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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 235 records · Page 13

Application of the Solute-Solvent EMF Cell to Measure Activity of NiF 2 in Molten FLiNaK

Electromotive force (emf) measurements made using a combination of solute- and solvent-based electrodes were used to determine the activity of NiF 2 in molten FLiNaK eutectic at 823 K across a concentration range of x NiF2 = 5.2 × 10 –4 –1.0 × 10 –2 . The solute emf values were measured using electrodes consisting of Ni wires immersed in FLiNaK with dissolved NiF 2 contained in graphite crucibles. The measured emf values were then converted to the FLiNaK Eutectic Potassium Electrode (FEKE) potential and used to quantify the activity of dissolved NiF 2 . This quantification was based upon comparative measurements of a reference solvent electrode consisting of a K-Bi alloy immersed in pure FLiNaK contained in a boron nitride crucible and a solute electrode. Short cell lives were characteristic of the measurements due to the corrosive nature of the fluoride salts. Quantifying the activity of NiF 2 will improve the utility of Ni 2+ /Ni reference electrodes in molten fluoride salts, which are notoriously difficult electrolytes to work with because of their reactivity. In conclusion, this work demonstrates the general nature of the solute-solvent approach as a repeatable, easily employed method for measuring the activity values of electroactive species in a variety of molten salts to improve understanding of the electroactive species behavior in these systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-efficiency helical traveling-wave tube with dynamic velocity taper and advanced multistage depressed collector

A NASA-sponsored research and development contract has been established with the Watkins-Johnson Company to fabricate high-efficiency 20-watt helical traveling wave tubes (TWTs) operating at 8.4 to 8.43 GHz. The TWTs employ dynamic velocity tapers (DVTs) and advanced multistage depressed collectors (MDCs) having electrodes with low secondary electron emission characteristics. The TWT designs include two different DVTs; one for maximum efficiency and the other for minimum distortion and phase shift. The MDC designs include electrodes of untreated and ion-textured graphite as well as copper which has been treated for secondary electron emission suppression. Objectives of the program include achieving at least 55 percent overall efficiency. Tests with the first TWTs (with undepressed collectors) indicate good agreement between predicted and measured RF efficiencies with as high as 30 percent improvement in RF efficiency over conventional helix designs.

Curren, Arthur N.↗

Versatile Graphitized Carbon Nanofibers in Energy Applications

Graphitized carbon nanofibers (CNFs) are the allotropic forms of carbon that offer exceptional electrical conductivity, high aspect ratio, large surface-to-volume ratio, flexibility, mechanical robustness, and structural stability. These properties render CNFs as useful materials in energy applications, including water electrocatalysis and electrochemical energy storage devices (EESDs). Graphitized CNFs manifest huge versatility in EESDs and have been employed as electrode materials, as supports for other electrode materials, and conductive additives. This perspective summarizes the production methods, structural aspects, and energy applications of graphitized CNFs. Different design strategies have been employed to produce CNFs with diverse and distinct morphologies and structures. Their fabrication methods, along with precursors and dopants or cocatalysts, impact the overall structural, functional, and topographical properties. Recent developments on the state-of-the-art interests of graphitic CNFs in lithium-ion batteries (LIBs), lithium–sulfur (Li–S) batteries, vanadium redox flow batteries (VRFBs), supercapacitors, and water splitting have explored the many possibilities in energy sectors. Finally, the assembly and functioning of CNFs in water splitting and EESDs as well as primary challenges are discussed in this perspective.

36 MATERIALS SCIENCE↗

Viscosity Analysis of Battery Electrode Slurry

We report the effects of component ratios and mixing time on electrode slurry viscosity. Three component quantities were varied: active material (graphite), conductive material (carbon black), and polymer binder (carboxymethyl cellulose, CMC). The slurries demonstrated shear-thinning behavior, and suspension properties stabilized after a relatively short mixing duration. However, micrographs of the slurries suggested their internal structures did not stabilize after the same mixing time. Increasing the content of polymer binder CMC caused the greatest viscosity increase compared to that of carbon black and graphite.

25 ENERGY STORAGE↗

Long-Term Structural and Chemical Stability of Carbon Electrodes in Vanadium Redox Flow Battery

Predicting the performance decay in carbon electrodes is critical to maximizing the longevity of redox flow battery (RFB) systems. This study investigates the effect of long-term cycling (over 8000 cycles) on the structural and chemical evolution of carbon electrodes. We find that the microstructural aspects such as graphitic stacking order and interlayer spacing along with overall morphological construct remains largely unchanged even after the prolonged cycling process. Conversely, significant changes in surface chemistry such as evolution of functional groups and point defects are evident from our combined multimodal spectroscopic and computational analysis. The XPS and FTIR analysis reveals chemical absorption of chloride counter anions at point defects within graphitic surface. Additionally, our results suggest that vanadium cation plays an important role in counter anion-carbon surface interaction and subsequently the surface chemistry evolutions. Our findings provide insights about surface chemical evolution that is critical for predicting electrode performance and longevity of RFB.

Modachur Sivakumar, Bhuvaneswari↗

Carbon Ores-Derived Critical Materials for Clean Energy Technology Applications

Presented at the 48th International Technical Conference on Clean Energy (Clearwater Clean Energy Conference), Clearwater, Florida, June 16-19, 2024. This presentation describes the Energy & Environmental Research Center’s development of the Upgraded Carbon Ores-to-Products (UCOP) technology to produce high‑quality graphite and other critical materials from coal and coal wastes for clean energy applications such as batteries and electrodes. It outlines the technical approach, including feedstock cleaning, controlled heat treatment, and graphitization, and presents results demonstrating high graphite purity, novel microstructures, and competitive performance relative to commercial graphite. The work highlights the potential for lower environmental impact and domestic supply chains for critical materials amid increasing global demand and supply‑chain constraints.

01 COAL, LIGNITE, AND PEAT↗

Secondary-electron-emission losses in multistage depressed collectors and traveling-wave-tube efficiency improvements with carbon collector electrode surfaces

Secondary-electron-emission losses in multistage depressed collectors (MDC's) and their effects on overall traveling-wave-tube (TWT) efficiency were investigated. Two representative TWT's and several computer-modeled MDC's were used. The experimental techniques provide the measurement of both the TWT overall and the collector efficiencies. The TWT-MDC performance was optimized and measured over a wide range of operating conditions, with geometrically identical collectors, which utilized different electrode surface materials. Comparisons of the performance of copper electrodes to that of various forms of carbon, including pyrolytic and iisotropic graphites, were stressed. The results indicate that: (1) a significant improvement in the TWT overall efficiency was obtained in all cases by the use of carbon, rather than copper electrodes, and (2) that the extent of this efficiency enhancement depended on the characteristics of the TWT, the TWT operating point, the MDC design, and collector voltages. Ion textured graphite was found to be particularly effective in minimizing the secondary-electron-emission losses. Experimental and analytical results, however, indicate that it is at least as important to provide a maximum amount of electrostatic suppression of secondary electrons by proper MDC design. Such suppression, which is obtained by ensuring that a substantial suppressing electric field exists over the regions of the electrodes where most of the current is incident, was found to be very effective. Experimental results indicate that, with proper MDC design and the use of electrode surfaces with low secondary-electron yield, degradation of the collector efficiency can be limited to a few percent.

Ramins, P.↗

Computational Analysis of Anode and Cathode Structuring Effects on Charge and Discharge in Graphite|LiNi 0.6 Mn 0.2 Co 0.2 O 2 Batteries

Structured electrodes (SEs) improve the rate capability of Lithium-ion batteries by engineering micrometer-scale electrolyte regions into the electrode, promoting rapid ionic transport. Prior research has focused on structuring one electrode (anode or cathode) with an analysis on either the charge or discharge performance. We present a holistic study using three-dimensional models to investigate the isolated effects of structuring either electrode and the combined effects of structuring both electrodes on the charge and discharge capacity of single-layer cells at 4 C and 6 C. Volumetric and gravimetric discharge energy density (Wh/L stack and Wh/kg stack ) and charge capacity (Ah/kg stack and Ah/L stack ) are evaluated for multi-layer pouch cell stacks. Pairing SE anodes with SE cathodes demonstrated improvements up to 15% in discharge Wh/kg stack and up to 33% in charge Ah/kg stack over a conventional cell; Energy required to charge per Ah/kg stack was improved by 13%–14%. SE cathodes paired with a conventional anode exhibited improvements of 0.3%–22% across all performance metrics evaluated. Conversely, pairing a SE anode with a conventional cathode demonstrated improved charge capacity up to 13% but showed a 2%–23% lower discharge energy density. The importance of aligning SEs in a cell from a performance and manufacturing perspective is also analyzed.

25 ENERGY STORAGE↗

Molten salt electrochemical upcycling of CO 2 to graphite for high performance battery anodes

The efficient transformation of CO 2 into a value-added material is a potential strategy to help mitigate climate effects caused by CO 2 emissions. One potential CO 2 conversion product is graphite which is an important and versatile material extensively used in many applications including as an anode for lithium-ion batteries (LIBs). Commercial graphite, however, is traditionally synthesized via the energy intensive Acheson process (>3000 °C) and the performance of such graphite can be limited under fast charging conditions which is important for vehicle electrification. We report the electrochemical transformation of CO 2 to highly crystalline nano-graphite with a controlled microstructure in a carbonate molten salt at 780 °C. The use of a nickel foam electrode and controlled electrochemical parameters during the molten salt conversion process yielded pure graphite at a lower temperature compared to the Acheson process. Moreover, when investigated as an anode material for LIBs, the CO 2 -converted graphite exhibited high reversible capacity, long cycle life, and excellent rate capability even under fast charging conditions. This process provides a way to potentially reduce carbon emissions through the utilization of waste CO 2 by converting it into value-added graphite suitable for fast charging, high-energy-density batteries for vehicle electrification.

25 ENERGY STORAGE↗

Preparation of thin film silver fluoride electrodes from constituent elements

The feasibility of preparing thin-film metal fluoride electrodes from the elemental constituents has been demonstrated. Silver fluoride cathodes were prepared by deposition of silver on a conducting graphite substrate followed by fluorination under controlled conditions using elemental fluorine. The resulting electrodes were of high purity, and the variables such as size, shape, and thickness were easily controlled.

Odonnell, P. M.↗

Production of graphene-derivatives using organic molecules for supercapacitors and beyond

Graphene is rapidly expanding for applications ranging from nanoelectronics to space exploration. A material with such enormous potential requires a variety of synthesis methods. Here, we report a library of relatively sustainable redox-active organic molecules for the reduction of graphene oxide (GO) namely N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), 7,7,8,8-tetracyanoquinodimethane (TCNQ), ferrocene (Ferro), and decamethylferrocene (DFerro). Among them, the reduction of GO using TMPD starts even with simple hand-shaking for just a few minutes. By controlling the sonication time under ambient conditions, one can control the electronic properties of the reduced graphene oxide (rGO). The resulting free-standing films delivered a capacitance of 185 F/g when tested them as supercapacitor electrodes. We also demonstrated that TMPD can exfoliate graphite into few-layer graphene sheets with simple sonication. Here, we further show that under mild heating, these molecules can serve as dopants during the reduction process to produce nitrogen-doped graphene. Our results may guide researchers to explore sustainable organic molecules for the large-scale production of graphene-based materials for diverse applications.

36 MATERIALS SCIENCE↗

Surface Stabilization with Fluorine of Layered Ultrahigh-Nickel Oxide Cathodes for Lithium-Ion Batteries

High-nickel layered oxide cathodes are key to meet the demands of the electric vehicle industry because of their high specific capacity. However, commercialization of these materials is hindered by critical challenges, such as phase transitions, particle cracking, aggressive surface reactivity, and thermal instability. Cation doping along with surface coating has proven to be an effective way to circumvent some of these issues to a large extent. Herein, fluorine coating is employed on a high-nickel Li[Ni 0.95 Mn 0.015 Co 0.02 Al 0.01 Mg 0.005 ]O 2 (NMCAM) cathode via a solution route. Detailed structural and electrochemical analyses indicate fluorine largely decorates the surface at low enough calcination temperatures. The cathode with 1 mol % fluorine coating exhibits a capacity retention of 71% after 500 cycles as compared to 59% for the control sample when cycled to a high cutoff voltage of 4.3 V in a full cell configuration with graphite anode. Post-mortem analysis of cycled electrodes reveals that surface reactivity is a major contributor to capacity fade as compared to particle cracking. Fluorine coating reduces surface reactivity and the depth to which rock-salt phase is formed on the surface during cycling. The thermal stability is also enhanced after fluorine coating as the material shows less heat release at high states of charge. Furthermore, this work demonstrates an effective, economical, and scalable way to stabilize the surface with fluorine and enhance the electrochemical performance of high-nickel cathodes.

25 ENERGY STORAGE↗

Pyrolytic graphite collector development program

Pyrolytic graphite promises to have significant advantages as a material for multistage depressed collector electrodes. Among these advantages are lighter weight, improved mechanical stiffness under shock and vibration, reduced secondary electron back-streaming for higher efficiency, and reduced outgassing at higher operating temperatures. The essential properties of pyrolytic graphite and the necessary design criteria are discussed. This includes the study of suitable electrode geometries and methods of attachment to other metal and ceramic collector components consistent with typical electrical, thermal, and mechanical requirements.

Wilkins, W. J.↗

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↗

Impacts of ruthenium valence state on the electrocatalytic activity of ruthenium ion-complexed graphitic carbon nitride/reduced graphene oxide nanosheets towards hydrogen evolution reaction

Design and engineering of effective electrode catalysts represents a critical first step for hydrogen production by electrochemical water splitting. Nanocomposites based on ruthenium atomically dispersed within a carbon scaffold have emerged as viable candidates. In the present study, ruthenium metal centers are atomically embedded within graphitic carbon nitride/reduced graphene oxide nanosheets by thermal refluxing. Subsequent chemical reduction/oxidation leads to ready manipulation of the ruthenium valence state, as evidenced in microscopic and spectroscopic measurements, and hence enhancement/diminishment of the electrocatalytic activity towards hydrogen evolution reaction in both acidic and alkaline media. Further, this is largely ascribed to the increased/reduced contribution of the Ru valence electrons to the density of state near the Fermi level which dictates the binding and reduction of hydrogen. Results from this study highlight the significance of the valence state of metal centers in the manipulation and optimization of the catalytic performance of single atom catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Beam impingement angle effects on secondary electron emission characteristics of textured pyrolytic graphite

Experimentally determined values of true secondary electron emission and relative values of reflected primary electron yield for untreated and ion-textured pyrolytic graphite over a range of primary electron energy levels and electron beam impingement angles are presented. Information required to develop high efficiency multistage depressed collectors (MDC's) for microwave amplifier traveling-wave tubes for space communication and aircraft applications is provided. To attain the highest possible MDC efficiencies, the electrode surfaces must have low secondary electron emission characteristics. Pyrolytic graphite, a chemically vapor-deposited material, is a particularly promising candidate for this application. The pyrolytic graphite surfaces studied were tested over a range of primary electron beam energies and beam impingement angles from 200 to 2000 eV and direct (0 deg) to near-grazing angles (85 deg), respectively. Surfaces both parallel to and normal to the planes of material deposition were examined. The true secondary electron emission and reflected primary electron yield characteristics of the pyrolytic graphite surfaces are compared to those of sooted control surfaces.

Curren, A. N.↗

Achieving SEI preformed graphite in flow cell to mitigate initial lithium loss

The irreversible lithium loss due to the formation of solid electrolyte interphase (SEI) in the initial cycle on the graphite anode greatly reduces the overall cell energy density of lithium ion batteries, that is, the lost Li ions from forming SEI lead to the decrease of Li ions for the intercalation. The method of cathode prelithiation has been widely explored to compensate this lithium loss. However, these cathode additives with high lithium contents inevitably lower the loading of the cathode active materials. In this work, we report a novel approach to solve this challenge, a facile graphite prelithiation method by preforming SEI layers on the surface of graphite powders (Pre-SEI graphite) utilizing a specially designed flow cell. The Li accommodation in the graphite anode can be controlled by the operating time and current density in the flow cell for the electrochemical SEI formation. As a result, we demonstrate a 10% initial Columbic efficiency increase of the LiFePO 4 electrode in a full cell configuration using the Pre-SEI graphite, compared with the pristine graphite anode. The electrochemical preformation of SEI on the graphite powders offers a complete solution to offset initial lithium loss without a sacrifice of active cathode material loading.

25 ENERGY STORAGE↗