anisotropy in pebble fuel manufacturing.

Raftery, Alicia [ORNL] (ORCID:0000000259076427)↗
DOE OSTI2024

Low-Temperature Annealing of Nanoscale Defects in Polycrystalline Graphite

Polycrystalline graphite contains multi-scale defects, which are difficult to anneal thermally because of the extremely high temperatures involved in the manufacturing process. In this study, we demonstrate annealing of nuclear graphite NBG-18 at temperatures below 28 °C, exploiting the electron wind force, a non-thermal stimulus. High current density pulses were passed through the specimens with a very low-duty cycle so that the electron momentum could mobilize the defects without heating the specimen. The effectiveness of this technique is presented with a significant decrease in electrical resistivity, defect counts from X-ray computed tomography, Raman spectroscopy, and nanoindentation-based mechanical characterization. Such multi-modal evidence highlights the feasibility of nanoscale defect control at temperatures about two orders of magnitude below the graphitization temperature.

Liu, Gongyuan↗
DOE OSTI2020

Determination of preferential binder oxidation in HTGR matrix material subjected to high temperature steam

Graphitic matrix material encapsulates tristructural isotropic (TRISO) coated fuel particles and is a structural component for both pebble and cylindrical fuel compacts in high temperature gas reactor (HTGR) designs. In an off-normal event involving steam exposure, the matrix material is exposed to oxidants, leading to degradation of the fuel compact and subsequent exposure of the TRISO particle fuel to oxidizing species. This study presents microstructural characterization of matrix material after exposure to high temperature (1200°C), 48 kPa steam in which the evolved microstructure demonstrated nonuniform degradation. Subsequent Raman spectroscopy determined the nature of the remaining material post-exposure. Finally, the electron microscopy characterization suggests and Raman spectroscopic analysis confirms, under off-normal conditions, the carbonized phenolic resin binder is preferentially oxidized ahead of the graphite flake filler and is responsible for the nonuniform degradation and enhanced depth of attack.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Energy Characterization of the UMD Electron Accelerator

Multiple different groups at Los Alamos National Laboratory have a cited interest in understanding the effects of ionizing radiation in materials. Of especial interest to the ISR division is understanding the effects in materials that are used in the space environment, where radiation is omnipresent and impossible to fully shield from. Development is under way to simulate the effects of radiation damage in detectors and electronics, primarily with particle transport codes such as Geant4 and RAMPART, a code that provides a user friendly interface to Geant4. However, these simulations need benchmarking to experimental tests, some of which have been performed at a variety of small electron accelerator facilities. One of these facilities is the Linear Electron Accelerator at the University of Maryland Radiation Facilities. This facility can provide electron beams on the order of 100 mA delivered in tight macropulse bunches, which allows for experiments where the behavior of electronics is monitored as a function of pulse number. While the beam rates per macropulse of this accelerator is monitored during an experiment via a current pick-off connected to a large graphite beamstop, the energy distribution of this electron beam is not measured during the experiment and has not been well characterized. The energy distribution of the beam is pertinent for these types of experiments, since dose is directly related to energy deposited in a medium. Further, these experiments are performed in open air and sample placement in the room can dictate what dose rate they receive per macropulse. We have created simulated dosemaps for the UMD vault room, but these simulations assume a given energy of the beam, both for calculating the dose and to simulate how much the beam diverges in the air. There have been two attempts now to characterize this accelerator beam energy with a plate type spectrometer, including the most recent experiment earlier this year to quantify the beam energy distribution. These results will also be compared to a dosimetry experiment performed by collaborators at the UMD facility, the details of which are described in Reference. Understanding the electron beam energy is important for future experiments, because the energy directly impacts the dose and radiation damage given to a sample and is important for properly simulating the electron beam when comparing simulation to experiment.

43 PARTICLE ACCELERATORS↗