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At least 757 records · Page 42

Irreparable Interphase Chemistry Degradation Induced by Temperature Pulse in Lithium‐Ion Batteries

Abstract While it is widely recognized that the operating temperature significantly affects the energy density and cycle life of lithium‐ion batteries, the consequence of electrode‐electrolyte interphase chemistry to sudden environmental temperature changes remains inadequately understood. Here, we systematically investigate the effects of a temperature pulse (T pulse) on the electrochemical performance of LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) pouch full cells. By utilizing advanced characterization tools, such as time‐of‐flight secondary‐ion mass spectrometry, we reveal that the T pulse can lead to an irreversible degradation of cathode‐electrolyte interphase chemistry and architecture. Despite negligible immediate impacts on the solid‐electrolyte interphase (SEI) on graphite anode, aggregated cathode‐to‐anode chemical crossover gradually degrades the SEI by catalyzing electrolyte reduction decomposition and inducing metallic dead Li formation because of insufficient cathode passivation after the T pulse. Consequently, pouch cells subjected to the T pulse show an inferior cycle stability to those free of the T pulse. This work unveils the effects of sudden temperature changes on the interphase chemistry and cell performance, emphasizing the importance of a proper temperature management in assessing performance.

Cui, Zehao↗

Evaluation of 72 Se/ 72 As generator and production of 72 Se for supplying 72 As as a potential PET imaging radionuclide

Here, positron-emitting 72 As is the PET imaging counterpart for beta-emitting 77 As. Its parent, no carrier added (n.c.a.) 72 Se, was produced for a 72 Se/ 72 As generator by irradiating an enriched 7° Ge metal-graphite target via the 70 Ge(α, 2 n) 72 Se reaction. Target dissolution used a fast, environmentally friendly method with 93% radioactivity recovery. Chromatographic parameters of the 72 Se/ 72 As generator were evaluated, the eluted n.c.a. 72 As was characterized with a phantom imaging study, and the previously reported trithiol and aryl-dithiol ligand systems were radiolabeled with the separated n.c.a. 72 As in high yield.

43 PARTICLE ACCELERATORS↗

Markets for carbon fiber composites

A growing market exists in the Unites States for the use of carbon or graphite fibers in civil aircraft. The results of an investigation of this fiber (CF) market are described. The overall objectives in this task were to estimate the current (1977) CF market by sector, to forecast the CF market to 1993, to characterize the civil aircraft sector, and to identify competitive materials.

Source record↗

Feasibility of characterizing laser-ablated carbon plasmas via planar laser induced fluorescence

Planar laser induced fluorescence (PLIF) imaging can potentially assess ion distributions and coupling in the context of super-Alfvenic ablation plasma expansions into magnetized background plasmas. In this feasibility study, we consider the application of PLIF to rapidly expanding carbon plasmas generated via energetic laser ablation of graphite. By utilizing hydrodynamic and collisional-radiative simulations, we identify schemes accessible to commercially available tunable lasers for the C I atom, the C II ion, and the C V ion. We then estimate the signal-to-noise ratios yielded by the schemes under reasonable experimental configurations.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Nanostructure-enhanced Phase Change Materials (NePCM) and HRD

Development and characterization of high aspect-ratio nanostructures tailored for dramatic improvements of thermal conductivity of phase change materials is proposed. This DOE renewal project builds upon a proven research record on development of a number of stable and functionality-proven colloids of metal oxide and metallic nanoparticles (avg. diameters less than 10 nm). These efforts followed original conceptualization and synergistic activities on promoting nanostructure-enhanced phase change materials (NePCM) and their utilization for thermal energy storage, waste heat recovery, thermal comfort, etc. Given this background, availability of promising preliminary results for the proposed target materials and formation of a new team of researchers, the investigators will focus on development of nanoadditives of metallic nanorods, functionalized carbon nanotubes, Graphene, graphite nanoplatelets, nanocomposites combining graphene with metal/metal oxide nanostructures and self-assembling carbon nanofiber-based nanomaterials. Specifically, the chemical synthesis group will identify procedures leading to nanorods of copper, copper oxide, silver and graphitic carbon exhibiting long-term stability against precipitation when dispersed in hydrocarbon solvents suitable for PCM applications. Important goals are to achieve nanorods with dimensions, including aspect ratio, that induce significant enhancements in thermal conductivity and also to control instabilities against rod precipitation during solvent freezing and melting. Another group will focus on developing complex nanoarchitectured nanocomposites through utilizing heterostructures that combine graphene with metal or metal oxide nanostructures. These heterostructures will be mixed with paraffin, fatty acids, or stearyl alcohol to realize novel NePCM. Fundamental studies will be performed by conducting materials and thermal characterization methods and structure-processing-properties relationships will be derived. In addition, growth mechanisms for the proposed heterostructures will be evaluated. Another research team will undertake a variety of approaches to functionalize the surfaces of nanostructured carbon-based materials, i.e. carbon nanotubes, Graphene and graphite nanoplatelets. The proposed techniques include both surfactant- and polymer-assisted dispersion of carbon nanotubes, Graphene and graphite nanoplatelets, in addition to microwave-initiated carbon nanotube growth to produce 3-D nanocarbon fillers for NePCM. Functionalized and pristine carbon nanotubes will also be subjected to a strong magnetic field to explore the effect of controlled alignment on the improved thermal conductivity. Microwave-initiated nanotube growth on the surfaces of the voids of graphite foam will be attempted to extend the previous work on thermal conductivity improvement of PCM that are impregnated into porous highly-conductive structures. Refinements of continuum modeling of colloids and most importantly, molecular dynamics-based mechanistic studies for carbon nanotubes and Graphene-based multi-component systems will be pursued. Finally, self-assembling carbon nanofiber-based NePCM will be investigated by another group. A highly-conductive carbon nanofiber network, which is created by a self-assembling approach, will host the PCM and enhance the thermal conductivity by several folds. Furthermore, the inert and relatively stable carbon nanofiber will be further utilized for creating low-mid range temperature NePCM and high-temperature NePCM by filling the porous space inside the self-assembling carbon nanofiber network with paraffin-based or salt-based PCM, respectively. Improved thermal energy charge/discharge performance and stable phase change temperature control features exhibited by this new generation of self-assembling carbon nanofiber-based NePCM will potentially impact many applications including solar energy storage systems.

25 ENERGY STORAGE↗

Synthesis of few layer graphene by direct exfoliation of graphite and a Raman spectroscopic study

The exfoliation of graphene from pristine graphite in a liquid phase was achieved successfully via sonication followed by centrifugation method. Ultraviolet–visible (UV–vis) spectra of the obtained graphene dispersions at different exfoliation time indicated that the concentration of graphene dispersion increased markedly with increasing exfoliation time. The sheet-like morphology of the exfoliated graphene was revealed by Scanning Electron Microscopy (SEM) image. Further, the morphological change in different exfoliation time was investigated by Atomic Force Microscopy (AFM). A complete structural and defect characterization was probed using micro-Raman spectroscopic technique. The shape and position of the 2D band of Raman spectra revealed the formation of bilayer to few layer graphene. Also, Raman mapping confirmed the presence of uniformly distributed bilayer graphene sheets on the substrate.

36 MATERIALS SCIENCE↗

Modification of surface functionality and interlayer spacing of multi-walled carbon nanotubes using {gamma}-rays

The surface functionality and interlayer spacing changes induced by {gamma}-ray irradiation were investigated in multi-walled carbon nanotubes (MWCNTs). The modification effect of MWCNTs irradiated in air and epoxy chloropropane (ECP) was characterized by x-ray photoelectron spectroscopy, Raman spectroscopy, and x-ray diffraction. The results indicated that {gamma}-ray irradiation in two different media improved the amount of oxygen-containing functional groups on nanotube surface, and the irradiation in ECP was more efficient. Compared with the pristine MWCNTs, the MWCNTs irradiated in air exhibited a decrease in width of G band and intensity ratio of D to G band in the Raman spectra and an increase in intensity and diffraction angle of (002) characteristic x-ray peak. However, the MWCNTs tended to show the opposite behaviors in Raman spectra and x-ray diffraction patterns after they were irradiated in ECP. This preliminary study suggests that {gamma}-ray irradiation in air can meaningfully decrease the interlayer distance of MWCNTs and improve the graphitization of MWCNTs, while irradiation in ECP disorders and breaks the structure of MWCNTs. It is worth expecting that MWCNTs can be functionalized by {gamma}-rays in reactive liquid and also be employed for preventing {gamma}-ray radiation from reaching sensitive materials at least for short term experiments in air.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Synthesis, characterization and conductivity studies of ZnFe{sub 2}O{sub 4} nanoparticles

Transition metal ferrites with general formula AB{sub 2}O{sub 4} (A=Co, Cu, Mn, Zn, B=Fe{sup +3}) could be used as an anode materials in lithium ion battery (LIB), because, lithium ion batteries fabricated using ferrite materials show the high capacity than commonly used graphite. The ZnFe{sub 2}O{sub 4} with cubic spinel structured material was prepared by acrylamide assisted citrate combustion process. Phase, structural coordination and thermal behavior of the prepared ZnFe{sub 2}O{sub 4} were confirmed by powder X-ray diffraction, FTIR spectra and TG/DTA thermogram respectively. Morphology and specific surface area of the ZnFe{sub 2}O{sub 4} were identified by SEM and BET surface analyzer respectively and its conductivity studies were made through impedance spectroscopy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Compression failure mechanisms in unidirectional composites

Compression failure mechanisms in unidirectional composites were examined. Possible failure modes of constituent materials are summarized and analytical models for fiber microbuckling are reviewed from a unified viewpoint. Due to deficiencies in available models, a failure model based on nonlinear properties and initial fiber curvature is proposed. The effect of constituent properties on composite compression behavior was experimentally investigated using two different graphite fibers and four different epoxy resins. The predominant microscopic scale failure mode was found to be shear crippling. In a soft resin, shear crippling was in the form of buckling of fibers on a microscopic scale. However, stiff resins failure was characterized by the formation of a kink band. For unidirectional laminates, compressive strength, and compressive modulus to a less extent, were found to increase with increasing magnitude of resin modulus. The change in compressive strength with resin modulus was predicted using the proposed nonlinear model.

Hahn, H. T.↗

Compression failure mechanisms in unidirectional composites

Compression failure mechanisms in unidirectional composites were examined. Possible failure modes of constituent materials are summarized and analytical models for fiber microbuckling are reviewed from a unified viewpoint. Due to deficiencies in available models, a failure model based on nonlinear properties and initial fiber curvature is proposed. The effect of constituent properties on composite compression behavior was experimentally investigated using two different graphite fibers and four different epoxy resins. The predominant microscopic scale failure mode was found to be shear crippling. In a soft resin, shear crippling was in the form of buckling of fibers on a microscopic scale. However, stiff resins failure was characterized by the formation of a kink band. For unidirectional laminates, compressive strength, and compressive modulus to a less extent, were found to increase with increasing magnitude of resin modulus. The change in compressive strength with resin modulus was predicted using the proposed nonlinear model.

Hahn, H. T.↗

Production and Characterization of Carbon Nanotubes and Nanotube-Based Composites

The Nobel Prize winning discovery of the Buckuball (C60) in 1985 at Rice University by a group including Dr. Richard Smalley led to the whole new class of carbon allotropes including fullerenes and nanotubes. Especially interesting from many viewpoints are single-walled carbon nanotubes, which structurally are like a single graphitic sheet wrapped around a cylinder and capped at the ends. This cylinders have diameter as small as 0.5 - 2 nm (1/100,000th the diameter of a human hair) and are as long as 0.1 - 1 mm. Nanotubes are really individual molecules and believed to be defect-free, leading to high tensile strength despite their low density. Additionally, these fibers exhibit electrical conductivity as high as copper, thermal conductivity as high as diamond, strength 100 times higher than steel at one-sixth the weight, and high strain to failure. Thus it is believed that developments in the field of nanotechnology will lead to stronger and lighter composite materials for next generation spacecraft. Lack of a bulk method of production is the primary reason nanotubes are not used widely today. Toward this goal JSC nanotube team is exploring three distinct production techniques: laser ablation, arc discharge and chemical vapor deposition (CVD, in collaboration with Rice University). In laser ablation technique high-power laser impinges on the piece of carbon containing small amount of catalyst, and nanotubes self-assemble from the resulting carbon vapor. In arc generator similar vapor is created in arc discharge between carbon electrodes with catalyst. In CVD method nanotubes grow at much lower temperature on small catalyst particles from carbon-containing feedstock gas (methane or carbon monoxide). As of now, laser ablation produces cleanest material, but mass yield is rather small. Arc discharge produces grams of material, but purity is low. CVD technique is still in baby steps, but preliminary results look promising, as well as perspective of scaling the process up. We are also working on necessary purification of nanotubes. Applications of nanotubes are in such various fields as lightweight composites, molecular electronics, energy storage (electrodes in Li ion batteries), flat panel displays, conductive polymers, etc. JSC nanotube team is focused on development of lightweight materials. We work on the injection thermoset epoxies reinforced with nanotubes. Early results show good wetting of nanotube surface with epoxy, which is very important. More research will be possible as more nanotubes become available.

Nikolaev, Pavel↗

Development and Performance of Tungsten-Coated Graphitic Foam for Plasma-Facing Components

High-density graphitic foam is an ideal low-Z plasma-facing material for deuterium-deuterium plasma experiments where tritium codeposition is not an issue. However, like all carbon, graphitic foam suffers from a precipitous drop in thermal conductivity at high temperatures, >600°C. To mitigate these problems, functionally graded layers of tungsten can be deposited to a thickness of 2 to 4 mm onto the plasma side of the foam using chemical vapor deposition. The graphitic foam then acts as a high-conductivity heat sink at temperatures below 600°C for the thin high-Z armor coating. The overall component weighs 18 times less than a comparable volume of tungsten and lacks the coefficient of thermal expansion joining issues between the CuCrZr tubing and the tungsten. This paper discusses the coating development and characterization and presents the results of recent plasma exposures in W7-X. It also reports on computational fluid dynamics heat transfer modeling and preparations for high heat flux testing of mock-ups. This hybrid plasma-facing component (PFC) consisting of innovative engineered materials may be a cost-effective, actively cooled solution for the divertors and other PFCs in long-pulse machines like W7-X and WEST.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Pulse-resolved intensity measurements at a hard X-ray FEL using semi-transparent diamond detectors

Solid-state ionization chambers are presented based on thin diamond crystals that allow pulse-resolved intensity measurements at a hard X-ray free-electron laser (FEL), up to the 4.5 MHz repetition rate that will become available at the European XFEL. Due to the small X-ray absorption of diamond the thin detectors are semi-transparent which eases their use as non-invasive monitoring devices in the beam. FELs are characterized by strong pulse-to-pulse intensity fluctuations due to the self-amplified spontaneous emission (SASE) process and in many experiments it is mandatory to monitor the intensity of each individual pulse. Two diamond detectors with different electrode materials, beryllium and graphite, were tested as intensity monitors at the XCS endstation of the Linac Coherent Light Source (LCLS) using the pink SASE beam at 9 keV. The performance is compared with LCLS standard monitors that detect X-rays backscattered from thin SiN foils placed in the beam. In conclusion, the graphite detector can also be used as a beam position monitor although with rather coarse resolution.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Effects of processing induced defects on laminate response - Interlaminar tensile strength

Four different layup methods were used in the present study of the interlaminar tensile strength of AS4/3501-6 graphite-reinforced epoxy as a function of defects from manufacturing-induced porosity. The methods were: (1) baseline hand layup, (2) solvent wipe of prepreg for resin removal, (3) moisture-introduction between plies, and (4) a low-pressure cure cycle. Pore characterization was conducted according to ASTM D-2734. A significant reduction is noted in the out-of-plane tensile strength as a function of increasing void content; the porosity data were used in an empirical model to predict out-of-plane strength as a function of porosity.

Gurdal, Zafer↗

A diamond detector for inertial confinement fusion X-ray bang-time measurements at the National Ignition Facility

An instrument has been developed to measure X-ray bang-time for inertial confinement fusion capsules; the time interval between the start of the laser pulse and peak X-ray emission from the fuel core. The instrument comprises chemical vapor deposited polycrystalline diamond photoconductive X-ray detectors with highly ordered pyrolytic graphite X-ray monochromator crystals at the input. Capsule bang-time can be measured in the presence of relatively high thermal and hard X-ray background components due to the selective band pass of the crystals combined with direct and indirect X-ray shielding of the detector elements. A five channel system is being commissioned at the National Ignition Facility at Lawrence Livermore National Laboratory for implosion optimization measurements as part of the National Ignition Campaign. Characteristics of the instrument have been measured demonstrating that X-ray bang-time can be measured with {+-} 30ps precision, characterizing the soft X-ray drive to +/- 1eV or 1.5%.

42 ENGINEERING↗

Local Structure Analysis and Modelling of Lignin‐Based Carbon Composites through the Hierarchical Decomposition of the Radial Distribution Function

Abstract Carbonized lignin has been proposed as a sustainable and domestic source of activated, amorphous, graphitic, and nanostructured carbon for many industrial applications as the structure can be tuned through processing conditions. However, the inherent variability of lignin and its complex physicochemical structure resulting from feedstock and pulping selection make the Process‐Structure‐Property‐Performance (PSPP) relationships hard to define. In this work, radial distribution functions (RDFs) from synchrotron X‐ray and neutron scattering of lignin‐based carbon composites (LBCCs) are investigated using the Hierarchical Decomposition of the Radial Distribution Function (HDRDF) modelling method to characterize the local atomic environment and develop quantitative PSPP relationships. PSPP relationships for LBCCs defined by this work include crystallite size dependence on lignin feedstock as well as increasing crystalline volume fraction, nanoscale composite density, and crystallite size with increasing reduction temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Non-Destructive Monitoring of Charge-Discharge Cycles on Lithium Ion Batteries using 7 Li Stray-Field Imaging

Magnetic resonance imaging provides a noninvasive method for in situ monitoring of electrochemical processes involved in charge/discharge cycling of batteries. Determining how the electrochemical processes become irreversible, ultimately resulting in degraded battery performance, will aid in developing new battery materials and designing better batteries. Here we introduce the use of an alternative in situ diagnostic tool to monitor the electrochemical processes. Utilizing a very large field-gradient in the fringe field of a magnet, stray-field-imaging (STRAFI) technique significantly improves the image resolution. These STRAFI images enable the real time monitoring of the electrodes at a micron level. It is demonstrated by two prototype half-cells, graphite ∥Li and LiFePO 4 ∥ Li, that the high-resolution 7 Li STRAFI profiles allow one to visualize in situ Li-ions transfer between the electrodes during charge/discharge cyclings as well as the formation and changes of irreversible microstructures of the Li components, and particularly reveal a non-uniform Li-ion distribution in the graphite.

25 ENERGY STORAGE↗

Evolution of the Raman spectra from single-, few-, and many-layer graphene with increasing disorder

We report on the micro-Raman spectroscopy of monolayer, bilayer, trilayer, and many layers of graphene (graphite) bombarded by low-energy argon ions with different doses. The evolution of peak frequencies, intensities, linewidths, and areas of the main Raman bands of graphene is analyzed as function of the distance between defects and number of layers. We describe the disorder-induced frequency shifts and the increase in the linewidth of the Raman bands by means of a spatial-correlation model. Also, the evolution of the relative areas A{sub D}/A{sub G}, A{sub D}{sup '}/A{sub G}, and A{sub G}{sup '}/A{sub G} is described by a phenomenological model. The present results can be used to fully characterize disorder in graphene systems.

36 MATERIALS SCIENCE↗