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At least 685 records · Page 38

Cycling Performance and Structure Evolution of Co-Free Lithium- and Manganese-Rich Layered Oxides in Lithium-Ion Batteries

Lithium- and manganese-rich (LMR) layered oxides are high-capacity cathode materials that are being considered for electric vehicle (EV) lithium-ion batteries (LIBs). Here, we investigate the electrochemical cycling behavior of cells containing a cobalt-free LMR oxide, 0.3Li 2 MnO 3 ·0.7LiMn 0.5 Ni 0.5 O 2 , paired with either Li or graphite anodes. Two- and three-electrode cells are cycled under varying conditions to examine the effects of oxide activation, upper cutoff voltage, separator type, and electrolyte composition. Post-cycling characterization of harvested electrodes, with electrochemical, X-ray absorption spectroscopy, and solid-state 6 Li nuclear magnetic resonance spectroscopy techniques, are used to correlate cell performance changes with redox state evolution in the oxide and Li inventory shifts in the cell. Our results show that capacity fade and impedance rise primarily originate at the graphite anode and LMR cathode, respectively. Notably, while Ni undergoes reversible redox, Mn shows no evidence of bulk redox activity even in highly-aged electrodes: only relithiated LMR electrodes show some reduction of Mn. Graphite electrodes degrade due to particle isolation and SEI growth, exacerbated by Mn dissolution and deposition on graphite anodes. These findings highlight the coupled structural and electrochemical degradation mechanisms in LMR/graphite cells and underscore lithium inventory retention and electrode interfacial stability as critical factors for enhancing long-term performance.

Badami, Pavan P. [Argonne National Laboratory (ANL↗

Response of fs-Laser-Irradiated Diamond by Ultrafast Electron Diffraction

Structural details of the proposed solid–liquid phase transition of carbon have remained elusive, despite years of study. While it is theorized that novel carbon materials form from a liquid precursor, experimental studies have lacked the temporal and spatial resolution necessary to fully characterize the purported liquid state. Here, in this work, we utilize megaelectronvolt-ultrafast electron diffraction (MeV-UED) to study laser irradiated submicron diamond thin films in a pump–probe scheme with picosecond time resolution to visualize potential structural changes of excited diamond. We probe the structure of diamond using a combination of fluences (13, 40 J/cm 2 ) and time delays (10, 25, 100 ps), but observe negligible changes in the static diffraction pattern of diamond and an overall decrease in diffraction intensity up to 100 ps after the excitation pulse. We thus conclude that no appreciable amount of liquid or graphitized carbon is present and highlight the structural resilience of bulk diamond to intense 800 nm ultrafast laser pulses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Development and demonstration of manufacturing processes for fabricating graphite/Larc-160 polyimide structural elements, part 4, paragraph C

Progress in the development of processes for production of Celion/LARC-160 graphite-polyimide materials, quality control methods, and the fabrication of Space Shuttle composite structure components is reported. The formulation and processing limits for three batches of resin are presented. Process improvements for simplification of the imidizing and autoclave cure cycles are described. Imidized and autoclave cured test panels were prepared. Celion/LARC-160 cure process verification and the fabrication of honeycomb sandwich panel elements and skin/stringer panels are described. C-scans of laminates imidized at 163 C to 218 C for periods from 30 to 180 minutes, and of process verification laminates made from different batches of prepreg are presented. Failure modes and load/strain characteristics of sandwich elements and C-scans of stringer to skin bond joints are also given.

Source record↗

Effects of charging rates on LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622)/graphite Li-ion cells

Enabling fast charging capability of lithium-ion battery is of great importance to widespread adoption of electric vehicles. Increasing the charging rates from state-of-the-art 2C (30 min) to 6C (10 min) requires deep understanding on the cell aging mechanism. Here, 400 mAh pouch cells are cycled at 1C, 4C and 6C charging rates with 1C discharging rate. Capacity fading, cathode structural changes, Li inventory loss, electrolyte composition changes and Li plating on graphite electrodes are thoroughly studied by various characterization techniques. The rapid capacity fading in cells at 6C charging rate is mainly due to Li inventory loss from cathode structure and metallic Li plating on graphite electrode at higher charging rate. Post-mortem analysis also revealed changes in electrolyte such as increased salt molarity and transesterification during fast charging.

25 ENERGY STORAGE↗

Impact response of composite fuselage frames

Graphite-epoxy frames were drop tested onto a concrete floor to simulate crash loadings. The frames have Z-shaped cross sections typical of designs often proposed for fuselage structure of advanced composite transports. A diameter of six feet for the frames was chosen to reduce specimen fabrication costs and to facilitate testing. Accelerometer, strain gage, and photographic measurements are presented which characterize the impact behavior of frames with differing masses to represent structural or seat/occupant masses. Failures of the graphite-epoxy frames involved complete separations through the cross section. All damage to the lightly loaded composite frames was confined to an area close to the impact point. Subsequent failures left and right of the impact point occurred for the more heavily loaded specimens.

Boitnott, Richard L.↗

A nonlinear analysis of infinitely long graphite-epoxy cylindrical panels loaded with internal pressure

The structural response of internally pressurized composite cylindrical panels, representative of a transport aircraft's fuselage skins, is predicted by means of a one-dimensional, geometrically nonlinear analysis. An analytical study is conducted for the response of 4-, 8-, and 16-ply graphite/epoxy skins. The results obtained indicate that the response is geometrically nonlinear, and that a boundary layer with a severe bending gradient exists at the panel edges. The importance of through-the-thickness shearing deformations in the bending boundary layer is illustrated through comparison of analyses based on Kirchhoff-Love and shear deformation theories. Numerical results for the bending boundary layer lengths of the different panels are presented, and two bending boundary layers are predicted with the shear deformation theory.

Boitnott, R. L.↗

Reliability of stiffened structural panels: Two examples

The reliability of two graphite-epoxy stiffened panels that contain uncertainties is examined. For one panel, the effect of an overall bow-type initial imperfection is studied. The size of the bow is assumed to be a random variable. The failure mode is buckling. The benefits of quality control are explored by using truncated distributions. For the other panel, the effect of uncertainties in a strain-based failure criterion is studied. The allowable strains are assumed to be random variables. A geometrically nonlinear analysis is used to calculate a detailed strain distribution near an elliptical access hole in a wing panel that was tested to failure. Calculated strains are used to predict failure. Results are compared with the experimental failure load of the panel.

Stroud, W. Jefferson↗

Historic and modern nuclear graphite impurities: Pathways to improved waste strategies

Graphite has been used in large volumes as a structural material and neutron moderator since the earliest days of nuclear fission. However, no international consensus exists on the disposal of irradiated graphite, leaving much of the historic radioactive graphite inventory in interim vault or silo storage. With several new graphite-moderated reactors planned or under construction, the issue of graphite waste management is becoming increasingly urgent. This paper reviews and quantifies impurities in both historic and modern nuclear graphite, with emphasis on nitrogen—responsible for much of the 14 C inventory—and chlorine, which plays a critical role in repository performance and design. Modern graphites, benefitting from stringent quality-control measures developed for non-nuclear industries, meet or exceed the ASTM Ultra-High Purity nuclear standards, even without halide purification. Both chlorine and nitrogen concentrations have declined over time. For chlorine, identified as a key impurity influencing U.S. waste repository design, we propose a target of 0.1 appm in as-fabricated billets as a reasonable benchmark. Nitrogen sources are traced throughout the graphite production process, with surface and bulk concentrations characterized for all materials studied. Modern graphites commonly exhibit nitrogen levels below 5 appm, with values approaching 1 appm achievable. Using such reduced-nitrogen grades is critical to keeping graphite-induced radioactivity below the greater-than-Class-C waste threshold, thereby avoiding disposal cost penalties of nearly an order of magnitude.

Chlorine↗

TREAT reactor LEU fuel-clad chemical interaction empirical modeling analysis

DOE is converting TREAT (Transient Reactor Test) facility from its existing highly enriched uranium (HEU) core to a low-enriched uranium (LEU) core. In order to assess the magnitude of chemical interaction between fuel and cladding materials during physical contact under expected TREAT operational limits, planned transients tests, and reactivity accident scenarios, a combination of experimental testing and thermodynamic modeling was performed to predict the expected chemical interactions among fuel and cladding chemical constituents. Thermodynamic calculations were then validated with empirical data from experiments that emulate TREAT's expected upper operational limits. Pellet samples composed of LEU oxide powder dispersed in a graphite matrix had intimate contact with zirconium-based alloy cladding. The samples were subjected to long-term isothermal heating under high vacuum. Specimen characterization consisted of scanning electron microscopy, x-ray diffraction analysis, and x-ray tomography. ThermoCalc software and Ellingham's diagrams were used for thermodynamic calculations. The X-ray tomography and SEM analysis of the pellets showed a homogeneous distribution of UO{sub 2} particles within the graphite matrix with isolated larger UO{sub 2} agglomerates. The SEM analysis showed the formation of a lamellar structure between the large UO{sub 2} agglomerate and the graphite matrix. This is an indication that diffusion is taking place at a rather moderate temperature and reaction time during the pellet fabrication. Secondary phases, with high Al and Mg content, were detected inside a UO{sub 2} agglomerate using SEM in SE/EBSD mode and chemical analysis with EDS. LEU feedstock impurities, as Al and Mg, seem to promote the chemical reactivity between UO{sub 2} particles and graphite matrix. XRD analysis of a pellet sample showed the presence of UO{sub 2} and graphite, but no other crystalline phases were detected with this technique. Thermodynamic analysis through the use of Ellingham diagrams showed that within TREAT's operational to reactivity accident temperature (278-820 Celsius degrees), UO{sub 2} can be reduced to U metal by Zr due to a more favorable ΔG for the oxidation of Zr.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Highly Conducting Graphite Epoxy Composite Demonstrated

Weight savings as high as 80 percent could be achieved if graphite polymer composites could replace aluminum in structures such as electromagnetic interference shielding covers and grounding planes. This could result in significant cost savings, especially for the mobile electronics found in spacecraft, aircraft, automobiles, and hand-held consumer electronics. However, such composites had not yet been fabricated with conductivity sufficient to enable these applications. To address this lack, a partnership of the NASA Lewis Research Center, Manchester College, and Applied Sciences, Inc., fabricated nonmetallic composites with unprecedented electrical conductivity. For these composites, heat-treated, vapor-grown graphite fibers were selected which have a resistivity of about 80 mW-cm, more than 20 times more conductive than typical carbon fibers. These fibers were then intercalated with iodine bromide (IBr). Intercalation is the insertion of guest atoms or molecules between the carbon planes of the graphite fibers. Since the carbon planes are not highly distorted in the process, intercalation has little effect on mechanical and thermal properties. Intercalation does, however, lower the carbon fiber resistivity to less than 10 mW-cm, which is comparable to that of metal fibers. Scaleup of the reaction was required since the initial intercalation experiments would be carried out on 20-mg quantities of fibers, and tens of grams of intercalated fibers would be needed to fabricate even small demonstration composites. The reaction was first optimized through a time and temperature study that yielded fibers with a resistivity of 8.7 2 mW-cm when exposed to IBr vapor at 114 C for 24 hours. Stability studies indicated that the intercalated fibers rapidly lost their conductivity when exposed to temperatures as low as 40 C in air. They were not, however, susceptible to degradation by water vapor in the manner of most graphite intercalation compounds. The 1000-fold scaleup experiments concluded that 114 C was near the optimum temperature, but that the intercalation time needed to be lengthened by a factor of 3.

Gaier, James R.↗

The optical properties and photocatalytic activity of CdS-ZnS-TiO{sub 2}/Graphite for isopropanol degradation under visible light irradiation

This research prepared a photocatalyst tablet of CdS-ZnS-TiO{sub 2} on a graphite substrate. The synthesis was conducted through chemical bath deposition method. The graphite substrate used was a waste graphite rod from primary batteries. The aims of this research are studying the crystal structure, the optical properties and the photocatalytic activity of the prepared material. The photocatalytic activity was determined through isopropanol degradation. The result shows that the TiO{sub 2}/Graphite provide direct transition gap energy at 2.91 eV and an indirect transition gap energy at 3.21 eV. Deposition of CdS-ZnS changed the direct transition gap energy to 3.01 eV and the indirect transition gap energy to 3.22 eV. Isopropanol degradation with the prepared catalyst produced new peaks at 223-224 nm and 265-266 nm confirming the production of acetone. The degradation follows first order with rate constant of 2.4 × 10{sup −2} min{sup −1}.

36 MATERIALS SCIENCE↗

Binder-Free Graphite Anodes for Next-Generation High-Performance Lithium-Ion Batteries

High-energy density anodes are crucial for next-generation lithium-ion batteries (LIBs) particularly for electric vehicle (EV) applications. Sluggish lithium-diffusion kinetics coupled with conventional anode fabrication processes containing polymeric binders hinder fast-charging capabilities and high-energy density of graphite. Herein, we introduce a binder-free graphite anode fabrication strategy using the electrospinning technique that contains ~2.41% carbon nanotubes (CNTs). Our strategy relies on the formation of an interconnecting conductive CNT network coupled with an ultrathin N-doped carbon coating on graphite particles from sacrificial binders. This combination enhances both structural integrity and electrical conductivity and, in turn, improves fast-charging capabilities and high energy density of LIBs. The binder-free graphite anode achieves ~335.0 mAh g–1 capacity at C/3 rate over 400 cycles with capacity retention of >95% and average Coulombic efficiencies >99.95%. These promising results suggest that the binder-free anode fabrication with a multifunctional design approach could elevate the energy-density limits of the graphite anodes, solving high-energy density requirements of EVs, and potentially provides a path forward for the development of economically feasible energy storage systems for various applications.

Ozcan, Muca [ORNL] (ORCID:0000000320020474)↗

Influence of extended exposure in space on mechanical properties of high-toughness graphite-epoxy composite material (A0019)

Graphite-epoxy composites are promising candidates for structural use in space vehicles because of their high strength and elastic modulus properties. The problem of low fracture toughness was solved by use of recently developed techniques of intermittent interlaminar bonding. Before this material can be adapted for space use, however, confidence must be gained that its mechanical properties are not degraded by exposure to the space environment. The objective of this experiment is to test the effect of extended exposure to a space environment on the mechanical properties of a specially toughened T300/5208 graphite-epoxy composite material. Specimens made by recently developed techniques of intermittent interlaminar bonding will be exposed and afterward tested for fracture toughness, tensile strength, and elastic modulus. The approach of this experiment is to provide a frame on which the specimens can be mounted with their flat sides normal to the Long Duration Exposure Facility radius, each specimen with an unobstructed exposure of about 2 pi sr. The specimens will be mounted so that they neither fracture from high stress nor fail from excessive heating during launch and return.

Felbeck, D. K.↗

Facile Dual-Protection Layer and Advanced Electrolyte Enhancing Performances of Cobalt-free/Nickel-rich Cathodes in Lithium-Ion Batteries

Despite cobalt (Co)-free/nickel (Ni)-rich layered oxides being considered as one of the promising cathode materials due to their high specific capacity, their highly reactive surface is one of the shortcomings that still hinder their practical usages in high-energy-density batteries. Herein, a polyimide/polyvinylpyrrolidone (PI/PVP, denoted as PP) coating layer is demonstrated as dual-protection for LiNi 0.96 Mg 0.02 Ti 0.02 O 2 (NMT) cathode material to suppress surface contamination against moisty air and to prevent unwanted side reactions between cathode and electrolyte during electrochemical cycling. The optimal PP-coated NMT (PP@NMT) preserves a clean surface without generation of lithium (Li) residues, structural degradation, and gas evolution after exposure to air with ~30% humidity for 2 weeks. Contrarily, the exposed bare NMT shows severe contamination, structural shrinkage due to Li loss, and increased gas release during charging. In addition, the exposed PP@NMT significantly enhances the electrochemical performance of graphite (Gr)||NMT cells by decreasing byproducts and maintaining structural stability. Moreover, the exposed PP@NMT achieves a high capacity retention of 86.7% after 500 cycles in Gr||NMT cells using an advanced localized high-concentration electrolyte. Furthermore, this work demonstrates a promising facile approach to the protection of Co-free/Ni-rich layered cathodes for their practical applications even after exposure to moisty air.

25 ENERGY STORAGE↗

Preparation of a Bimetal Using Mechanical Alloying for Environmental or Industrial Use

Following the 1976 Toxic Substances Control Act ban on their manufacture, PCBs remain an environmental threat. PCBs are known to bio-accumulate and concentrate in fatty tissues. Further complications arise from the potential for contamination of commercial mixtures with other more toxic chlorinated compounds such as polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Until recently, only one option was available for the treatment of PCB-contaminated materials: incineration. This may prove to be more detrimental to the environment than the PCBs themselves due to the potential for formation of PCDDs. Metals have been used for the past ten years for the remediation of halogenated solvents and other contaminants in the environment; however, zero-valent metals alone do not possess the activity required to dehalogenate PCBs. Palladium has been shown to act as an excellent catalyst for the dechlorination of PCBs with active metals. This invention is a method for the production of a palladium/magnesium bimetal capable of dechlorinating PCBs using mechanical milling/mechanical alloying. Other base metals and catalysts may also be alloyed together (e.g., nickel or zinc) to create a similarly functioning catalyst system. Several bimetal catalyst systems currently can be used for processes such as hydrogen peroxide synthesis, oxidation of ethane, selective oxidation, hydrogenation, and production of syngas for further conversion to clean fuels. The processes for making these bimetal catalysts often involve vapor deposition. This technology provides an alternative to vapor deposition that may provide equally active catalysts. A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts. Preferably, the hydrogenation catalyst is a bimetallic particle formed from a zero-valent iron or zero-valent magnesium particle coated with palladium that is impregnated onto a high-surface-area graphite support. The zero-valent metal particles should be microscale or nanoscale zero-valent magnesium or zero-valent iron particles. Other zero-valent metal particles and combinations may be used. Additionally, the base material may be selected from a variety of minerals including, but not limited to, alumina and zeolites. The catalytic metal is preferably selected from the group consisting of noble metals and transition metals, preferably palladium. The mechanical milling process includes milling the base material with a catalytic metal impregnated into a high-surface-area support to form the hydrogenation catalyst. In a preferred mechanical milling process, a zero-valent metal particle is provided as the base material, preferably having a particle size of less than about 10 microns, preferably 0.1 to 10 microns or smaller, prior to milling. The catalytic metal is supported on a conductive carbon support structure prior to milling. For example, palladium may be impregnated on a graphite support. Other support structures such as semiconductive metal oxides may also be used.

Quinn, Jacqueline↗

Electrically Conductive Amine Functionalized Reduced Graphite Oxide Foam for CO 2 Removal from the Air

Rapid regeneration of CO 2 adsorbents is critical to improving the productivity of direct air capture (DAC) systems. In this study, we codesigned a material to have appropriate electrical conductivity and CO 2 adsorption properties to enable efficient CO 2 capture from air. Specifically, we present a poly(ethylenimine) (PEI)-impregnated thermally annealed graphite oxide (TAGO900) foam adsorbent tailored for vacuum-assisted electrically driven thermal swing adsorption (V-ETSA). This structured adsorbent leverages the high electrical conductivity of the reduced graphite oxide framework to enable fast and direct heating of the adsorbent material by electrical resistance heating (Joule heating). An optimal sample, 40 wt % PEI (molecular weight 25k) impregnated TAGO900, shows the best balance between adsorption capacity (1.54 mmol g –1 ) and adsorption rates (0.016 mmol g –1 min –1 ) using fixed bed breakthrough experiments at 25 °C and 70% RH using 50 sccm 400 ppm of CO 2 /N 2 flow. Compared to conventional temperature vacuum swing adsorption (TVSA), the V-ETSA approach achieves substantially faster CO 2 desorption, achieving average desorption rates (including cooling time) of 0.09 mmol g –1 min –1 ─approximately 2.5 times faster than TVSA under similar operating conditions. The maximum desorption rate reaches 0.23 mmol/g/min during the desorption stage. These results underscore the importance of the direct heating strategy, such as Joule heating, for fast and highly productive vacuum swing adsorption in DAC systems.

amines↗

Additive Manufactured Ultra-Fine Lattice Structures for Propulsion Catalysts

Traditional mono-propulsion catalysts consist of coated ceramic or graphite foams that possess anisotropic mechanical and fluid properties limiting design, cost, availability, and operational use. Ultra-fine lattice structures are repeating unit cells with ligament thickness as small as 100 μm produced via Additive manufacture (AM). These lattice structures have the potential to replace coated foams used in a mono-propellant system catalysts. AM ultra-fine lattice structures are designed to mimic the operational intent of coated foams but with improved design flexibility, compressive strength, and flow behavior printed from into a single part directly from the preferred platinum metal alloy. The investigation objective was to conduct feasibility studies of AM ultra-fine lattice structures capable of replacing coated foams with superior functionality. NASA MSFC identified desired lattice characteristics and created designs while EOS developed optimized laser powder bed fusion AM parameters to manufacture Ti6Al4V and tungsten specimens. Optimized designs, computational tools, AM parameters, and post-process methods were developed. Specimens underwent x-ray micro-focus CT, metallographic inspection, compression testing, and flow testing. Results demonstrate that AM ultra-fine lattices improved geometric and performance repeatability with the potential for significantly increased availability while decreasing cost and lead time.

Omar R Mireles↗