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DOE OSTI2023

Effect of Si Content on Extreme Fast Charging Behavior in Silicon–Graphite Composite Anodes

Commercial Li-ion batteries typically incorporate a small amount of high-capacity silicon (Si)-based materials in the composite graphite-based anode to increase the energy density of the battery. However, very little is known about the effects of Si on the fast-charging behavior of composite anodes. Herein, we examine the effects of the Si/graphite ratio in the composite anode on the fast-charging behavior of full cells. We show that addition of Si increases the rate capability from 1C to 8C and improves the capacity retention in early cycles at 6C due to reduced overpotential in constant current charging cycles. The impacts of Si content on fast-charging aging were identified by Post-Test characterization. Despite realizing benefits of available capacity and reduced Li plating at 6C, silicon–electrolyte interactions lead the time-dependent cell performance to fade quickly in the long term. The Post-Test analysis also revealed the thickening of the electrode and nonuniform distribution of electrolyte decomposition products on the Si-containing anodes, as well as the organic-rich solid electrolyte interphase (SEI), which are the factors behind cell degradation. Our study sheds insight on the advantages and disadvantages of Si/graphite composite anodes when they are used in fast-charging applications and guides further research in the area by designing an optimized composition of Si incorporated in a mature graphite matrix.

25 ENERGY STORAGE↗

DOE OSTI2021

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

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

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2012

High psedocapacitance of MnO2 nanoparticles in graphitic disordered mesoporous carbon at high scan rates

Nanocomposites composed of MnO{sub 2} and graphitic disordered mesoporous carbon (MnO{sub 2}/C) were synthesized for high total specific capacitance and redox pseudocapacitance (C{sub MnO{sub 2}}) at high scan rates up to 200 mV s{sup -1}. High resolution transmission electron microscopy (HRTEM) with energy dispersive X-ray spectroscopy (EDX) demonstrated that MnO{sub 2} nanodomains were highly dispersed throughout the mesoporous carbon structure. According to HRTEM and X-ray diffraction (XRD), the MnO{sub 2} domains are shown to be primarily amorphous and less than 5 nm in size. For these composites in aqueous 1 M Na{sub 2}SO{sub 4} electrolyte, C{sub MnO{sub 2}} reached 500 F/g{sub MnO{sub 2}} at 2 mV s{sup -1} for 8.8 wt% MnO{sub 2}. A capacitance fade of only 20% over a 100-fold change in scan rate was observed for a high loading of 35 wt% MnO{sub 2} with a C{sub MnO{sub 2}} of 310 F/g{sub MnO{sub 2}} at the highest scan rate of 200 mV s{sup -1}. The high electronic conductivity of the graphitic 3D disordered mesoporous carbon support in conjunction with the thin MnO{sub 2} nanodomains facilitate rapid electron and ion transport offering the potential of improved high power density energy storage pseudocapacitors.

36 MATERIALS SCIENCE↗

DOE OSTI2012

High pseudocapacitance of MnO2 nanoparticles in graphitic disordered mesoporous carbon at high scan rates

36 MATERIALS SCIENCE↗

DOE OSTI2012

2012 Gordon Research Conference on Graphitic Carbon Materials, Chemistry and Physics of - Formal Schedule and Speaker/Poster Program

The Gordon Research Conference on GRAPHITIC CARBON MATERIALS, CHEMISTRY AND PHYSICS OF was held at the Davidson College, Davidson, North Carolina, June 17 – 22, 2012. The Conference was well-attended with 95 participants (attendees list attached). The attendees represented the spectrum of endeavor in this field coming from academia, industry, and government laboratories, both U.S. and foreign scientists, senior researchers, young investigators, and students. Of the 95 attendees, 41 voluntarily responded to a general inquiry regarding ethnicity which appears on our registration forms. Of the 41 respondents, 49% were Minorities – 5% Hispanic, 44% Asian and 0% African American. Approximately 2% of the participants at the 2012 meeting were women. In designing the formal speakers program, emphasis was placed on current unpublished research and discussion of the future target areas in this field. There was a conscious effort to stimulate lively discussion about the key issues in the field today. Time for formal presentations was limited in the interest of group discussions. In order that more scientists could communicate their most recent results, poster presentation time was scheduled. Attached is a copy of the formal schedule and speaker program and the poster program. In addition to these formal interactions, "free time" was scheduled to allow informal discussions. Such discussions are fostering new collaborations and joint efforts in the field. Carbon materials play an extremely important role in our society. They not only constitute the largest supply of energy we use today (i.e., coal) but also are the bases of many important technologies ranging from pencils, adsorbents, and metal strengtheners, to batteries and many others. Recent studies on graphitic carbon, including fullerenes, carbon nanotubes, and graphene, have further revealed novel optical and electrical properties, making it possible to use them for new applications in renewable energy as well as microelectronics. Moreover, there are many novel and exciting phenomena in these materials such as molecular magnetism, catalysis, many-body and relativistic quantum mechanics, etc.

36 MATERIALS SCIENCE↗

DOE OSTI2012

Graphite and Beryllium Reflector Critical Assemblies of UO 2 (Benchmark Experiments 2 and 3)

A series of experiments was carried out in 1962-65 at the Oak Ridge National Laboratory Critical Experiments Facility (ORCEF) for use in space reactor research programs. A core containing 93.2 wt% enriched UO 2 fuel rods was used in these experiments. The first part of the experimental series consisted of 252 tightly packed fuel rods (1.27-cm triangular pitch) with graphite reflectors, the second part used 252 graphite-reflected fuel rods organized in a 1.506-cm triangular-pitch array, and the final part of the experimental series consisted of 253 beryllium-reflected fuel rods in a 1.506-cm-triangular-pitch configuration and in a 7-tube-cluster configuration. Fission rate distribution and cadmium ratio measurements were taken for all three parts of the experimental series. Reactivity coefficient measurements were taken for various materials placed in the beryllium reflected core. All three experiments in the series have been evaluated for inclusion in the International Reactor Physics Experiment Evaluation Project (IRPhEP) and the International Criticality Safety Benchmark Evaluation Project (ICSBEP) Handbooks. The evaluation of the first experiment in the series was discussed at the 2011 ANS Winter meeting. The evaluations of the second and third experiments are discussed below. These experiments are of interest as benchmarks because they support the validation of compact reactor designs with similar characteristics to the design parameters for a space nuclear fission surface power system.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2013

Nitrogen-Doped Graphitic Nanoribbons: Synthesis, Characterization and Transport

Nitrogen-doped graphitic nanoribbons (Nx-GNRs), synthesized by chemical vapor deposition (CVD) using pyrazine as a nitrogen precursor, are reported for the first time. Scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) reveal that the synthesized materials are formed by multi-layered corrugated graphitic nanoribbons (GNRs) which in most cases exhibit the formation of curved graphene edges (loops). This suggests that during growth, nitrogen atoms promote loop formation; undoped GNRs do not form loops at their edges. Transport measurements on individual pure carbon GNRs exhibit a linear I-V (current-voltage) behavior, whereas Nx-GNRs show reduced current responses following a semiconducting-like behavior, which becomes more prominent for high nitrogen concentrations. To better understand the experimental findings, electron density of states (DOS), quantum conductance for nitrogen doped zigzag and armchair single-layer GNRs are calculated for different N doping concentrations using Density Functional Theory (DFT) and non-equilibrium Green functions. These calculations confirm the crucial role of nitrogen atoms in the transport properties, confirming that the nonlinear I-V curves are due to the presence of nitrogen atoms within the Nx-GNRs lattice that act as scattering sites. These characteristic Nx-GNRs transport could be advantageous in the fabrication of electronic devices including sensors in which metal-like undoped GNRs are unsuitable.

Jia, Xiaoting↗

DOE OSTI2013

EFFECTS OF SIZE AND GEOMETRY ON THE EQUIBIAXIAL FLEXURAL TEST OF FINE GRAINED NUCLEAR GRAPHITE

Reduction of specimen size is an essential requirement for neutron irradiation effect studies of materials since space in nuclear reactors for those studies are often very limited and costly. Reducing the specimen size can dramatically reduce the cost of these studies, the irradiation exposure to personnel involved in post irradiation examination and the volume of radioactive waste. In this study, 4 specimen sizes were systematically varied to examine the size effect on the equibiaxial flexure test of fine grain nuclear graphite in non-irradiated conditions at room temperature. A statistically significant sample population of 30 was used for each specimen geometry or dimension. The results showed that the round shaped samples followed weibull distribution with Weibull modulus of 25 to 35. The average strength followed the trend of the weakest link theory. The 2 sizes of square shaped samples had Weibull modulus of 29 and 40. Data from round and square samples agree with others reasonably and collectively follow the Weibull scaling theory. It is concluded that the equibiaxial flexural test using adequate population of small specimens provides useful and reliable information on the statistical strength properties for fine-grained nuclear graphite materials.

Shih, Chunghao↗

DOE OSTI2015

Metal-bonded graphite foam composites

A metal-bonded graphite foam composite includes a ductile metal continuous phase and a dispersed phase that includes graphite foam particles.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Patterned structures of graphene and graphitic carbon and methods for their manufacture

A patterned graphene or graphitic body is produced by providing a three-dimensionally patterned carbonaceous body; coating the body with a catalytic metal whereby is formed a coating having an inner surface proximal the body and an outer surface distal the body; and annealing the coated body under time and temperature conditions effective to form a graphene or graphitic layer on the outer surface of the catalytic metal coating.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Post Irradiation Examination Results of the NT-02 Graphite Fins NUMI Target

The NT-02 neutrino target in the NuMI beamline at Fermilab is a 95 cm long target made up of segmented graphite fins. It is the longest running NuMI target, which operated with a 120 GeV proton beam with maximum power of 340 kW, and saw an integrated total proton on target of 6.1 1020. Over the last half of its life, gradual degradation of neutrino yield was observed until the target was replaced. The probable causes for the target performance degradation are attributed to radiation damage, possibly including cracking caused by reduction in thermal shock resistance, as well as potential localized oxidation in the heated region of the target. Understanding the long-termstructural response of target materials exposed to proton irradiation is critical as future proton accelerator sources are becoming increasingly more powerful. As a result, an autopsy of the target was carried out to facilitate post-irradiation examination of selected graphite fins. Advanced microstructural imaging and surface elemental analysis techniques were used to characterize the condition of the fins in an effort to identify degradation mechanisms, and the relevant findings are presented in this paper.

43 PARTICLE ACCELERATORS↗

DOE OSTI2018

Patterned structures of graphene and graphitic carbon and methods for their manufacture

36 MATERIALS SCIENCE↗

DOE OSTI2022

DEVELOPMENT OF AN APPROACH FOR DOWNBLENDING AND DISPOSITION OF IRRADIATED GRAPHITE FUEL

The IGR reactor, a pulse-type test experimental reactor, reached full power in 1961. The reactor contains a center axial experimental ampoule that is subjected to a large pulse of neutrons (neutron flux maximum density of 7×1016 n/cm2·s, peak power 10GW) when the reactor is operated. The fuel form for the IGR reactor is graphite cubes and rods impregnated with highly enriched (90%) uranyl-dinitrate (UO2(NO3)2·6H2O). This fuel is eligible for return to Russia for reprocessing under the Russian Research Reactor Fuel Return program. However due to some technical and licensing issues it was decided to immobilize this fuel in Kazakhstan. The disposition approach thus selected for the spent HEU fuel involves down-blending of the fuel followed by cementation. Development of the process for down-blending and subsequent cementation requires a process that satisfies many criteria, including fissile content, compressive strength, permeability, and containment of radioactivity, among others. One key goal of the final product is to meet the criteria for termination of safeguards. This paper will describe the overall challenge associated with disposition of irradiated HEU graphite spent fuel, the identification of the objectives of the disposition process, and the constraints associated with development of the process and the waste form.

Gaines, Kris↗

DOE OSTI2022

Methods and systems for microwave assisted production of graphitic materials

Systems and methods for plasma based synthesis of graphitic materials. The system includes a plasma forming zone configured to generate a plasma from radio-frequency radiation, an interface element configured to transmit the plasma from the plasma forming zone to a reaction zone, and the reaction zone configured to receive the plasma. The reaction zone is further configured to receive feedstock material comprising a carbon containing species, and convert the feedstock material to a product comprising the graphitic materials in presence of the plasma.

Zeller, Kurt W.↗

DOE OSTI2022

Session 3: Irradiation and Thermal Stesses - NRC Graphite Behavior Model

Graphite anisotropic microstructure Graphite crystal structure and basal planes Response to irradiation and temperature C-axis and a-axis behavior The effect of porosity Nano-and micro-length scale Microscopic to macroscopic response Material property changes Defect length-scale factors Internal stress build-up Irradiation induced dimensional change Temperature effects Stress increases & property changes

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2024

Preliminary Benchmark Uncertainties for Deimos, a HALEU-Fueled and Graphite-Moderated Advanced Reactor Testbed

Many advanced reactor concepts will make use of various uranium fuels with levels of enrichment higher than previously seen in current light water reactors. In particular, High-Assay Low Enriched Uranium (HALEU), that is uranium enriched to 235 U ≈ 20 w/o%, is planned to be used in over ten new reactor concepts. HALEU is attractive for advanced reactors as it enables longer intervals between refueling. Unfortunately, little to no experience with HALEU is available in experimental literature raising concerns for not only licensing advanced re actors but also fabrication and transportation of HALEU fuels. This is where Deimos, a Los Alamos National Laboratory internal project, comes in. Deimos is a new critical experiment scheduled for FY24 at the National Criticality Experiments Research Center (NCERC). Deimos is a graphite moderated, graphite and beryllium reflected critical experiment making use of HALEU TRi-structural ISOtropic (TRISO) fuel from the Compact Nuclear Power System (CNPS). This transaction entails a brief description of efforts to benchmark Deimos for inclusion into the International Criticality Safety

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

DOE OSTI2024

Rechargeable Li-ion battery with halogen intercalated graphite electrode

The disclosure provides rechargeable lithium ion batteries comprising at least one lithium salt-graphite composite electrode. In particular, the disclosure provides a rechargeable “water-in-bisalt” lithium ion battery with a high potential where at least a portion of the lithium salt is phase separated from the aqueous electrolyte, and where the anionic-redox reaction occurs within the graphitic lattice.

Wang, Chunsheng↗

DOE OSTI2026

NuMI Graphite Target Fin Removal Assembly

Materials scientists want to study the irradiated graphite target from the Neutrino at the Main Injector (NuMI) beam line. In order to gather these irradiated graphite fins from the target canister, it will have to be done remotely. Therefore, a removal assembly will need to be created in order to do this efficiently and well. This project aims to make progressive steps towards deploying the final target removal assembly. Furthermore, calculations related to the removal assembly design were done, and tests were planned to discover further information about the feasibility of this design. The main result from this project is the deflection of the cantilever arm, which is 0.354 inches due to the weight of the beam and cutting tool. Additionally, more results of this project are the testing assembly CAD model and the feasibility of design. This project concludes that there is still more work that needs to be done for the removal assembly to be deployed, but there were foundational steps that were made in the implementation of this design. Finally, there should be further steps and tests to determine the feasibility of this removal assembly.

Malovski, Azra [NIU, DeKalb]↗