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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 19 records

Synthesizing Highly Crystalline Graphite Powder from Bulk Polyethylene Waste for Lithium-Ion Battery Anodes

Upcycling plastic waste into graphite can potentially be used, in conjunction with other methods, to manage existing waste materials and diversify graphite supply chains. However, synthesizing large quantities of crystalline graphite powder from plastic waste, particularly polyethylene (PE), remains a challenge because PE decomposes into light gases during thermal processing, and simple methods do not exist at any appreciable size scale to address this challenge. In this work, a method is developed for air processing bulk forms of PE waste to create a stable carbon char that does not readily decompose during high-temperature processing. This method employs solid additives in the form of salts, which are combined with the PE melt during air processing to increase the effective surface area of the melt and improve the oxygen-driven chemistry that stabilizes the PE for high-temperature processing. After removing the solid salt additives from the PE-derived char, it is converted into a highly crystalline bulk graphite powder using a Fe-based low-temperature (<1500 °C) catalytic process. The PE-derived graphite powder showed excellent electrochemical performance as an anode material for lithium-ion batteries (LIBs) with a capacity of up to 302 mAh/g at 0.5 discharge/charge cycles per hour (0.5 C) and capacity retention of 100% after 415 cycles. This method illustrates there are opportunities for upcycling large quantities of PE waste to produce graphite powders.

Huynh, Ngoc Tien [NETL Site Support Contractor, Na↗

Synthesizing Highly Crystalline Graphite Powder from Bulk Polyethylene Waste for Lithium-Ion Battery Anodes

Upcycling plastic waste into graphite can potentially be used, in conjunction with other methods, to manage existing waste materials and diversify graphite supply chains. However, synthesizing large quantities of crystalline graphite powder from plastic waste, particularly polyethylene (PE), remains a challenge because PE decomposes into light gases during thermal processing and simple methods do not exist at any appreciable size scale to address this challenge. In this work, a method is developed for air processing bulk forms of PE waste to create stable carbon char that does not readily decompose during high-temperature processing. This method employs solid additives in the form of salts, which are combined with the PE melt during air processing to increase the effective surface area of the melt and improve the oxygen-driven chemistry that stabilizes PE for high-temperature processing. After removal of the solid salt additives from the PE-derived char, it is converted into a highly crystalline bulk graphite powder using an Fe-based catalytic process. The PE-derived graphite anode in a lithium-ion coin cell showed a specific capacity of 345 mAh/g at 0.05C with an initial Coulombic efficiency of 87% and reversible capacity retention of ~100% at different current rates. It also showed a specific capacity of up to 313 mAh/g at 0.5 discharge/charge cycles per hour (0.5C) and Coulombic efficiency of 99.9% after 250 cycles, indicating excellent electrochemical performance as an anode material for lithium-ion batteries. This method illustrates that there are opportunities for upcycling large quantities of PE waste to produce graphite powders suitable for use in LIBs.

25 ENERGY STORAGE↗

Synthesizing Highly Crystalline Graphite Powder from Bulk Polyethylene Waste for Lithium-Ion Battery Anodes

Upcycling plastic waste into graphite can potentially be used, in conjunction with other methods, to manage existing waste materials and diversify graphite supply chains. However, synthesizing large quantities of crystalline graphite powder from plastic waste, particularly polyethylene (PE), remains a challenge because PE decomposes into light gases during thermal processing, and simple methods do not exist at any appreciable size scale to address this challenge. In this work, a method is developed for air processing bulk forms of PE waste to create a stable carbon char that does not readily decompose during high-temperature processing. This method employs solid additives in the form of salts, which are combined with the PE melt during air processing to increase the effective surface area of the melt and improve the oxygen-driven chemistry that stabilizes the PE for high-temperature processing. After removing the solid salt additives from the PE-derived char, it is converted into a highly crystalline bulk graphite powder using a Fe-based low-temperature (<1500 °C) catalytic process. The PE-derived graphite powder showed excellent electrochemical performance as an anode material for lithium-ion batteries (LIBs) with a capacity of up to 302 mAh/g at 0.5 discharge/charge cycles per hour (0.5 C) and capacity retention of 100% after 415 cycles.

Huynh, Ngoc Tien↗

Synthesizing Highly Crystalline Graphite Powder for Lithium-Ion Battery Anodes from Bulk Polyethylene Waste

Upcycling plastic waste into graphite can potentially be used to manage existing waste materials and diversify graphite supply chains. However, synthesizing large quantities of crystalline graphite powder from plastic waste, particularly polyethylene (PE), remains a challenge because PE decomposes into light gases during thermal processing, and simple methods do not exist at any appreciable size scale to address this challenge. In this work, a method is developed for air processing bulk forms of PE waste to create a stable carbon char, then be converted into a highly crystalline bulk graphite powder using a Fe-based catalytic process. The PE-derived graphite demonstrates excellent electrochemical performance as an anode material for lithium-ion batteries.

Gao, Yuan↗

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↗

Highly Crystalline Graphite Synthesis from Coal with a Sustainable Process

Synthetic graphite is made predominantly from a petroleum-derived needle coke using the Acheson method. This involves heating the needle coke at elevated temperatures of ~ 3000 °C for more than 7 days. High-temperature heating is the most technically challenging, expensive, and energy-intensive aspect of graphite manufacturing. We will present a strategy for synthesizing high-quality graphite powder from coal using a low-temperature catalytic graphitization process. The use of a catalyst drops the processing temperatures to 1500 °C and processing times to a few hours. The graphite produced with this process has been characterized and has been shown to have comparable physical/chemical properties with commercially sourced graphite materials. We will also present a sustainable method to recover and reuse the catalyst and acid used to retrieve the catalyst. This overcomes a long-standing technical hurdle associated with using catalysts for manufacturing graphite.

crystalline graphite powder↗

Low-Temperature Production of Battery Grade Graphite from Coal with Recovery and Reuse of the Catalyst

Synthetic graphite is made predominantly from a petroleum-derived needle coke using the Acheson method. This involves heating the needle coke at elevated temperatures of ~ 3000 °C for more than 7 days. High-temperature heating is the most technically challenging, expensive, and energy-intensive aspect of graphite manufacturing. We will present a strategy for synthesizing high-quality battery-grade graphite powder from coal using a low-temperature catalytic graphitization process. The use of a catalyst drops the processing temperatures to 1500 °C and processing times to a few hours. The graphite produced with this process has been tested as a battery anode and has been shown to outperform anodes made with commercially sourced graphite materials. We will also present a sustainable method to recover and reuse the catalyst and acid used to retrieve the catalyst. This overcomes a long-standing technical hurdle associated with using catalysts for manufacturing graphite.

Kim, Ki-Joong↗

Nickel-Graphite Composite Compliant Interface and/or Hot Shoe Material

Next-generation high-temperature thermoelectric-power-generating devices will employ segmented architectures and will have to reliably withstand thermally induced mechanical stresses produced during component fabrication, device assembly, and operation. Thermoelectric materials have typically poor mechanical strength, exhibit brittle behavior, and possess a wide range of coefficient of thermal expansion (CTE) values. As a result, the direct bonding at elevated temperatures of these materials to each other to produce segmented leg components is difficult, and often results in localized microcracking at interfaces and mec hanical failure due to the stresses that arise from the CTE mismatch between the various materials. Even in the absence of full mechanical failure, degraded interfaces can lead to increased electrical and thermal resistances, which adversely impact conversion efficiency and power output. The proposed solution is the insertion of a mechanically compliant layer, with high electrical and thermal conductivity, between the low- and high-temperature segments to relieve thermomechanical stresses during device fabrication and operation. This composite material can be used as a stress-relieving layer between the thermoelectric segments and/or between a thermoelectric segment and a hot- or cold-side interconnect material. The material also can be used as a compliant hot shoe. Nickel-coated graphite powders were hot-pressed to form a nickel-graphite composite material. A freestanding thermoelectric segmented leg was fabricated by brazing the compliant pad layer between the high-temperature p- Zintl and low-temperature p-SKD TE segments using Cu-Ag braze foils. The segmented leg stack was heated in vacuum under a compressive load to achieve bonding. The novelty of the innovation is the use of composite material that re duces the thermomechanical stresses en - countered in the construction of high-efficiency, high-temperature therm - o-electric devices. The compliant pad enables the bonding of dissimilar thermoelectric materials while maintaining the desired electrical and thermal properties essential for efficient device operation. The modulus, CTE, electrical, and thermal conductances of the composite can be controlled by varying the ratio of nickel to graphite.

Firdosy, Samad A.↗

Kinetics of the Formation of Intercalation Compounds in Crystalline Graphite

Crystalline graphite has a structure that can be best described as an ordered stack of flat aromatic layers. It is known to form intercalation compounds with bromine and nitric acid. Their formation was studied using thermal measurements and analytical techniques. Samples of graphite treated with either bromine or nitric acid were prepared by contacting these reagents with powdered graphite.

crystalline graphite intercalation compounds kinet↗

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↗

Development of CdO-graphite-Ag coatings for gas bearings to 427 C

Graphite is one of the most commonly known lubricants. Its effectiveness in a range between room temperature (RT) and 540 C is reportedly improved by adding cadmium oxide. CdO-graphite powder in a gas carrier has been used in numerous applications that rely on dry lubrication. A coating of this composition was developed and successfully tested in foil air bearings for long periods up to a temperature of 427 C and at a normal contacting load (during starting and stopping) of 14 kPa based on bearing projected area. The addition of ultra-fine silver to the CdO-graphite has improved the coating endurance. At 427 C, the CdO-graphite-Ag coating performed better than CdO-graphite without silver, both for extended periods at 14 kPa loading and for limited periods at 35 kPa. At 288 C, the coating was tested for an extended period up to 28 kPa and has also successfully completed high-speed shock tests to an acceleration level of 100g.

Bhushan, B.↗

Factors affecting the thermal shock resistance of several hafnia based composites containing graphite or tungsten

The thermal shock resistance of hafnia based composites containing graphite powder or tungsten fibers was investigated in terms of material properties which include thermal expansion, thermal conductivity, compressive fracture stress, modulus of elasticity, and phase stability in terms of the processing parameters of hot pressing pressure and/or density, degree of stabilization of the hafnia, and composition. All other parameters were held constant or assumed constant. The thermal shock resistance was directly proportional to the compressive fracture stress to modulus of elasticity ratio and was not affected appreciably by the small thermal expansion or thermal conductivity changes. This ratio was found to vary strongly with the composition and density such that the composites containing graphite had relatively poor thermal shock resistance, while the composites containing tungsten had superior thermal shock resistance.

Lineback, L. D.↗

Experimental and computational studies on high-entropy carbide MoNbTaVWC 5 under high pressures

High-entropy carbide, MoNbTaVWC 5 , was synthesized from oxide precursors of the constituent metals, mixed with graphite powder in a microwave-generated hydrogen plasma at 26.66 kPa and 2100 °C. Ambient x-ray diffraction analysis confirms the full conversion of oxide precursors into a single-phase, face-centered cubic structure with a lattice parameter a = 4.3309 Å. Nanoindentation measured a hardness of 24.5 ± 1.3 GPa and an elastic modulus of 386 ± 22 GPa. The synthesized sample, mixed with a copper pressure marker, was studied by the radial x-ray diffraction technique with beryllium gasketing in a diamond anvil cell up to 70 GPa. The experimentally measured pressure–volume curve and shear strength were compared with theoretical predictions using the special quasi-random structure technique and density functional theory. MoNbTaVWC 5 achieved a 12% volume compression at 70 GPa and exhibited a high shear strength of 6.6 GPa. The present study demonstrates that the high-entropy carbide MoNbTaVWC 5 exhibits exceptional incompressibility and high strength under extreme conditions.

36 MATERIALS SCIENCE↗

Fabrication of Advanced Nanocarbon-Metal Composites for Improved Energy Efficiency

We fabricated nanocarbon metal composites (NCMC) of Al alloys with a process called “electrocharging assisted process” (EAP). This method consists of the application of a high current to a mixture of liquid metal and carbon particles. We investigated aluminum alloys (6061 and 1350) and used activated carbon and graphite powder as the source of carbon. The high current induces the formation of carbon chains and ribbons in the liquid metal. Upon solidification of the metal an epitaxial relation between the carbon nanostructures and the metal lattice is produced. The purpose of the project was to find the parameters during the reaction that would give rise to a high density of nanoribbons extending throughout the metal such that the electrical conductivity and the mechanical strength of the composite increased and that the method could be extended to large scale manufacturing. For this purpose, we designed two reactors for the incorporation of nanocarbon ribbons in aluminum metal. The first reactor was designed to have more control of the region with the high current density. However, there were problems with getting good mixing of the carbon in small volumes. A second reactor was designed with a stirrer that allowed for better mixing of the carbon by the introduction of argon gas through the shaft of the stirrer. NCMC were fabricated with a series of parameters to understand the role of current, time of applied current, type and shape of the cathode electrode and stirring speed of the mixture. We analyzed the composites by Raman scattering to gain information on the crystallite size of the nanocarbon, XRD to obtain the crystal structure of the composite, SEM and TEM to characterize the grain size of the aluminum grains and the quality of the crystal structure. We also measured the electrical conductivity and mechanical properties of selected samples. The nanocomposites showed increase in crystallite size of the nanocarbon with a linear dependence of the crystallite size on the duration of the applied current. There is a minimum current density necessary for the crystallite size to increase compared to the ~ 10 nm size of the activated carbon source used in the fabrication. The electrical conductivity of the nanocomposites increased with crystallite size of the nanocarbon and with the concentration of converted carbon. The maximum increase in electrical conductivity was 5.7% above the baseline for samples with ~ 4 wt % nanocarbon with crystallite size larger than 30 nm. These samples presented a hardness ~ 8% higher than the baseline samples with no carbon.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Electrically conductive, black thermal control coatings for spacecraft application. I - Silicate matrix formulation

The formulation of the graphite silicate paints MH-11 and MH-11Z, which will serve as electrically conductive, heat-resistant thermal control coatings for the Galileo spacecraft's 400 Newton engine plume shield, 10 Newton thruster plume shields, and external shunt radiators, is described, and performance results for these paints are reported. The MH-11 is produced by combining a certain grade of graphite powder with a silicate base to produce a black, inorganic, electrically conductive, room temperature cure thermal control paint having high temperature capability. Zinc oxide is added to the MH-11 formulation to produce the blister resistant painta MH-11Z. The mechanical, chemical, thermal, optical, and radiation characteristics of the coatings are reported. The formulation, mixing, application, and surface preparation of the substrates are described, and a method of determining the electrical resistance of the coatings is demonstrated.

Bauer, J. L.↗

Hairy carbon electrodes studied by cyclic voltammetry and battery discharge testing

Hairy carbon is a new material developed by growing submicron carbon filaments on conventional carbon substrates. Typical substrate materials include carbon black, graphite powder, carbon fibers, and glassy carbon. A catalyst is used to initiate hair growth with carbonaceous gases serving as the carbon source. To study the electrochemical behavior of hairy carbons, cyclic voltammetry (CV) and discharge testing were conducted. In both cases, hairy carbon results surpassed those of the substrate material alone.

Chung, Deborah D. L.↗