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At least 703 records · Page 39

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.↗

Enhanced photocatalytic performance in atomic layer deposition grown TiO{sub 2} thin films via hydrogen plasma treatment

The authors report the effect of hydrogen plasma treatment on TiO{sub 2} thin films grown by atomic layer deposition as an effective approach for modifying the photoanode materials in order to enhance their photoelectrochemical performance. Hydrogen plasma treated TiO{sub 2} thin films showed an improved absorption in the visible spectrum probably due to surface reduction. XPS analysis confirmed the formation of Ti{sup 3+} states upon plasma treatment. Hydrogen plasma treatment of TiO{sub 2} films enhanced the measured photocurrent densities by a factor of 8 (1 mA/cm{sup 2} at 0.8 V versus normal hydrogen electrode) when compared to untreated TiO{sub 2} (0.12 mA/cm{sup 2}). The enhancement in photocurrent is attributed to the formation of localized electronic states in mid band-gap region, which facilitate efficient separation and transportation of photo excited charge carriers in the UV region of electromagnetic spectrum.

36 MATERIALS SCIENCE↗

Influence of particle size, cycling rate and temperature on the lithiation process of anatase TiO 2

The nature of a phase transition plays an important role in controlling the kinetics of reaction of an electrode material in a lithium-ion battery. The actual phase transition path can be affected by particle size and cycling rate. In this study, we investigated the phase transition process during the electrochemical Li intercalation of anatase TiO 2 as a function of particle size (25 nm and 100 nm), cycling rate (1C, 2C, 5C, 10C, 20C) and temperature (room temperature and 80 °C) by in situ synchrotron X-ray diffraction. The phase transition was found to be affected by the particle size: the 100 nm particles react simultaneously via a conventional nucleation and growth, i.e. two-phase, mechanism, while the 25 nm particles react sequentially via a two-phase mechanism. The Li miscibility gap decreases with increasing cycling rate, yet the phase separation was not suppressed even at a cycle rate of 20C. An increase in temperature from room temperature to 80 °C significantly improves the electrode's electrochemical performance despite undergoing a two-phase reaction. The failure to observe a continuous structural transition from tetragonal TiO 2 to orthorhombic Li 0.5 TiO 2 even at high rates and elevated temperature was attributed to the high energy barrier of a continuous phase transition path.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Electron Microscopy Investigation of Sodiation of Titanium Disulfide Nanoflakes

Two-dimensional (2D) metal sulfides show great promises for their potential applications as electrode materials of sodium ion batteries because of the weak interlayer van der Waals interactions which allow the reversible accommodation and extraction of sodium ions. The sodiation of metal sulfides can undergo a distinct process compared to that of lithiation, which is determined by their metal and structural types. Yet, the structural and morphological evolution during its electrochemical sodiation is still unclear. In this report, we studied the sodiation reaction dynamics of TiS 2 by employing in situ transmission electron microscopy and first-principles calculations. During the sodium ion intercalation process, we observed multiple intermediate phases (phase II, phase Ib, and phase Ia), different from its lithiation counterpart, with varied sodium occupation sites and interlayer stacking sequences. Further insertion of Na ions prompted a multi-step extrusion reaction which led to the phase separation of Ti metal from the Na 2 S matrix, with its 2D morphology expanded to a 3D morphology. In contrast to regular conversion electrodes, TiS 2 still maintained a compacted structure after a full sodiation. Frist-principles calculations reveal that the as-identified phases are thermodynamically preferred at corresponding intercalation/extrusion stages compared to other possible phases. The current work provides the fundamental mechanistic understanding of the sodiation process of 2D transition metal sulfides.

25 ENERGY STORAGE↗

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.↗

Electrocatalytic Reduction of CO 2 at Au Nanoparticle Electrodes: Effects of Interfacial Chemistry on Reduction Behavior

Nanoscale Au electrocatalysts demonstrate the extraordinary ability to reduce CO 2 at low overpotentials with high selectivity to CO. Here, we investigate the role of surface chemistry on CO 2 reduction behavior using Au 25 and 5 nm Au nanoparticles. Onset potentials for CO 2 reduction at Au 25 nanoparticles in Nafion binders are shifted anodically by 190 mV while the hydrogen evolution reaction is shifted cathodically by 300 mV relative to Au foil. The net effect of this beneficial separation in onset potentials is relatively high Faradayic efficiencies for CO (90% at 0.8 V versus RHE) at high current densities. Experimental results show Faradayic efficiencies for CO are greatest using electrodes made with Nafion-immobilized Au 25 nanoparticles. Likewise, CO 2 reduction onset potential shifts are greater for smaller nanoparticles and when Nafion binders are used instead of (sulfonate-free) polyvinylidene fluoride. X-ray photoelectron spectroscopy analysis reveals Au nanoparticles may react with the sulfonates of Nafion binders. Here, the results suggest sulfonate interfaces may alter the binding energies of key species or lead to favorable reconstructions, either of which ultimately results in remarkable improvements in Faradayic efficiencies relative to Au foil electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Hybrid Constant and Oscillatory Field Ion Mobility Analyzer Using Structures for Lossless Ion Manipulations

Here we explore the combination of constant and oscillatory fields applied in a single device to affect the continuous separation and filtering of ions based on their mobilities. The device explored allows confining and manipulating ions utilizing a combination of radio frequency (rf), direct current (DC) fields, and traveling waves (TW) in a structures for lossless ion manipulations (SLIM) module. We have investigated theoretically and experimentally a concept for continuous filtering of ions based on their mobilities where ions are mobility separated and selected by passage through two regions, both of which incorporated combined TW and constant fields providing opposing forces on the ions. The SLIM module was composed of two surfaces with mirror-image arrays of electrodes and had two regions where the different TW and opposing DC fields could be applied. The filtering capabilities are determined by the applied DC gradient and the TW parameters, such as speed, amplitude, and the TW sequence (i.e., the duty cycle of the traveling wave). The effects of different parameters on the sensitivity and the ion mobility (IM) resolution of the device have been investigated. By appropriately choosing the DC gradient and TW parameters for the two sections, it is possible to transmit ions of a selected mobility while filtering out others of both higher and lower mobility. The novel device described here provides a basis for the targeted analysis of compounds based upon the continuous selection of ions according to their mobility and without the need for high electric fields or pulsed injection. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

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↗

Experimental analysis on the effects of DC arc discharges at various flow regimes

This paper addresses the control of the boundary layer on a compression ramp by means of DC electrical arc discharges. The development and realization of the control system are first described and then assessed in the wind tunnel. The objective of the research was to control the supersonic flow using the minimum amount of energy. The array of electrodes was located at the base of a ramp, where a low momentum flow develops. The electrical discharge was generated by a custom designed electronic facility based on high-voltage ignition coils. The slanted tungsten electrodes were insulated by mounting them in a ceramic support. The discharge evolution was studied through high-speed flow visualizations, while electrical measurements at the high-voltage section of the circuitry allowed to estimate the energy release. The development of a high-speed short exposure Schlieren imaging technique, based on a very short duration laser pulse illumination and a double shot CCD camera, allowed to observe the macroscopic effects associated with the arc establishment between the electrodes (glow, sound wave and heat release). Due to the long residence time, the thermal perturbation spread along the streamwise direction. Cross correlation of Schlieren images with short time separation revealed that in supersonic conditions, the discharges led to an overall acceleration of the flow field underneath the oblique shock wave.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

3D Printing of Customized Li‐Ion Batteries with Thick Electrodes

Abstract The growing demand for rechargeable lithium‐ion batteries (LIBs) with higher capacity in customized geometries underscores the need for new battery materials, architectures, and assembly strategies. Here, the design, fabrication, and electrochemical performance of fully 3D printed LIBs composed of thick semisolid electrodes that exhibit high areal capacity are reported. Specifically, semisolid cathode and anode inks, as well as UV curable packaging and separator inks for direct writing of LIBs in arbitrary geometries are created. These fully 3D printed and packaged LIBs, which are encased between two glassy carbon current collectors, deliver an areal capacity of 4.45 mAh cm −2 at a current density of 0.14 mA cm −2 , which is equivalent to 17.3 Ah L −1 . The ability to produce high‐performance LIBs in customized form factors opens new avenues for integrating batteries directly within 3D printed objects.

Wei, Teng‐Sing↗

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↗

Statistical modelling of discharge behavior of atmospheric pressure dielectric barrier discharge

In this work, stochastic behavior of atmospheric pressure dielectric barrier discharge (DBD) has been investigated. The experiment is performed in a DBD reactor consisting of a pair of stainless steel parallel plate electrodes powered by a 50 Hz ac high voltage source. Current pulse amplitude distributions for different space gaps and the time separation between consecutive current pulses are studied. A probability distribution function is proposed to predict the experimental distribution function for the current pulse amplitudes and the occurrence of the transition regime of the pulse distribution. Breakdown voltage at different positions on the dielectric surface is suggested to be stochastic in nature. The simulated results based on the proposed distribution function agreed well with the experimental results and able to predict the regime of transition voltage. This model would be useful for the understanding of stochastic behaviors of DBD and the design of DBD device for effective operation and applications.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Silicone Molding and Lifetime Testing of Peripheral Nerve Interfaces for Neuroprostheses

Implantable peripheral nerve cuffs have a large application in neuroprostheses as they can be used to restore sensation to those with upper limb amputations. Modern day prosthetics, while lessening the pain associated with phantom limb syndrome, have limited fine motor control and do not provide sensory feedback to patients. Sensory feedback with prosthetics requires communication between the nervous system and limbs, and is still a challenge to accomplish with amputees. Establishing this communication between the peripheral nerves in the arm and artificial limbs is vital as prosthetics research aims to provide sensory feedback to amputees. Peripheral nerve cuffs restore sensation by electrically stimulating certain parts of the nerve in order to create feeling in the hand. Cuff electrodes have an advantage over standard electrodes as they have high selective stimulation by bringing the electrical interface close to the neural tissue in order to selectively activate targeted regions of a peripheral nerve. In order to further improve the selective stimulation of these nerve cuffs, there is need for finer spatial resolution among electrodes. One method to achieve a higher spatial resolution is to increase the electrode density on the cuff itself. Microfabrication techniques can be used to achieve this higher electrode density. Using L-Edit, a layout editor, microfabricated peripheral nerve cuffs were designed with a higher electrode density than the current model. This increase in electrode density translates to an increase in spatial resolution by at least one order of magnitude. Microfabricated devices also have two separate components that are necessary to understand before implantation: lifetime of the device and assembly to prevent nerve damage. Silicone molding procedures were optimized so that devices do not damage nerves in vivo, and lifetime testing was performed on test microfabricated devices to determine their lifetime in vivo. Future work of this project would include fabricating some of the designed devices and seeing how they compare to the current cuffs in terms of their electrical performance, lifetime, shape, and mechanical properties.

59 BASIC BIOLOGICAL SCIENCES↗

The electrochemical generation of useful chemical species from lunar materials

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O-containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700-850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Tsai, Kan J.↗

Hall Magnetohydrodynamic Power Generation and Drag Augmentation Using A Coaxial-Electrode Configuration During Hypersonic Entry

For interplanetary missions, a spacecraft must reduce its relative velocity from orbital speeds of multiple kilometers per second to zero in order to safely land on the surface of a planetary body. During this phase known as planetary reentry, the spacecraft undergoes high speed above Mach 5 up to Mach 30. This hyper-sonic flight regime imposes a strong bow shock in front of the vehicle that imparts extreme aerodynamic and thermal effects. In addition, during portions of this regime, a plasma is formed in the post-shock flow-field around the vehicle due to these high temperatures. Interaction between an applied magnetic field with this electrically conductive fluid, or magnetohydrodynamic (MHD) interaction, can be utilized to convert kinetic energy from the flow into storable electrical energy. Onboard MHD energy generation can benefit the spacecraft by increasing the power of active thermal control components and vehicle control systems during reentry. MHD interaction also exerts a Lorentz body force on the plasma flow that can be manipulated to act as an additional drag force through the vehicle body. MHD drag augmentation can benefit the spacecraft with an additional control mechanism that operates without moving parts. This can be utilized at higher altitudes and subsequently reduce convective heat transfer to the vehicle. MHD interaction with plasma flow suggests that both power generation and drag augmentation can be integrated together in one design. Modern numerical studies have only demonstrated the viability and potential of MHD energy generation and drag modulation separately for implementation into future spacecraft designs [1] [2] [3]. Steeves et. al. presented one possible generator design specifically for reentry vehicles that utilized a modular panel with two embedded electromagnets and two extruding electrodes for air plasma to flow between. Fujino et. al. presented results that indicated increased total drag with a permanent magnet embedded in the blunt body of the Orbital Reentry Experiment (OREX) trajectory. Furthermore, experimental investigations of these two MHD applications have been limited and separate due to the difficult technical nature of experimental de-sign and analysis. For MHD energy generation, there have been two designs which used a cylindrical fore-body with two embedded permanent magnets and two outward facing curved electrodes for tangency to an artificially ionized plasma that flowed along the body length [4] [5]. The first design was studied using an air microwave (MW) ionized supersonic plasma wind tunnel and the second design used radio frequency (RF) ionization of Argon, but both physically demonstrated the feasibility of MHD energy generation in reentry plasma conditions. For MHD drag modulation, one study involved a small-scale cylindrical blunt body embedded with permanent magnets immersed in plasma flow in an arcjet tunnel [6], and another utilized a spherical permanent magnet enclosed with a spherical forebody that was evaluated in a shock expansion tunnel [7]. Both experimental studies provided physical evidence of drag augmentation due to MHD interactions. Therefore, because of the multi-faceted effects of MHD along with both applications having been deemed feasible and beneficial during reentry, this indicates that a coupled power generation and drag modulation design could be achievable. The axi-symmetric nature of blunt bodies for reentry suggests that a spherical set of two ring electrodes near the nose along the body axis. Based on first principles, flow along the walls of the spherical body can then produce MHD interactions between the electrodes. As a result, two currents are generated: a Hall current that produces power and a primary inductive current that augments the drag force. The goal of this work is to provide a simulated design of a coaxial-electrode con-figuration for power generation and drag modulation for experimental testing.

E. Leong↗

Ultra-High Resolution Ion Mobility Separations Utilizing Traveling Waves in a 13 m Serpentine Path Length Structures for Lossless Ion Manipulations Module

We report the development and initial evaluation of a 13-m path length Structures for Lossless Manipulations (SLIM) module for achieving high resolution separations using traveling waves (TW) with ion mobility (IM) spectrometry. The TW SLIM module was fabricated using two mirror-image printed circuit boards with appropriately configured RF, DC and TW electrodes and positioned with a 2.75-mm inter-surface gap. Ions were effective confined between the surfaces by RF-generated pseudopotential fields and moved losslessly through a serpentine path including 44 “U” turns using TWs. The ion mobility resolution was characterized at different pressures, gaps between the SLIM surfaces, TW and RF parameters. After initial optimization the SLIM IM-MS module provided about 5-fold higher resolution separations than present commercially available drift tube or traveling wave IM-MS platforms. Peak capacity and peak generation rates achieved were 246 and 370 s-1, respectively, at a TW speed of 148 m/s. The high resolution achieved in the TW SLIM IM-MS enabled e.g., isomeric sugars (Lacto-N-fucopentaose I and Lacto-N-fucopentaose II) to be baseline resolved, and peptides from a albumin tryptic digest much better resolved than with existing commercial IM-MS platforms. The present work also provides a foundation for the development of much higher resolution SLIM devices based upon both considerably longer path lengths and multi-pass designs.

Environmental Molecular Sciences Laboratory↗

Microstructural Analysis of the Effects of Thermal Runaway on Li-Ion and Na-Ion Battery Electrodes

Thermal runaway is a phenomenon that occurs due to self-sustaining reactions within batteries at elevated temperatures resulting in catastrophic failure. Here, the thermal runaway process is studied for a Li-ion and Na-ion pouch cells of similar energy density (10.5 Wh, 12 Wh, respectively) using accelerating rate calorimetry (ARC). Both cells were constructed with a z-fold configuration, with a standard shutdown separator in the Li-ion and a low-cost polypropylene (PP) separator in the Na-ion. Even with the shutdown separator, it is shown that the self-heating rate and rate of thermal runaway in Na-ion cells is significantly slower than that observed in Li-ion systems. The thermal runaway event initiates at a higher temperature in Na-ion cells. The effect of thermal runaway on the architecture of the cells is examined using X-ray microcomputed tomography, and scanning electron microscopy (SEM) is used to examine the failed electrodes of both cells. In conclusion, from examination of the respective electrodes, likely due to the carbonate solvent containing electrolyte, it is suggested that thermal runaway in Na-ion batteries (NIBs) occurs via a similar mechanism to that reported for Li-ion cells.

25 ENERGY STORAGE↗