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31 records · Page 2

Rare earth elements from waste

Rare earth elements (REEs) are critical materials in electronics and clean technologies. With the diminishing of easily accessible minerals for mining, the REE recovery from waste is an alternative toward a circular economy. Present methods for REE recovery suffer from lengthy purifications, low extractability, and high wastewater streams. Here, we report an ultrafast electrothermal process (~3000°C, ~1 s) based on flash Joule heating (FJH) for activating wastes to improve REE extractability. FJH thermally degrades or reduces the hard-to-dissolve REE species to components with high thermodynamic solubility, leading to ~2× increase in leachability and high recovery yields using diluted acid (e.g., 0.1 M HCl). The activation strategy is feasible for various wastes including coal fly ash, bauxite residue, and electronic waste. The rapid FJH process is energy-efficient with a low electrical energy consumption of 600 kWh ton –1 . The potential for this route to be rapidly scaled is outlined.

01 COAL, LIGNITE, AND PEAT↗

Developing a Facile Technology for Converting Domestic US Coal into High-Value Graphene

Universal Matter Ltd. was formed in July 2019 to scale-up and commercialize a breakthrough process, Flash Joule Heating (FJH), to transform different coal grades, into high-quality graphene. This graphene is made using a high-voltage electric discharge that brings the carbon source to temperatures higher than 3,000 K in less than 10 milliseconds. The short burst of electricity breaks all chemical bonds in the feedstock and reorders the carbon atoms into exceptionally thin layers of a special type of graphene, at an estimated $100 per ton in electricity cost. This process is capable of producing 1-5 layer-thick high-quality graphene (with defects of <0.05% and purity of >99%) in a green, practical, and cost-effective process. The graphene produced in the FJH process is a very special kind of graphene called “turbostratic graphene” (TG). TG offers superior physical properties compared to other graphene structures on a similar weight basis. Unlike graphene made from graphite using traditional techniques, the graphene layers in TG stack in an irregular pattern that allows the graphene powder to be exfoliated more easily and blend more evenly within other materials. The TG produced using our FJH technology is the most economical graphene product that opens up significant large volume markets for end-use applications; it would allow the use of TG made from coal for commercial applications in several market segments including energy storage, sensors, hyper-lubricants, reinforced plastics, and building materials such as concrete.

01 COAL, LIGNITE, AND PEAT↗

Nondestructive flash cathode recycling

Effective recycling of end-of-life Li-ion batteries (LIBs) is essential due to continuous accumulation of battery waste and gradual depletion of battery metal resources. The present closed-loop solutions include destructive conversion to metal compounds, by destroying the entire three-dimensional morphology of the cathode through continuous thermal treatment or harsh wet extraction methods, and direct regeneration by lithium replenishment. Here, we report a solvent- and water-free flash Joule heating (FJH) method combined with magnetic separation to restore fresh cathodes from waste cathodes, followed by solid-state relithiation. The entire process is called flash recycling. This FJH method exhibits the merits of milliseconds of duration and high battery metal recovery yields of ~98%. After FJH, the cathodes reveal intact core structures with hierarchical features, implying the feasibility of their reconstituting into new cathodes. Relithiated cathodes are further used in LIBs, and show good electrochemical performance, comparable to new commercial counterparts. Life-cycle-analysis highlights that flash recycling has higher environmental and economic benefits over traditional destructive recycling processes.

25 ENERGY STORAGE↗

Waste plastic- and coke-derived flash graphene as lubricant additives

Lubricants play an essential role in reducing wear in mechanical systems. Carbon nanomaterial additives, such as graphene, have been found to significantly improve tribological performance when used as lubricant additives. Here, in this study, post-consumer plastic and metallurgical coke are converted into turbostratic flash graphene (FG) through flash Joule heating (FJH). The FG is then added to either poly(alpha olefin) 6 or 9 (PAO 6 or PAO 9). Adding waste plastic-derived FG (WPFG) and metallurgical coke-derived FG (MCFG) to lubricants resulted in a significant decrease in the coefficient of friction (CoF), wear scar diameter (WSD), and roughness during four-ball testing. WPFG and MCFG decrease the CoF in PAO 9 by 6% and 9% at 0.1 mg mL -1 , respectively, and in PAO 6 by 23% and 6% at 0.5 mg mL -1 , respectively. WPFG and MCFG decrease the WSD of steel balls in PAO 9 by 14% and 8% at 0.5 mg mL -1 , respectively, and in PAO 6 by 12% and 14% at 0.5 mg mL -1 , respectively, by forming a coating-like layer between the metal surfaces. Roughness decreased by 38% and 32% for WPFG and MCFG in PAO 6, respectively, and by 35% and 29% for WPFG and MCFG in PAO 9, respectively. Finally, preliminary life cycle analyses demonstrate that production of FG produces up to 99% less greenhouse gas emissions, requires 98% less energy, and consumes 99.9% less water when compared to conventional production techniques of graphene. Hence, metallurgical coke and waste plastic are shown to be ready feedstocks for high-quality FG lubricant additives.

36 MATERIALS SCIENCE↗

Pore Resolved Simulations of Joule Heating in Fibrous Media using an Embedded Boundary Method

Joule heating has been regarded as an energy-efficient and sustainable method for heating materials and gases at large scales. The modeling of local temperature effects at pore-resolved scales for such systems, however, has been difficult to achieve due to challenges in coupling thermo-chemical processes in complex porous media and in large representative volume elements (RVEs). To this end, we developed an electro-thermal model at the pore scale to study Joule heating effects in large heterogeneous systems with different microstructures. This was achieved using the level set method to implicitly delineate distinct regions within the domain, and an embedded boundary method to facilitate heat exchange across the fluid-solid interface. Moreover, we applied this method to investigate unsteady non-linear electro-thermal effects in non-woven fibrous graphite conductors for RVEs with characteristic lengths of 2 mm, with different fiber orientations, porosity (80% – 90%) and fiber diameters (10 – 20µm). The coupled equations were solved numerically and they produced peak temperatures greater than 2000 K resulting in heating rates as high as 80,000 K/s. Moreover, the results depended strongly on the microstructure of the fiber skeleton and current density. Geometries with large fibers (∼ 20µm) had the highest average and peak temperatures with the mean temperature increasing by 3.9 % while the peak temperature increased by 9.9 %. Anisotropic domains on the other hand had the lowest mean and peak temperatures with peak and mean temperatures of 2293 K and 1437.7K respectively representing a corresponding 12.1% and 5.1% drop in the temperatures. An increase in porosity from 80% to 90%, however, led to an increase in the peak temperature by 5.1%.

Joule heating↗

Coupling Amorphization and Compositional Optimization of Ternary Metal Phosphides toward High-Performance Electrocatalytic Hydrogen Production

Amorphous materials, with abundant active sites and unique electronic configurations, have the potential to outperform their crystalline counterparts in high-performance catalysis for clean energy. However, their synthesis and compositional optimization remain underexplored due to the strict conditions required for their formation. Here, in this study, we report the synthesis of ternary platinum-nickel-phosphorus (PtNiP) amorphous nanoparticles (ANPs) within milliseconds by flash Joule heating, which features ultrafast cooling that enables the vitrification of metal precursors. Through compositional optimization, the Gibbs free energy of hydrogen adsorption for Pt 4 Ni 4 P 1 ANPs is optimized at 0.02 eV, an almost ideal value, even surpassing that of the benchmark metallic platinum catalyst. As a result, the PtNiP ANPs exhibited superior activity in electrocatalytic hydrogen evolution in acid electrolyte (η 10 ∼ 14 mV, Tafel slope ∼ 18 mV dec –1 , and mass activity 5× higher than state-of-the-art Pt/C). Life-cycle assessment and technoeconomic analysis suggest that, compared to existing processes, our approach enables notable reductions in greenhouse gas emission, energy consumption, and production cost for practical electrolyzer catalyst manufacturing.

36 MATERIALS SCIENCE↗

Flash healing of laser-induced graphene

The advancement of laser-induced graphene (LIG) technology has streamlined the fabrications of flexible graphene devices. However, the ultrafast kinetics triggered by laser irradiation generates intrinsic amorphous characteristics, leading to high resistivity and compromised performance in electronic devices. Healing graphene defects in specific patterns is technologically challenging by conventional methods. Herein, we report the rapid rectification of LIG’s topological defects by flash Joule heating in milliseconds (referred to as F-LIG), whilst preserving its overall structure and porosity. The F-LIG exhibits a decreased I D /I G ratio from 0.84 – 0.33 and increased crystalline domain from Raman analysis, coupled with a 5-fold surge in conductivity. Pair distribution function and atomic-resolution imaging delineate a broader-range order of F-LIG with a shorter C-C bond of 1.425 Å. The improved crystallinity and conductivity of F-LIG with excellent flexibility enables its utilization in high-performance soft electronics and low-voltage disinfections. Notably, our F-LIG/polydimethylsiloxane strain sensor exhibits a gauge factor of 129.3 within 10% strain, which outperforms pristine LIG by 800%, showcasing significant potential for human-machine interfaces.

36 MATERIALS SCIENCE↗

Converting plastic waste pyrolysis ash into flash graphene

Pyrolysis of plastic waste (PW), a commercial method of recycling, is currently economically challenging and produces up to 20% by mass valueless pyrolysis ash (PA) as a byproduct. Here, direct, facile upcycling of PW-derived PA into high purity turbostratic flash graphene (tFG) is demonstrated. The tFG displays excellent dispersibility, yielding a concentration of 2.84 mg/mL in aqueous surfactant solution. The tFG was used to fabricate tFG-PVA nanocomposites, and low doses of tFG (0.1%–1%) improve failure strain by 15%–30% when compared to the samples of neat PVA. Furthermore, the addition of tFG to PVA films showed decreased hydrophilic interactions, increasing the water contact angle by 235% and adsorbing 500% less water than neat PVA. The tFG was also added to Portland cement paste as well as concrete, and exhibited 43% and 25% increases in compressive strength, respectively. The tFG is used directly in both composite applications, requiring no purification or chemical functionalization, unlike many other products used in nanocomposites.

54 ENVIRONMENTAL SCIENCES↗

Flash Recycling of Graphite Anodes

The ever-increasing production of commercial lithium-ion batteries (LIBs) will result in a staggering accumulation of waste when they reach their end of life. A closed-loop solution, with effective recycling of spent LIBs, will lessen both the environmental impacts and economic cost of their use. Presently, <5% of spent LIBs are recycled and the regeneration of graphite anodes has, unfortunately, been mostly overlooked despite the considerable cost of battery-grade graphite. Here, in this work, an ultrafast flash recycling method to regenerate the graphite anode is developed and valuable battery metal resources are recovered. Selective Joule heating is applied for only seconds to efficiently decompose the resistive impurities. The generated inorganic salts, including lithium, cobalt, nickel, and manganese, can be easily recollected from the flashed anode waste using diluted acid, specifically 0.1 M HCl. The flash-recycled anode preserves the graphite structure and is coated with a solid-electrolyte-interphase-derived carbon shell, contributing to high initial specific capacity, superior rate performance, and cycling stability, when compared to anode materials recycled using a high-temperature-calcination method. Life-cycle-analysis relative to current graphite production and recycling methods indicate that flash recycling can significantly reduce the total energy consumption and greenhouse gas emission while turning anode recycling into an economically advantageous process.

36 MATERIALS SCIENCE↗

Electrochemical grand potential-based phase-field simulation of electric field-assisted sintering

Here, an electrochemical grand potential functional was proposed to describe the sintering of an ionic ceramic green body. The resultant phase-field description enables simulation of the consolidation of an arbitrary number of granular particles and their interactions with the surrounding void phase. The model includes the effects of charged vacancies and the associated interactions between internal and applied electric fields. Defect segregation to grain boundaries is also accounted for, as well as enhanced interfacial defect mobilities. The model was parameterized for Y 2 O 3 . Simulations of two-particle systems showed that the applied electric field had an increasingly important impact on neck growth as particle size increased. A sudden rapid increase in temperature occurred for larger field strengths, which has been reported to be correlated to the onset of a flash event in flash sintering. Simulations of many particles showed that internal heat generation by Joule heating was localized at particle–particle contacts (grain boundaries), even though their conductivities were lower than nearby internal particle-void interfaces. A percolative path for ionic charge across the green body and the ceramic sintered solid was thus defined, accelerating the Joule heating process as the porosity of the green body is removed.

36 MATERIALS SCIENCE↗

Multicycle flash sintering of cubic Y 2 O 3 -stabilized ZrO 2 : An in situ energy dispersive synchrotron x-ray diffraction study with high temporal resolution

The current induced unit cell volume changes, (111) Bragg peak full width at half maximum (FWHM) and its integrated intensity in 8 % Y 2 O 3 stabilized ZrO 2 (8 %YSZ) solid state electrolyte was monitored during a triple-flash sintering experiment by in situ energy dispersive x-ray diffraction using a polychromatic synchrotron probe (max, photon energy 200 keV) with 2 second temporal resolution. The first spontaneous singularity in the unit cell volume (+0.54 %) was observed at 899 °C under 15 V/mm applied field intensity, which was associated with 13 mA/mm 2 current draw and an increase in density to 97 %. Following anelastic relaxation of the unit cell volume under open circuit conditions, the same applied field was applied twice in a row which resulted in additional induced singularities at 925 °C (+0.48 %) and 944 °C (+0.42 %). A floating baseline, which was above the thermal expansion baseline, was observed from 833 to 969 °C and was attributed to Joule heating. In conclusion, the singularity at 899 °C is associated with a sharp change in (111) FWHM and a 34 % decrease in integrated peak area that was attributed to changes in the distribution of oxygen vacancies and the changes in their concentration as induced by the applied field in the spontaneous transient stage of flash sintering.

36 MATERIALS SCIENCE↗

High Voltage Surge Protection by a Varistor-Filled Air Gap

The electric discharge across a varistor granule filled air gap under a fast-rising voltage pulse was investigated for surge protection applications. The effects of temperature and pressure on the arc and the electrical conduction were analyzed by the characteristic changes in voltage waveforms triggered by a fast-rising high voltage pulse. In addition to the gap size, experimental results show that competing mechanisms among arc conduction, conduction through the varistor granule network, thermionic emission from Joule heating at granule-to-granule contact points, and the magnitude of the switching voltage dictate the maximum surge protection voltage for the filled air gap. Experimental evidence indicated that accumulated degradation was created at small contact points between varistor granules by repetitive assaults from longer duration, high voltage pulses. The uniqueness of using varistor over other dielectric granules in an air gap for surge protection is identified and discussed.

36 MATERIALS SCIENCE↗

Coupling between interfacial charge and mechanical deformation at high temperatures in ceramics. Final report

Basic research, under this project, has led to new fundamental discoveries in the effect of electric field (and temperature) on diffusion kinetics, electroluminescence and electronic conductivity in ceramic materials. For example, yttria stabilized zirconia sinters in just seconds well below 1000°C, while, at the same time, exhibiting a highly non-linear rise in conductivity, and intense electroluminescence. The phenomenon has been shown to occur in nearly all ceramics whether they are ionic or electronic conductors, or insulators. The rise in conductivity leads to Joule heating but in-situ measurements with a platinum standard at APS and Brookhaven (NSLS-II) have shown that the temperatures are much below what would have been needed to sinter in a few seconds. We have explored the hypothesis that huge concentrations of Frenkel pairs of vacancies and interstitials are produced. While these point defects accelerate sintering (by the interstitials being transported to the pores and the vacancies to the grain boundaries), they may also produce electron-hole pairs which can impart high electrical conductivity or recombine to emit photons. Many measurements, including in-situ measurements of lattice expansion are consistent with this hypothesis. However, the energy barrier for generating Frenkels in zirconia for example is much larger than can be expected at temperature and electrical fields in these experiments. Most recent work suggests that short wavelength phonons play a critical role in the genesis of the “flash” phenomenon. For example, the Debye temperature has been shown to be the lower bound for initiating flash. Molecular dynamics simulations have shown that large concentrations of Frenkel pairs can form under the proliferation of “optical” phonons at the edge of the Brillouin zone, that is with a wavelength at or below the lattice parameter. This project has led to the development of new experimental techniques as well as a software hardware interface for process and control and data analysis in real time, with a time scale of less than one second. This approach spells a new paradigm in materials science research. It potential impact on high rate manufacturing is self evident.

36 MATERIALS SCIENCE↗