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NASA NTRS1981

Absorption of visible radiation in atmosphere containing mixtures of absorbing and nonabsorbing particles

The presence of a strongly absorbing material, tentatively identified as graphitic carbon, or 'soot', is indicated by measurements of single-scattering albedo of tropospheric aerosols. Although theoretical calculations based on models of the ways in which soot may mix with other aerosol materials yield the single-scattering albedo values of 0.6, accounted for by a minimum 20% soot by volume, in urban regions and 0.8, yielded by 1-5% soot by volume, in rural settings, it is found that these same values can be produced by similar amounts of the iron oxide magnetite. Magnetite is shown to be indistinguishable from soot by optical measurements performed on bulk samples, and calculation of various mixtures of soot indicate the difficulty of determining aerosol composition by optical scattering techniques.

Ackerman, T. P.↗

NASA NTRS1995

Ferrix Chloride-Graphite Intercalation Compounds Prepared From Graphite Flouride

The reaction between graphite fluoride and ferric chloride was observed in the temperature range of 300 to 400 C. The graphite fluorides used for this reaction have an sp(sup 3) electronic structure and are electrical insulators. They can be made by fluorinating either carbon fibers or powder having various degrees of graphitization. Reaction is fast and spontaneous and can occur in the presence of air. The ferric chloride does not have to be predried. The products have an sp(sup 2) electronic structure and are electrical conductors. They contain first-stage FeCl3 intercalated graphite. Some of the products contain FeCl2 (center dot) 2H2O, others contain FeF3, in concentrations that depend on the intercalation condition. The graphite intercalated compounds (GIC) deintercalated slowly in air at room temperature, but deintercalated quickly and completely at 370 C. Deintercalation is accompanied by the disappearance of iron halides and the formation of rust (hematite) distributed unevenly on the fiber surface. When heated to 400 C in pure N2 (99.99 vol%), this new GIC deintercalates without losing its molecular structure. However, when the compounds are exposed to 800 C N2, in a quartz tube, they lost most of their halogen atoms and formed iron oxides (other than hematite), distributed evenly in or on the fiber.

Hung, Ching-Cheh↗

DOE OSTI2020

Magnetite nanoparticle anchored graphene cathode enhances microbial electrosynthesis of polyhydroxybutyrate by Rhodopseudomonas palustris TIE-1

Microbial electrosynthesis (MES) is an emerging technology that can convert carbon dioxide (CO 2 ) into value-added organic carbon compounds using electrons supplied from a cathode. However, MES is affected by low product formation due to limited extracellular electron uptake by microbes. Herein, a novel cathode was developed from chemically synthesized magnetite nanoparticles and reduced graphene oxide nanocomposite (rGO-MNPs). This nanocomposite was electrochemically deposited on carbon felt (CF/rGO-MNPs), and the modified material was used as a cathode for MES production. The bioplastic, polyhydroxybutyrate (PHB) produced by Rhodopseudomonas palustris TIE-1 (TIE-1), was measured from reactors with modified and unmodified cathodes. Results demonstrate that the magnetite nanoparticle anchored graphene cathode (CF/rGO-MNPs) exhibited higher PHB production (91.31 ± 0.9 mg l -1 ). This is ~4.2 times higher than unmodified carbon felt (CF), and 20 times higher than previously reported using graphite. This modified cathode enhanced electron uptake to -11.7 ± 0.1 μ A cm -2 , ~5 times higher than CF cathode (-2.3 ± 0.08 μ A cm -2 ). The faradaic efficiency of the modified cathode was ~2 times higher than the unmodified cathode. Electrochemical analysis and scanning electron microscopy suggest that rGO-MNPs facilitated electron uptake and improved PHB production by TIE-1. Overall, the nanocomposite (rGO-MNPs) cathode modification enhances MES efficiency.

Materials Science↗

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 OSTI2026

Techno-Economic Analysis of Recycling Strategies for Catalyst and Acid During Catalytic Graphitization

With the aim of meeting the urgent demand for active anode materials (AAM) in energy storage systems, bio-based graphite (biographite) emerges as an affordable solution to de-risk the turbulent supply chain of critical minerals. Anode grade biographite requires high crystallinity and purity, which can be achieved by catalytic graphitization with iron, followed by acid washing. Therefore, a well-conceived process integration that recycles catalyst can be the starting point to commercialization. This study evaluates closed-loop catalyst recovery, and byproducts valorization scenarios through a technoeconomic framework to help understand the scale-up potential of biographite. For the acid washing, three reactors in series meet the required biographite purity at 99.95%. Iron and acid recovery can reduce material consumption and waste generation by ~95%, albeit at the expense of ~80% increase in capital costs. Recovery scenarios present similar capital and operational expenses, yielding minimum selling prices (MSP) near $6 kg-1 of biographite. Monte Carlo methodology reveals that feedstock price accounts for ~60% of MSP variance, followed by plant capacity ~20%. The likelihood of reaching a competitive profit margin of 30% in the U.S. AAM market sits at 85% average for recovery scenarios, and 103% when iron oxide is sold as byproduct. Additionally, an IRR >= 15% can be achieved for half of Monte Carlo simulations, representing promising early-stage results. Biographite production offers a strategic pathway to stabilize the anode market beyond China by integrating established technologies for a scalable, economically viable, and sustainable process. The role of catalyst recovery and byproducts utilization is critical for advancing the biomaterials industry.

97 MATHEMATICS AND COMPUTING↗

NASA NTRS1976

Effects of atomic oxygen on graphite ablation

It is shown that a previously derived semiempirical equation for describing observed ablation rates of isotropic graphites cannot be applied to low-density flows containing dissociated oxygen. Experimentally determined reaction probabilities of isotropic graphites to molecular and atomic oxygen are used to calculate heat-transfer rates and stagnation-point ablation rates for typical conditions. Integrated mass losses are computed for a group of flight trajectories which start from geosynchronous orbit and enter earth's atmosphere in a skipping motion following near-elliptic decaying orbits. A comparison of the results with those obtained by the equation under question shows excellent agreement for steep trajectories, but large discrepancies for shallow trajectories. The differences are attributed to surface oxidation by atomic oxygen.

Park, C.↗

NASA NTRS2011

Online Oxide Contamination Measurement and Purification Demonstration

Liquid metal sodium-potassium (NaK) has advantageous thermodynamic properties indicating its use as a fission reactor coolant for a surface (lunar, martian) power system. A major area of concern for fission reactor cooling systems is system corrosion due to oxygen contaminants at the high operating temperatures experienced. A small-scale, approximately 4-L capacity, simulated fission reactor cooling system employing NaK as a coolant was fabricated and tested with the goal of demonstrating a noninvasive oxygen detection and purification system. In order to generate prototypical conditions in the simulated cooling system, several system components were designed, fabricated, and tested. These major components were a fully-sealed, magnetically-coupled mechanical NaK pump, a graphite element heated reservoir, a plugging indicator system, and a cold trap. All system components were successfully demonstrated at a maximum system flow rate of approximately 150 cc/s at temperatures up to 550 C. Coolant purification was accomplished using a cold trap before and after plugging operations which showed a relative reduction in oxygen content.

Bradley, D. E.↗

DOE OSTI2020

Neutronic Consideration of TREAT Facility Fuel SiC Recladding

The Transient Reactor Test (TREAT) Facility is an air-cooled reactor composed of graphite-urania fuel encapsulated in zirconium alloy canisters and surrounded by ~2 ft (~61 cm) of nuclear grade graphite. The primary role of TREAT is to provide in-pile nuclear-heated safety research via transient testing [1]. Benchmark efforts have demonstrated sensitivity of TREAT neutronics models to graphite cross section data and key neutron poisons found in the fuel assemblies [2]. During fabrication of TREAT fuel assemblies, a small concentration of boron was inadvertently introduced with variable concentration into the aggregate of fuel blocks prepared for TREAT use. The concentration of boron, and its respective uncertainty, represent the most sensitive component in a neutronics study; unfortunately, nothing can be done to reduce or otherwise mitigate its impact. Hydrogen in the fuel blocks reduces the mean free path of the core and its true quantity and uncertainty is approximated. The hydrogen remains from pitch binder used in the fuel fabrication process and was not completely released due to incomplete fuel graphitization. Destructive fuel testing is necessary to quantify the actual hydrogen content and to improve benchmark model quality. A third neutron poison of some significance is the hafnium impurity in the Zircaloy-3 (Zry-3) assembly cladding. The quantity of hafnium is expected to be within nominal manufacturing limits for nuclear grade zircaloy. Recladding the fuel assemblies with material that is less neutron absorbing is expected to benefit reactor neutron economy. Moreover, TREAT’s total transient energy is restricted based on the rate of Zry-3 oxidation in TREAT’s air coolant environment. Hence, cladding with more benign air reaction kinetics could dramatically uprate the facility’s experimental capability. Silicon carbide (SiC) has been proposed as a candidate material for recladding TREAT assemblies, as SiC/SiC demonstrate favorable properties within nuclear environments [3]. The current operational limits of TREAT are restricted by the oxidation of Zry-3. Change of the cladding to SiC could feasibly double the current temperature limitation. Recladding opportunities allow for previously damaged fuel assemblies to be returned to service, as Zry-3 is not commercially available. The initial effort required to consider proceeding with any recladding effort is to neutronically characterize key reactor parameters while replacing Zry-3 with SiC. A characterization summary, with respective results, is provided herein.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2020

Dual 3D Ceramic Textile Electrodes: Fast Kinetics for Carbon Oxidation Reaction and Oxygen Reduction Reaction in Direct Carbon Fuel Cells at Reduced Temperatures

Abstract Direct carbon fuel cells (DCFCs) are an efficient energy‐conversion technology capable of generating electricity with carbon‐dioxide‐capture chemistry with solid carbon as fuels. The efficiency and performance of DCFCs depend on the kinetics of the carbon oxidation reactions (COR) and the oxygen reduction reactions (ORR), each occurring at anode and cathode, respectively. The limited active sites paired with reduced temperatures greatly decrease the efficiency of the electrochemical reactions. Ultraporous dual‐3D ceramic textiles (dual‐3DCT) are integrated into electrolyte‐supported DCFCs to enhance charge and mass transfer at the electrodes. Improved COR at the anode is achieved by the synergy between the 3DCT NiO–Ce 0.8 Gd 0.2 O 1.95 (GDC) structure and optimal carbon fuel choice. In a comparative study, DCFCs using graphitic carbon (GC) as fuel show the best COR performance when compared to DCFCs utilizing alternative fuels such as carbon black (CB) and activated carbon (AC). The 3DCT Sm 0.5 Sr 0.5 CoO 3‐δ –GDC (SSC–GDC) composite cathode shows electrochemical performance superior to that of the conventional screen‐printed SSC–GDC. A peak power density of 392 mW cm −2 at 600 °C is obtained in a DCFC using the 3DCT‐anode/electrolyte/3DCT‐cathode configuration, an unprecedented value for any reported DCFC as of yet. This points toward promising applications of dual‐3DCT electrodes for reduced‐temperature DCFCs.

Bian, Wenjuan↗

DOE OSTI2014

Extraordinary suppression of carrier scattering in large area graphene oxide films

In this study, we find that thermal treatment in ethanol vapor has a remarkable suppression effect of carrier scattering occurring between reduced graphene oxide (rGO) flakes in large area films. We observe excellent electrical properties such as high carrier mobility (∼5 cm{sup 2}/Vs) and low sheet resistance (∼40 KΩ/□) for the rGO films. From the electrical conductivity analysis of large area rGO films using two-dimensional variable range hopping model and structural analysis using Raman spectra measured from the rGO films, we reveal that the significant effect is caused by the expansion of conjugated π-electron system in rGO flake due to the efficient restoration of graphitic structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2022

Crossover Effects in Lithium–Metal Batteries with a Localized High Concentration Electrolyte and High–Nickel Cathodes

While crossover effects, such as transition–metal dissolution, are well–understood in lithium–ion batteries, there is a limited understanding of the effect of crossed–over chemical species in cells with oxide cathodes and lithium–metal anodes. In this work, the effects of cathode–to–anode and anode–to–cathode crossover are explored in cells with a high–nickel cathode, lithium–metal anode, and a localized high–concentration electrolyte (LHCE). Dramatic differences are found among cells; a lithium–metal anode paired with a high–nickel cathode has three times less solid–electrolyte interphase growth than a lithium–metal anode paired with lithium metal. Meanwhile, the cathode paired with lithium metal has 2–3 times higher capacity fade than the same cathode paired with graphite. Decomposition and crossover of the FSI salt is identified as the main source of these changes. The fluorine in the salt is first stripped off at the lithium–metal anode, and the remaining sulfur and nitrogen cross over to the cathode. Although the reduction in fluorine content harms the surface stability of the cathode, the lithium–metal anode benefits from the increased fluorine content. Furthermore, because the lithium–metal anode is typically the bottleneck for cells with thin lithium, crossover is a major factor in the enhanced performance of lithium–metal batteries with LHCE.

25 ENERGY STORAGE↗

DOE OSTI2021

Time-Resolved X-ray Operando Observations of Lithiation Gradients across the Cathode Matrix and Individual Oxide Particles during Fast Cycling of a Li-Ion Cell

Lithiated transition metal oxides serve as active materials in the positive electrode (cathode) of lithium-ion cells. During electrochemical cycling, lithium ions intercalate and deintercalate into these oxide particles. This behavior causes two types of lithiation gradients to emerge: (i) a bulk gradient across the depth of the cathode matrix (averaged over individual oxide particles) and (ii) a microscopic gradient across the particles themselves, which also depends on their location in the electrode. Here we show how both gradients can be studied using operando X-ray diffraction during 4C charge and 4C discharge. The oxide (de)lithiation is estimated from the unit cell parameters by indexing the X-ray diffraction spectra. By fitting the lithiation profiles with orthogonal polynomials, the bulk gradients across the electrode thickness are quantified. These gradients develop as the current flows through the cell and dissipate during open-circuit and potentiostatic-hold periods. Further details of lithiation dynamics can be obtained through shape analysis of the Bragg peaks. In particular, from electrochemical model simulations, we show that the width and skewness of the (003) peak track (de)lithiation fronts moving across the individual oxide particles.

(003) peak↗

DOE OSTI2014

Status of the NGNP graphite creep experiments AGC-1 and AGC-2 irradiated in the advanced test reactor

The United States Department of Energy's Next Generation Nuclear Plant (NGNP) Program will be irradiating six nuclear graphite creep experiments in the Advanced Test Reactor (ATR) located at the Idaho National Laboratory (INL). The graphite experiments will be irradiated over the next six to eight years to support development of a graphite irradiation performance data base on the new nuclear grade graphites now available for use in high temperature gas reactors. The goals of the irradiation experiments are to obtain irradiation performance data, including irradiation creep, at different temperatures and loading conditions to support design of the next generation nuclear plant (NGNP) very high temperature gas reactor, as well as other future gas reactors. The experiments will each consist of a single capsule that will contain six peripheral stacks of graphite specimens, with half of the graphite specimens in each stack under a compressive load, while the other half of the specimens will not be subjected to a compressive load during irradiation. The six peripheral stacks will have three different compressive loads applied to the top half of three diametrically opposite pairs of specimen stacks, while a seventh stack will not have a compressive load. The specimens will be irradiated in an inert sweep gas atmosphere with on-line temperature and compressive load monitoring and control. There will also be sampling the sweep gas effluent to determine if any oxidation or off-gassing of the specimens occurs during irradiation of the experiment.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2024

4.6 V Moisture‐Tolerant Electrolytes for Lithium‐Ion Batteries

Abstract Commercial LiPF 6 ‐based electrolytes face limitations in oxidation stability (4.2 V) and water tolerance (10 ppm). While replacing LiPF 6 with lithium bis(trifluoromethane)sulfonimide (LiTFSI) improves water tolerance, it induces Al current collector corrosion above 3.7 V vs. Li/Li + . To address this, lithium cyano(trifluoromethanesulfonyl)imide (LiCTFSI) is proposed here as a non‐corrosive, moisture‐tolerant alternative. The 2.0 M LiCTFSI/propylene carbonate (PC)‐fluoroethylene carbonate (FEC) (7:3 by volume) electrolyte enables LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) cathodes to reach 210 mAh g −1 (2.8‐4.6 V) with a cycle life of 500. Full cells with NCM811||graphite (2.0 mAh cm −2 ) show 77.8% capacity retention after 500 cycles. Even with 2000 ppm moisture in the electrolyte, full cells maintain high cycling stability, reducing the need for costly dry rooms. The electrolyte’s low freezing point and high thermal stability enable the operation from ‐20 °C to 60 °C, delivering 168 mAh g −1 at ‐20 °C and retaining 94% capacity after 100 cycles at 60 °C. In contrast, cells with commercial LiPF 6 electrolyte deliver 71 mAh g −1 at ‐20°C and retain 52.7% after 100 cycles at 60 °C. This novel salt offers a cost‐effective solution for developing robust, high‐performance batteries suitable for extreme conditions.

Zhang, Nan↗

NASA NTRS1979

Second generation PMR polyimide/fiber composites

A second generation polymerization monomeric reactants (PMR) polyimdes matrix system (PMR 2) was characterized in both neat resin and composite form with two different graphite fiber reinforcements. Three different formulated molecular weight levels of laboratory prepared PMR 2 were examined, in addition to a purchased experimental fully formulated PMR 2 precurser solution. Isothermal aging of graphite fibers, neat resin samples and composite specimens in air at 316 C were investigated. Humidity exposures at 65 C and 97 percent relative humidity were conducted for both neat resin and composites for eight day periods. Anaerobic char of neat resin and fire testing of composites were conducted with PMR 15, PMR 2, and an epoxy system. Composites were fire tested on a burner rig developed for this program. Results indicate that neat PMR 2 resins exhibit excellent isothermal resistance and that PMR 2 composite properties appear to be influenced by the thermo-oxidative stability of the reinforcing fiber.

Cavano, P. J.↗

DOE OSTI2017

A novel coronene//Na 2 Ti 3 O 7 dual-ion battery

Here we construct a novel sodium dual-ion battery (Na-DIB) with a conventional alkyl/alkylene carbonate electrolyte by using reduced-graphene-oxide-coated Na 2 Ti 3 O 7 (NTO@G) as the anode and coronene, a polycyclic aromatic hydrocarbon (PAH), as the cathode. The coronene//NTO@G configuration delivers a specific energy of 77 W h kg -1 , based on the total active mass in both electrodes, and excellent cycling stability with 80% capacity retention after 5000 cycles. In addition, this device can work well in a wide range of temperatures from -20 to 40 °C. Furthermore, the results demonstrate a proof-of-concept Na-DIB that avoids the challenges of conventional dual-graphite DIBs by utilizing non-graphite intercalation anode and cathode, and a carbonate-based electrolyte without any additives.

25 ENERGY STORAGE↗

DOE OSTI2015

What Makes Fluoroethylene Carbonate Different?

Rechargeable lithium-ion batteries containing silicon-based negative electrodes have the potential to revolutionize electrical energy storage, but carbonate solvents (such as ethylene carbonate) that are commonly used in graphite Li-ion batteries, yield unsatisfactory performance when used with such Li alloying electrodes. It has been found by trial-and-error that additions of the closely related carbonate additive, fluoroethylene carbonate (FEC) to conventional electrolytes, yields a robust solid electrolyte interphase (SEI) on the LixSiy alloy surface. Several mechanisms for this protective action have been considered in the literature and modeled theoretically; however, at present these mechanisms remain speculative. In this study, we use radiolysis, laser photoionization, electron paramagnetic resonance, and transient absorption spectroscopy to establish the redox chemistry of FEC. While the oxidation chemistry is similar to that of other carbonates, the reduction chemistry is strikingly different. Specifically, one-electron reduction of FEC causes the fission of two (instead of one) C-O bonds, resulting in concerted defluorination and decarboxylation. This reaction yields the vinoxyl radical that can abstract an H atom from FEC, initiating both the chain reaction causing FEC decomposition and radical polymerization involving the reaction products. The resulting polymer can further defluorinate yielding the interior radicals that migrate and recombine to produce a highly cross-linked network. We suggest that the outer SEI resulting from FEC addition has elastomeric properties, which account for its cohesion during expansion and contraction of silicon particles in the course of Li alloying/dealloying cycling.

electron paramagnetic resonance↗

DOE OSTI2024

Production of Readily Compressible Dies for the Enhanced Sintering of Solids (PRESS) Preliminary Investigations

Non-oxide ceramics, which consist of predominantly carbides, borides, and nitrides, are of great interest to modern engineering because of their resistance to extreme conditions. Properties of such materials include high temperature resistance, high hardness, chemical resistance, and high fracture toughness. However, the main method for manufacturing parts of these materials is by machining cylindrical billets to the desired geometry. Not only does this produce waste, but the cost of machining is high since the part materials are of such high hardness. This method is used because these non-oxide ceramics must be sintered to high density using simultaneous heat and pressure within a hot-pressing unit. These units are inherently restricted to cylindrical geometries. A proposed way to expand the capabilities of a hot-press is by using intermediate compressible dies. This method consists of surrounding a ceramic part green body with a material that will shrink at the same rate as the part and survive the hot-pressing conditions. At the end, the compressible die material would be removed leaving a nearly net shaped hot-pressed part. In this study, graphite powder was investigated as the compressible die material with its shrinkage rate being controlled by particle size mixing. Both ceramic materials and graphite were then cast into parts and compressible dies respectively to show the feasibility of the compressible die hot-pressing method.

36 MATERIALS SCIENCE↗