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At least 433 records · Page 24

Electrochemical Recovery of Rare-Earth Elements from Coal Fly Ash Using Ionic Liquids as both Extractant and Electrolyte

Rare-earth elements (REEs) are critical for medical technologies, electronics, and clean energy. Coal fly ash (CFA), a byproduct of coal combustion, offers a promising alternative REE source. However, efficient extraction and separation of REEs from CFA remain challenging due to the complex composition of CFA. This study introduces a sustainable method for REE recovery using a recyclable ionic liquid, betainium bis(trifluoromethylsulfonyl)imide ([Hbet]- [Tf 2 N]), which serves both as the extractant from CFA and as the electrolyte in electrodeposition. In the first stage, [Hbet][Tf 2 N] preferentially extracts REEs from CFA through leaching. In the second stage, the REE-enriched ionic liquid undergoes electrochemical deposition using amperometry techniques, where REEs are reduced and deposited onto the electrode. The deposition experiments were conducted from −0.5 to −2.0 V vs a Pt quasireference electrode in a three-electrode setup comprising titanium as the working electrode and platinum as both the reference and counter electrodes. Varying the applied potential enabled potential-dependent preferential REE deposition. At −0.5 V, neodymium (Nd) showed preferential recovery, reaching 25% with a separation factor of 37 over other REEs. In contrast, applying a more negative potential increased overall deposition, yielding ∼50% Nd recovery and 10−20% recovery for the remaining REEs. After recovery, the ionic liquid was regenerated and reused for a subsequent electrochemical recovery cycle. Overall, this study demonstrates a feasible approach for REE recovery from CFA waste, with potential to enhance resource utilization within the REE supply chain.

coal fly ash↗

Effects of low-frequency voltage on nonlinear standing wave excitation, plasma uniformity, and ion dynamics in dual-frequency asymmetric capacitive discharges

Abstract It is known that in very-high-frequency (VHF) capacitively coupled plasmas, the higher harmonics generated by nonlinear sheath motion can enhance the standing wave effect (SWE), which can lead to center-peaked plasma density profiles. In this work, an improved nonlinear electromagnetic model incorporating a transmission line model, an electron momentum balance model, a bulk plasma model, a collisionless nonlinear numerical sheath model, and an ion Monte-Carlo collision (MCC) model is developed to study the effects of low-frequency (LF) voltage V L on the nonlinear standing wave excitation, plasma uniformity, and ion energy and angular distribution functions (IEDFs and IADFs) in dual-frequency (DF) asymmetric capacitive argon discharges at relatively low pressure of 3 Pa. The plasma diffusion in the radial direction and ion dynamics within the LF oscillating sheath are self-consistently considered. The LF voltage V L at 2 MHz varies from 0 to 700 V while the HF voltage V H at 60 MHz is fixed at 100 V. Simulation results indicate that without the addition of an LF source (i.e. V L = 0 V), there are a considerable number of high-order harmonics with short wavelengths, leading to significant SWE and central peak in the radial plasma density profile. Nevertheless, the high-order harmonic excitations tend to be weakened and merely occur around the phase of the full LF sheath collapse due to a shorter characteristic damping time of the surface waves as V L increases. This, combined with increased surface wavelengths of both the driving frequency and the higher harmonics at a higher V L , leads to suppressed standing waves and improved plasma uniformity. Meanwhile, the simulations show that both the low and the high energy peaks of IEDF move towards higher energies, and the energy peak separation width ΔEbecomes wider with the increase of V L . The IEDF at the radial center of the powered electrode exhibits a broader ΔEthan that at the edge. For the IADF, an increased V L results in more ions incident on the electrode with a smaller deflection angle. Because of a thinner sheath and a higher sheath voltage at the electrode center, the peak value of IADF at the electrode center is greater than that at the edge.

Physics↗

Rapid flow fractionation of particles combining liquid and particulate dielectrophoresis

Rapid, size-based, deposition of particles from liquid suspension is accomplished using a nonuniform electric field created by coplanar microelectrode strips patterned on an insulating substrate. The scheme uses the dielectrophoretic force both to distribute aqueous liquid containing particles and, simultaneously, to separate the particles. Size-based separation is found within nanoliter droplets formed along the structure after voltage removal. Bioparticles or macromolecules of similar size can also be separated based on subtle differences in dielectric property, by controlling the frequency of the AC current supplied to the electrodes.

King, Michael R.↗

Suppressing electrolyte-lithium metal reactivity via Li + -desolvation in uniform nano-porous separator

Lithium reactivity with electrolytes leads to their continuous consumption and dendrite growth, which constitute major obstacles to harnessing the tremendous energy of lithium-metal anode in a reversible manner. Considerable attention has been focused on inhibiting dendrite via interface and electrolyte engineering, while admitting electrolyte-lithium metal reactivity as a thermodynamic inevitability. Here, we report the effective suppression of such reactivity through a nano-porous separator. Calculation assisted by diversified characterizations reveals that the separator partially desolvates Li + in confinement created by its uniform nanopores, and deactivates solvents for electrochemical reduction before Li 0 -deposition occurs. The consequence of such deactivation is realizing dendrite-free lithium-metal electrode, which even retaining its metallic lustre after long-term cycling in both Li-symmetric cell and high-voltage Li-metal battery with LiNi 0.6 Mn 0.2 Co 0.2 O 2 as cathode. The discovery that a nano-structured separator alters both bulk and interfacial behaviors of electrolytes points us toward a new direction to harness lithium-metal as the most promising anode.

25 ENERGY STORAGE↗

Effects of spatiotemporal plasma power distribution on the modeling of ignition kernel evolution in quiescent and turbulent methane/air mixtures

Abstract The present work improves a phenomenological plasma-assisted combustion model by integrating the spatiotemporal distribution of plasma power density, thereby considering the evolution of plasma streamers in the modeling, and subsequently, better predicting the ignition kernel evolution. The improved phenomenological model is validated against experiments representing the plasma discharge and post-discharge ignition kernel evolution. Specifically, the new model demonstrates a more accurate prediction of ultrafast gas heating and O 2 dissociation during the plasma discharge, compared to the original model. In addition, the new model is found to closely match the experimental pressure wave and heated channel profiles post-discharge without the need for tuning the energy deposition (unlike the original model), highlighting its accuracy of post-discharge ignition kernel dynamics. The improved phenomenological model is then employed to investigate ignition kernel evolution for a stoichiometric methane-air discharge across various discharge gap configurations. Simulations reveal a non-uniform temperature and streamer distribution progressing from the electrode tips toward the center, contrasting uniform cylindrical discharges previously described in the original model. Streamer propagation is observed to be faster for larger gaps when maintained at the same average electric field for different discharge gaps. The tendency of smaller gaps to produce detached toroidal ignition kernels is observed, while larger gaps promote cylindrical and attached ignition kernels. Interactions between successive ignition kernels from consecutive discharges varied significantly, with the smallest gap (1 mm) promoting the quenching of the preceding ignition kernel due to the initial kernel–kernel separation. The intermediate gap (2 mm) promotes detached kernel growth. In contrast, in the largest gap (4 mm), kernels consistently combine and expand attached to electrodes. The impact of homogeneous isotropic turbulence is also explored, showing the persistence of ignition kernels early on but eventually quenching due to enhanced radical and heat losses with pronounced turbulence intensity.

Johnson, Praise Noah↗

Reaction–Diffusion Coupling Facilitates the Sequential Precipitation of Metal Ions from Battery Feedstock Solutions

Here, the development of new technologies for chemical separations is urgently needed to meet the surging demand for critical materials that has strained resources and caused environmental challenges. Inspired by the classic Liesegang experiment, we demonstrated the separation of critical metal ions based on the coupling of ion diffusion and precipitation kinetics. For this purpose, a model feedstock solution simulating dissolved battery electrodes was placed on top of a hydrogel loaded with a precipitating agent, namely sodium hydroxide. As the lithium, manganese, cobalt, and nickel ions diffused into the gel, a gradient of precipitates formed along the length of the reactor. Elemental analysis of the spatially distributed precipitates showed the enrichment of nickel near the gel-solution interface, followed by the formation of an almost pure (>96%) manganese product further along the reactor. Optimization experiments revealed that a sodium hydroxide concentration of 10 mM and a gel/solution volume ratio of 2:1 favored efficient separations. The robustness of the method was demonstrated in four out of five feedstock compositions of typically used battery cathodes. Our proof-of-concept experiments present a paradigm for critical materials separations that does not require specialty chemicals, binding agents, membranes, or toxic solvents.

25 ENERGY STORAGE↗

Process intensification for generating and decomposing formic acid, a liquid hydrogen carrier

We preview two processes that facilitate using formic acid (HCOOH) as a liquid hydrogen carrier to store renewably-generated electrical energy and then release it to generate electrical power cleanly for backup or emergency applications. First, we show that simultaneously oxidizing an organic solute (typically a waste stream) can assist the electrochemical synthesis of formic acid by lowering the cell potential. The electrolyser comprises a hybrid 3-chamber PEM stack that reduces CO₂ via a gas-diffusion cathode boosted by the oxidation of aqueous methanol. However, the extent of the boosting needs to be optimized across the whole operation of the cell. Next, we present results from an intensified reactor for decomposing formic acid back into H₂ and CO₂ at elevated pressure so that the H₂ can be used in a fuel cell. The reactor combines three operations: Vaporization of the formic acid, its decomposition, and separation of the product stream. Their close coupling affords energy savings and a compact design that could be mounted on a mobile skid. We briefly discuss the electrode catalyst that facilitates the first process and two thermally activated catalysts (Ir supported on covalent triazine framework and Pd supported on carbon) that enable the second process.

25 ENERGY STORAGE↗

Capacitive Deionization for the Extraction and Recovery of Butyrate

Separation processes underpin chemical manufacturing, energy and fuel production, resource recovery, and water purification. Capacitive deionization (CDI) is an electrochemical separation technique based on electrosorption of charged species from an aqueous solution. This work reports the development and application of CDI for the extraction and recovery of butyrate, a carboxylate anion that is key to bioenergy production, among other applications. Electrosorption of sodium butyrate was evaluated using a bench-scale CDI system with activated carbon cloth electrodes. Applying an external potential (1.2 V) enhanced the adsorption capacity of activated carbon for butyrate by 250%. Reversible electrosorption was also demonstrated by extracting and recovering butyrate at 1.2 and 0 V, respectively. Performance metrics including butyrate adsorption and desorption capacities, adsorption and desorption rates, charge efficiency, energy consumption, and recovery are reported. Furthermore, this study also investigates the long-term operational stability of the system by cycling the cell more than 1000 times using 1.2 and 0 V for charging and discharging, respectively. Subsequent physicochemical characterization indicates increased oxygen content (from similar to 2% to >8%), decreased specific surface area (by similar to 20%), and decreased pore volume (by similar to 20%), attributed to carbon oxidation. Overall, this work informs the design of CDI for organic anion separation and recovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Operation-Induced BiVO4 Surface Reconstruction Modulates Photoelectrochemical Glycerol Photooxidation Stability and Activity

Abstract Operation-induced surface reconstruction of photoelectrodes is underexplored as a path to control stability and performance. We show how adaptive junctions form via surface reconstruction of BiVO4 during glycerol photooxidation and how these surfaces affect electrolyte-dependent kinetics and durability. Preferential V dissolution in both acidic and alkaline media forms a Bi-rich layer. In situ measurements through a dual-working-electrode platform quantify the changes in photovoltage and charge-transfer resistance derived from adaptive junction formation, while enabling quantitative separation of the driving forces for charge separation and interfacial catalysis. The reconstructed surface in acidic media improves hole-transfer kinetics, functions as a glycerol-oxidation catalyst, and imparts photostability. Surface reconstruction in alkaline media exhibits the opposite behavior, impeding hole injection. This instability is mitigated by trace Ni2+ ions, which drive in situ surface activation without cocatalyst pre-deposition. This study shows the significance of surface reconstruction in the design of durable photoelectrodes for applications targeting organic electro-oxidation.

Yang, Jin Wook↗

PC8B-4-X562 fuel cell electrical power supply, operations manual

The PC8B-4 fuel cell electrical power supply is an electrical powerplant designed to convert the chemical reaction of hydrogen and oxygen into electrical energy. It utilizes catalyzed electrodes with a potassium hydroxide electrolyte. The powerplant and test stand control unit are described together with a specifications summary. Separate sections deal with: performance, reactants supply and control, heat removal, water removal instrumentation, operation, and safety considerations.

Source record↗

Capacitors Would Help Protect Against Hypervelocity Impacts

A proposal investigates alternatives to the present bumper method of protecting spacecraft against impacts of meteoroids and orbital debris. The proposed method is based on a British high-voltage-capacitance technique for protecting armored vehicles against shaped-charge warheads. A shield, according to the proposal, would include a bare metal outer layer separated by a gap from an inner metal layer covered with an electrically insulating material. The metal layers would constitute electrodes of a capacitor. A bias potential would be applied between the metal layers. A particle impinging at hypervelocity on the outer metal layer would break apart into a debris cloud that would penetrate the electrical insulation on the inner metal layer. The cloud would form a path along which electric current could flow between the metal layers, thereby causing the capacitor to discharge. With proper design, the discharge current would be large enough to vaporize the particles in the debris cloud to prevent penetration of the spacecraft. The shield design can be mass optimized to be competitive with existing bumper designs. Parametric studies were proposed to determine optimum correction between bias voltage, impacting particle velocity, gap space, and insulating material required to prevent spacecraft penetration.

Edwards, David↗

Development of a Cold-Walled Molten Regolith Electrolysis Reactor for Lunar Oxygen Production

On the lunar surface, production of commodi-ties to support human presence, such as water, food and oxygen, and sustain the growth of a per-manent outpostwill likely require the use oflocal resources. The moon is covered almost entirely withfragmented oxide minerals known as regolithhundreds of meter thick.As a resource, it is rich in oxygen (> 42 wt.%) bound in a solid state with a variety of metals. The molten regolith electrolysis (MRE)reactor is a promising technology for the production of gaseous oxygen from the lunar reg-olithin a simple, single-stepreaction that requires minimalconsumable materials, produces oxygen and metals with high electrical efficiency and high yields from any regolithcomposition.This process involvesmelting regolith to~1600°C then electro-lyzing the molten pool to separate metal and oxy-gen ions that are then collected as liquid metal and gaseous oxygen at the respective electrodes. Lab-scale demonstrations of the MRE technology have previously reliedon external heating sources to bring the entirety of the reactor up to the operating temperaturewhich creates corrosive interfaces be-tween the molten regolith and the containment ma-terial in the reactor, limiting the overall lifespan of a reactor[1]. The Gaseous Lunar Oxygen from Regolith Electrolysis (GaLORE) project is focused on the development of a “cold-walled” or “Joule-heated” reactor design in which an internal heating source is used to selectively melt a pool of regolith between the electrodes of the reactor, leaving a shell of solidified regolith between the molten pool and the containment vessel of the reactor. This next generation reactor concept has been under development as molten oxide electrolysis (MOE) by MIT and Boston Metal for the production of iron from pure ores for terrestrial application [2]. The GaLORE project in engaged in early development of the technology for use with varying lunar regolith compositionsin the lunar environment. Thermal modelling of a proposed cold-walledreac-tor design were used as a scaffold to develop pa-rameters for a feasible reactor shape and size as well as target energy consumption[3]. The current development effort for the cold-walled reactor de-sign will be presented as a trade study of the most promising techniques for melting regolithwithin the constraints imposed by the lunar environment.Heater devices are designed to accommodate lim-ited electrical power availabilityon the moon, a wide range of regolith compositions that may be seen on the moon, limited metals available for re-placing consumed parts,and the low thermal con-ductivity of granular regolith in vacuum.Heater de-vices will be down-selectedbased on performance measurements within the above operationalcon-straints,and selected devices will be integrated into a reactor with electrodes to begin producing oxygen. [1]Sibille,L.,Sadoway, D.R.,Sirk, A., Tripathy,P.,Melendez, O., Standish, E., Dominguez, J. A., Stefanescu, D.M.,Curreri, P.A., Poizeau,S.,2009. “Recent Advancesin Scale-up Development of Molten Regolith Electrolysis for Oxygen Production in support of a Lunar Base.”AIAA 2009-659, 47th AIAA Aerospace Sciences Meeting, 5 -8 January 2009, Orlando, FL. [2] Boston Metal, https://www.boston-metal.com/moe-technology/#moe-process[3]Schreiner, S.S.,Sibille, L., Dominguez, J.A., Hoffman, J.A., 2016. "A parametric sizing model for Molten Regolith Electrolysis reactors to pro-duce oxygen on the Moon." Advances in Space Research 57.,7,1585-1603.

K D Grossman↗

Physical model and experimental validation of a high temperature proton exchange membrane electrochemical hydrogen pump cell for efficient single-stage extraction of low concentration hydrogen gas

There is interest in valorization of existing natural gas infrastructure to facilitate the co-transportation of hydrogen via blending of hydrogen gas initially at limited concentrations of 1–20 vol% H2 and to subsequently extract hydrogen at fuel cell quality standards (SAE J2719/ISO14687-2). High temperature proton exchange membrane electrochemical hydrogen pump (HT-PEM EHP) based on phosphoric acid doped polybenzimidazole (PA-PBI) exhibits good performance at elevated temperatures (>120 °C), which provides desirable tolerance to non-methane natural gas constituents that are problematic for lower temperature based EHP. To better understand the suitability of the HT-PEM EHP for such gas separation processes, a two-dimensional model of EHP based on PA-PBI was developed. The model is validated for several relevant operating conditions and across cells with differing amounts of phosphoric acid content in the electrodes. Operando micro x-ray computed tomography (CT) imaging of an HT-PEM EHP was used to further validate physical parameters and assumptions of the model. The impacts of pressure, relative humidity of the anode feed, and concentration of feed gases on separation performance are investigated. This study shows that a specific energy of separation of 5.1 kWh/kg H2 at a hydrogen recovery factor (HRF) of 50 vol% can be achieved in a single stage with the EHP, producing fuel cell quality hydrogen purity of 99.99 vol% H2 from a 2 vol% H2/CH4 feed blend, while pressurizing the product H2 at a pressure ratio of 1.3 relative to feed pressure.

Stansberry, John M↗

Separation of Single-Walled Carbon Nanotubes with DEP-FFF

A process using a modified dielectrophoresis device separates single-walled carbon nanotubes (SWNTs) according to their polarizability in electric fields. This depends on the size and dielectric constant of individual nanotubes and easily separates metallic from semiconducting nanotubes. Separation by length has also been demonstrated. Partial separation (enrichment) according to bandgap (which is linked to polarizability) has also been shown and can be improved to full separation of individual types of semiconducting SWNTs with better control over operational parameters and the length of SWNT starting material. This process and device can be scaled affordably to generate useful amounts of semiconducting SWNTs for electronic device development and production. In this study, a flow injection dielectrophoresis technique was used with a modified dielectrophoresis device. The length, width, and height of the modified chamber were 28, 2.5, and 0.025 cm, respectively. On the bottom of the chamber, there are two arrays of 50-m-wide, 2-m-thick gold electrodes, which are connected to an AC voltage generator and are alternately arranged so that every electrode is adjacent to two electrodes of the opposite polar. There is an additional plate electrode on the top of the chamber that is negatively biased. During the experiment, a syringe pump constantly pumps in the mobile phase, 1-percent sodium dodecylbenzene sulfonate (SDBS) solution, into the chamber. The frequency and voltage are set to 1 MHz and 10 V peak-to-peak, respectively. About 150 micro-L of SWNTs in 1- percent SDBS decanted solution are injected to the mobile phase through a septum near the entrance of the chamber. The flow rate of the mobile phase is set to 0.02 cu cm/min. The injected SWNTs sample flows through the chamber before it is lead into a fluorescence flow-through cell and collected for further analysis. The flow-through cell has three windows, thus allowing the fluorometer to collect fluorescence spectrum and visible absorption spectrums simultaneously. Dielectrophoresis field-flow fractionation (DEP-FFF) generally depends on interaction of a sedimentation force and DEP force for particle separation, and SWNTs are neutrally buoyant in water. In this innovation, the third electrode was added to create a sedimentation force based on DC electrophoresis. This makes this particular device applicable to separations on any neutrally buoyant particles in solution and a more general process for a broad range of nanomaterials sorting and separations.

Schmidt, Howard K.↗

Fabrication and testing of silver-hydrogen cells

Silver electrodes containing various additives were fabricated and tested in single electrode cells in order to improve the electrochemical utilization of sintered silver cathodes in Ag-H2 aerospace batteries. A standard stack arrangement was used which featured a NASA-developed organic-inorganic separator. All cells were cycled in a regime designed to remove 75% of the cells nominal capacity based on 3.3 gms/AHr Ag utilization. In cases where performance degradation was observed, the main feature mode appeared to be corrosion of either the expanded silver current collector or the connection between the silver electrode and the electrode tab. Promising silver electrodes from single electrode studies were used in the construction of 35 AHr Ag-H2 cells. Two such cells were constructed and installed in heavy walled pressure vessels for testing. Based on the data obtained from all cells tested during the program, four lightweight 35 AHr cells were fabricated. During acceptance testing these cells yielded an average gravimetric energy density of 30 WHr/1b.

Debicarri, D. J.↗

Interfacial Chemistry Involved in Selective Separation of NMC/LMO and LCO/LMO Binary Cathode Materials by Froth Flotation Using Oleic Acid

The variability in cathode compositions within recycled lithium-ion battery (LIB) feedstocks poses a significant challenge to efficient downstream refining processes. This study demonstrates the feasibility of using froth flotation with oleic acid as a collector to selectively separate lithium nickel-manganese-cobalt oxide (NMC) and lithium cobalt oxide (LCO) from lithium manganese oxide (LMO) materials. Laboratory-scale flotation tests achieved an 80% separation efficiency in a single stage, producing a froth product with >90% purity of NMC/LCO at approximately 90% yield. Concurrently, the LMO materials were enriched in the sink product with ∼90% purity and ∼90% yield. This approach was further validated using recycled cathode materials, confirming its applicability to realistic feedstocks. The underlying mechanism governing the selective separation of NMC/LCO from LMO was investigated using ζ-potential measurements, contact angle measurements, bubble-particle attachment experiments, and X-ray photoelectron spectroscopy (XPS) analysis. Both contact angle and bubble-particle attachment results confirmed that oleic acid adsorption rendered NMC and LCO surfaces hydrophobic, thereby enhancing flotation recovery. At pH 5, oleic acid adsorbed preferentially onto NMC and LCO surfaces via electrostatic interactions, while exhibiting minimal adsorption on LMO surfaces. However, separation efficiency deteriorated at higher pH, which was attributed to the co-flotation of LMO materials caused by oleate chemisorption on MnOH + species. This work establishes froth flotation as a viable cathode/cathode separation strategy, providing a low-cost, scalable pathway to preconcentrate and enrich nickel-rich and cobalt-rich cathode active materials from incompatible cathode chemistries for direct recycling or hydrometallurgical processing. Furthermore, this study reveals, for the first time, the mechanism of oleate adsorption on the surface of different cathode materials.

PH↗

Unraveling the Ion Adsorption Kinetics in Microporous Carbon Electrodes: A Multiscale Quantum-Continuum Simulation and Experimental Approach

With the understanding that sorption in porous carbon electrodes is crucial to many environmental and energy technologies, such as capacitive deionization (CDI), supercapacitor energy storage, and activated carbon filters. In each of these examples, a practical model that can describe ion electrosorption kinetics is highly desirable for accelerating material design. Here, we proposed a multiscale model to study the ion electrosorption kinetics in porous carbon electrodes by combining quantum mechanical simulations with continuum approaches. Our model integrates the Butler-Volmer (BV) equation for sorption kinetics and a continuously stirred tank reactor (CSTR) formulation with atomistic calculations of ion hydration and ion-pore interactions based on density functional theory (DFT). We validated our model experimentally by using ion mixtures in a flow-through electrode CDI device and developed an in-line UV absorption system to provide unprecedented resolution of individual ions in the separation process. We showed that the multiscale model captures unexpected experimental phenomena that cannot be explained by the traditional ion electrosorption theory. The proposed multiscale framework provides a viable approach for modeling separation processes in systems where pore sizes and ion hydration effects strongly influence the sorption kinetics, which can be leveraged to explore possible strategies for improving carbon-based and, more broadly, pore-based technologies

36 MATERIALS SCIENCE↗