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At least 109 records · Page 6

Effects of processing conditions on flash sintering of commercial ZrN

Flash sintering (FS) is a potentially rapid and low-cost manufacturing technique for advanced ceramics. There are still many unknowns about ceramic FS, especially for highly conductive high-temperature ceramics (HTC), which often display decreased bulk conductivity with increasing temperature. This study qualitatively characterizes the flash behavior of highly conductive HTC materials using zirconium nitride (ZrN) as an example. The effects of processing parameters (e.g., DC voltage/electrical field strength, voltage ramp rate, post-flash holding time, mechanical pressure, sample milling, and choice of electrode materials) on ZrN flash behavior are also qualitatively studied and linked to samples microstructure and hardness. It is observed that best densification was achieved using 5 min Spex-milled ZrN powder under 25 MPa of applied pressure and constant 8 V DC. The potential mechanism for ZrN FS and the similarity and difference from FS of conventional oxides like YSZ have been proposed based on experimental observations, and the directions for future research are also pointed out.

Flash Sintering↗

Effect of choked flow on terminal characteristics of MPD thrusters

A one-dimensional steady real gas MPD accelerator model based on data for various electrode lengths and anode orifice radii is presented. The model relates the electric field to the boundary conditions in a form that agrees with experiment over parametric variations in current and mass flow. The electric field is sensitive to the formulations and assumptions bound into the analysis, and is useful in the modeling of outflow properties. It is shown that the location of the sonic point in the arc chamber shifts upstream for high current operation, and the relation between terminal voltage and current is demonstrated. Experiments using an anode suggested by the theory yield a thrust efficiency 1.5 times that of the unmodified thruster.

King, D. Q.↗

Quantifying concentration distributions in redox flow batteries with neutron radiography

Abstract The continued advancement of electrochemical technologies requires an increasingly detailed understanding of the microscopic processes that control their performance, inspiring the development of new multi-modal diagnostic techniques. Here, we introduce a neutron imaging approach to enable the quantification of spatial and temporal variations in species concentrations within an operating redox flow cell. Specifically, we leverage the high attenuation of redox-active organic materials (high hydrogen content) and supporting electrolytes (boron-containing) in solution and perform subtractive neutron imaging of active species and supporting electrolyte. To resolve the concentration profiles across the electrodes, we employ an in-plane imaging configuration and correlate the concentration profiles to cell performance with polarization experiments under different operating conditions. Finally, we use time-of-flight neutron imaging to deconvolute concentrations of active species and supporting electrolyte during operation. Using this approach, we evaluate the influence of cell polarity, voltage bias and flow rate on the concentration distribution within the flow cell and correlate these with the macroscopic performance, thus obtaining an unprecedented level of insight into reactive mass transport. Ultimately, this diagnostic technique can be applied to a range of (electro)chemical technologies and may accelerate the development of new materials and reactor designs.

Science & Technology - Other Topics↗

Building the next high voltage dc photogun polarized source for the ILC at JLab

During the ILC Global Design Effort (2007) two 200 kV high voltage photoguns based on an inverted insulator geometry were developed in 2010 and successfully tested at Jefferson Lab (JLab). One of the photoguns has been operated at 130 kV in the CEBAF accelerator for the JLab nuclear physics program. The inverted insulator replaces the electrode support structure, consequently significantly less metal prone to field emission is biased and surfaces contributing to the vacuum load are significantly reduced. Implementing a biased anode, and using a larger laser spot size has made this the state of the art polarized beam source with ~200 C charge lifetime from SSL GaAs photocathodes. However, operating at the design 200 kV voltage has been hindered by field emission at ~190 kV. To reliably operate without field emission requires lengthy conditioning applying 50-100 kV beyond the voltage needed for beam operations, without breakdown or damage to the insulator. Over the past decade, JLab has developed two photoguns with a larger version of the commercial inverted insulators used in the ILC design. One photogun operated at 300 kV for magnetized beam studies, and the concept has been implemented in the BNL polarized photogun. The second photogun has recently been installed in CEBAF to operate at 200 kV field emission free. Higher voltage photoguns help the ILC and CLIC achieve higher bunch charge (2013 TDR), and additionally provide margin for operating with shorter laser pulse length and/or smaller laser spot size (better emittance at higher peak current). Such photogun designs need to reach ~400 kV without breakdown or insulator damage to operate field emission free at > 300 kV. This also allows for direct injection into a SRF booster. JLab submitted a proposal to HEP for developing in partnership with industry an inverted geometry insulator to fit commercial 400 kV cables. This contribution describes JLab experience developing and testing high voltage photoguns, and what is needed to sufficiently condition for voltage levels higher than beam operational voltage.

Hernandez-Garcia, Carlos↗

Pt Nanoparticles on Atomic-Metal-Rich Carbon for Heavy-Duty Fuel Cell Catalysts: Durability Enhancement and Degradation Behavior in Membrane Electrode Assemblies

Proton exchange membrane fuel cells (PEMFCs) are a promising zero-emission power source for heavy-duty vehicles (HDVs). However, long-term durability of up to 25,000 h is challenging because current carbon support, catalyst, membrane, and ionomer developed for traditional light-duty vehicles cannot meet the stringent requirement. Therefore, understanding catalyst degradation mechanisms under the HDV condition is crucial for rationally designing highly active and durable platinum group metal (PGM) catalysts for high-performance membrane electrode assemblies (MEAs). Herein, we report a PGM catalyst consisting of platinum nanoparticles with a high content (40 wt %) on atomic-metal-site (e.g., MnN 4 )-rich carbon support. MEAs with the Pt (40 wt %)/Mn–N–C cathode catalyst achieved significantly enhanced performance and durability, generating 1.41 A cm –2 at 0.7 V under HDV conditions (0.25 mgPt cm –2 and 250 kPa abs pressure) and retaining 1.20 A cm –2 after an extended and accelerated stress test up to 150,000 voltage cycles. Electron microscopy studies indicate that most fine Pt nanoparticles are retained on or/and in the carbon support covered with the ionomer throughout the catalyst layer at the end of life. During the long-term stability test, the observed electrochemical active surface area reduction and performance loss primarily result from Pt depletion in the catalyst layer due to Pt dissolution and redeposition at the interface of the cathode and membrane. Importantly, the first-principle density functional theory calculations further reveal a support entrapment effect of the Mn–N–C, in which the MnN 4 site can specifically adsorb the Pt atom and further retard the Pt dissolution and migration, therefore enhancing long-term MEA durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Voltage Droplet Dispenser Developed

Various techniques have been applied to deploying individual droplets for many applications, such as the study of the combustion of liquid fuels. Isolated droplet studies are useful in that they allow phenomena to be studied under well-controlled and simplified conditions. A high-voltage droplet dispenser has been developed that is extremely effective in dispensing a wide range of droplets. The dispenser is quite unique in that it utilizes a droplet bias voltage, as well as an ionization pulse, to release the droplet. The droplet is deployed from the end of a needle. A flat-tipped, stainless steel needle attached to a syringe dispenses a known value of liquid that hangs on the needle tip. Somewhat below the droplet is an annular ring electrode. A bias voltage, followed by a voltage pulse, is applied to attract the droplet sufficiently to pull it off the needle. The droplet and needle are oppositely charged relative to the annular electrode. The needle is negatively charged, and the annular ring is positively charged.

Eichenberg, Dennis J.↗

Simplified calculation of the area specific impedance for solid-state battery design

Simplified algebraic area specific impedance (ASI) correlations have been developed for solid-state composite battery electrodes made of a single ion conducting electrolyte, conductive additive, and intercalation active material. Two ASI expressions were developed, one for short times ( i.e. , pulsed power operation) and another for the pseudo steady state operation (i.e., sustained discharge for energy estimation). A full electrochemical model based on porous electrode theory was developed to examine the accuracy of the simplified ASI expressions. The simplified expressions agree favorably with full model results over a wide range of parameters (i.e. , electrode thicknesses, electrolyte conductivities, solid-state diffusion coefficients, specific surface areas, etc.) and conditions (i.e. , C-rates, states of charge, and pulse times). Under most conditions, the error between the full model and the correlations is well below 7 %. Higher errors were observed for the pseudo steady state expression at high/ low states of charge where the assumption of uniform reaction distributions loses validity. Here, the short time ASI has higher error at low states of charge due to the nonlinearity of the open circuit voltage equation, which is assumed linear in the formulation of the simplified algebraic expression.

25 ENERGY STORAGE↗

Theoretical Understanding of Effects of Operating Modes on the Performance Durability of Solid Oxide Cells: A Comparison between Potentiostatic and Galvanostatic Operations

In solid oxide cells (SOCs), the choice between galvanostatic (constant current) and potentiostatic (constant voltage) modes does not significantly affect the performance of SOCs as long as the cell components remain unchanged and intact. However, the degradation of cell components, which leads to changes in electrochemical and physical properties of the cell, elevates the importance of the selected operating mode. This paper aims to investigate the effects of galvanostatic and potentiostatic operating modes on the evolving properties of SOCs and their subsequent influence on performance durability. Employing non-equilibrium thermodynamic analysis, a crucial approach for understanding the degradation phenomena within an active electrochemical system, this study aims to provide in-depth insights into how these operating modes affect the longevity and efficacy of SOCs. Key findings include: In cases where oxygen electrode (OE) degradation is accelerated by higher partial pressure of oxygen ( p O 2 ), operating under constant voltage electrolysis can mitigate the high p O 2 at the OE|electrolyte (OE|EL) interface. Conversely, if OE degradation occurs more rapidly under a lower p O 2 , constant current electrolysis is more effective in suppressing degradation by achieving a high p O 2 at the OE|EL interface. For degradation of the fuel electrode (FE) due to higher p O 2 , constant current electrolysis is beneficial for more stable performance, which helps maintain low p O 2 at the FE|EL interface. When FE degradation is accelerated by lower p O 2 , constant voltage electrolysis can avert low p O 2 at the FE|EL interface. In practical scenarios, more complex degradation mechanisms come into play, especially when p O 2 significantly deviates from initial conditions. Degradation in one electrode can influence p O 2 in the other electrode, a phenomenon more pronounced in potentiostatic than in galvanostatic electrolysis.

Electrochemistry↗

The role of oxygen in porous molybdenum electrodes for the alkali metal thermoelectric converter

A model for chemical reactions in porous molybdenum electrodes is presented which is based on thermochemical and kinetic data, known sodium-molybdenum-oxygen chemistry, X-ray diffraction analysis of molybdenum and molybdenum oxide electrodes, and the electrochemical behavior of the cell. Enhanced sodium transport through the electrode in its optimum performance state is found to be due to the high sodium ion conductivity of molten Na2MoO4 in the pores, and the electrical conduction to the molybdenum matrix by Na2Mo3O6. The decline of electrode performance is shown to be due to a combination of loss mechanisms for the Na-Mo-O compounds including reduction at short circuit, disproportionation of Na2Mo3O6 at open circuit, and the evaporation of Na2MoO4 at elevated temperature. It is suggested that operation of the cell at moderate voltage of about 0.5 V corresponding to maximum power may be a more stable condition for the porous electrode than open-circuit stand or short-circuit, where degradation reactions are heightened.

Williams, R. M.↗

Voltage breakdown analyses in anion exchange membrane water electrolysis – the contributions of catalyst layer resistance on overall overpotentials

Despite many recent advances, overpotentials remain high for anion exchange membrane water electrolyzers (AEMWEs). Voltage breakdown analyses (VBA) can help decouple the origins of overpotentials and facilitate design decisions to improve cell performance, but studies investigating how to adapt and apply VBA to AEMWEs are lacking. Specifically, catalyst layer resistances and their contributions to overpotentials are not consistently quantified in water electrolysis and are rarely quantified for AEMWEs. This work presents a systematic methodology for VBA tailored to AEMWEs, including an approach to Tafel analysis in the absence of a reference electrode and under conditions where both the oxygen evolution reaction and hydrogen evolution reaction exhibit significant overpotentials. Catalyst layer resistance contributions are diagnosed via changes in the catalyst layer thickness, transport layer porosity, ionomer content, and electrolyte concentration. In this study, we explain discrepancies between inherent catalytic kinetics and device level performance and identify catalyst layer design strategies to reduce catalyst layer resistances.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermal Control Utilizing an Thermal Control Utilizing an Two-Phase Loop with High Heat Flux Source

The electric field applied in dielectric fluids causes an imbalance in the dissociation-recombination reaction generated free space charges. The generated charges are redistributed by the applied electric field resulting in the heterocharge layers in the Vicinity of the electrodes. Proper design of the electrodes generates net axial flow motion pumping the fluid. The electrohydrodynamic (EHD) conduction pump is a new device that pumps dielectric fluids utilizing heterocharge layers formed by imposition of electrostatic fields. This paper evaluates the experimental performance of a two-phase breadboard thermal control loop consisting of an EHD conduction pump, condenser, pre-heater, high heat flux evaporator (HE), transport lines, and reservoir (accumulator). The generated pressure head and the maximum applicable heat flux are experimentally determined at various applied voltages and sink temperatures. Recovery from dryout condition by increasing the applied voltage to the pump is also demonstrated.

Jeong, Seong-Il↗

Failure Modes in Capacitors When Tested Under a Time-Varying Stress

Steady step surge testing (SSST) is widely applied to screen out potential power-on failures in solid tantalum capacitors. The test simulates the power supply's on and off characteristics. Power-on failure has been the prevalent failure mechanism for solid tantalum capacitors for decoupling applications. On the other hand, the SSST can also be reviewed as an electrically destructive test under a time-varying stress. It consists of rapidly charging the capacitor with incremental voltage increases, through a low resistance in series, until the capacitor under test is electrically shorted. Highly accelerated life testing (HALT) is usually a time-efficient method for determining the failure mechanism in capacitors; however, a destructive test under a time-varying stress like SSST is even more effective. It normally takes days to complete a HALT test, but it only takes minutes for a time-varying stress test to produce failures. The advantage of incorporating specific time-varying stress into a statistical model is significant in providing an alternative life test method for quickly revealing the failure modes in capacitors. In this paper, a time-varying stress has been incorporated into the Weibull model to characterize the failure modes. The SSST circuit and transient conditions to correctly test the capacitors is discussed. Finally, the SSST was applied for testing polymer aluminum capacitors (PA capacitors), Ta capacitors, and multi-layer ceramic capacitors with both precious metal electrode (PME) and base-metal-electrodes (BME). It appears that testing results are directly associated to the dielectric layer breakdown in PA and Ta capacitors and are independent on the capacitor values, the way the capacitors being built, and the manufactures. The testing results also reveal that ceramic capacitors exhibit breakdown voltages more than 20 times the rated voltage, and the breakdown voltages are inverse proportional to the dielectric layer thickness. The possibility of ceramic capacitors in front-end decoupling applications to block the surge noise from a power supply is also discussed.

Liu, David (Donhang)↗

Simulating Discharge Curves of an All-Aqueous TRAB to Identify Pathways for Improving System Performance

Thermally regenerative ammonia batteries (TRABs) are an emerging technology that use low temperature heat (T < 150 °C) to recharge a flow battery that produces electrical power on demand. The all-aqueous copper TRAB can provide high power densities and thermal energy efficiencies relative to other devices that harvest energy from waste heat, but its performance is adversely impacted by the crossover of undesired species through the membrane and lower cell voltages compared to conventional batteries. In this work, we developed a numerical model to simulate discharge curves while accounting for crossover inefficiencies without tracking all electrolyte species through the membrane. The model was able to successfully reproduce discharge curves across a diverse range of battery conditions using a single fitting parameter to account for decay of electrode standard potential due to species crossover with minimal error (< 5%). The model was then used to simulate different design scenarios to estimate changes in energy output from alterations to the aspects of the battery electrolyte chemistry. Results from this study are used to identify pathways for improving future TRAB designs with respect to energy capacity and cost-effectiveness of the technology.

25 ENERGY STORAGE↗

Humidity Testing of PME and BME Ceramic Capacitors with Cracks

Cracks in ceramic capacitors are one of the major causes of failures during operation of electronic systems. Humidity testing has been successfully used for many years to verify the absence of cracks and assure quality of military grade capacitors. Traditionally, only precious metal electrode (PME) capacitors were used in high reliability applications and the existing requirements for humidity testing were developed for this type of parts. With the advance of base metal electrode (BME) capacitors, there is a need for assessment of the applicability of the existing techniques for the new technology capacitors. In this work, variety of different PME and BME capacitors with introduced cracks were tested in humid environments at different voltages and temperatures. Analysis of the test results indicates differences in the behavior and failure mechanisms for BME and PME capacitors and the need for different testing conditions.

reliability↗

Molecular Ionic Composites: A New Class of Polymer Electrolytes to Enable All-Solid-State and High-Voltage Lithium Batteries (Final Project Report for DOE EERE VTO grant EE0008860)

Based on a newly discovered class of solid PE materials, that is, molecular ionic composites (MICs), the major goal of this project is to develop solid-state lithium conductors targeted for use in transportation applications. MICs form a mechanically stiff, electrochemically stable, and thermally stable matrix. Specific objectives include the following: (1) development of robust MIC electrolyte thin films (~ 20 µm) to serve as simultaneous nonflammable separators and dendrite-blocking Li + conductors, (2) electrochemical quantification of key performance metrics including electrolyte stability, interfacial reactions, and suitability/compatibility with a range of electrode materials, and (3) comprehensive investigation of ion transport mechanisms and electrode-electrolyte interfacial reactivity under practical operating conditions using NMR and synchrotron X-ray analyses.

25 ENERGY STORAGE↗

Facile Fabrication of Self‐Assembly Functionalized Polythiophene Hole Transporting Layer for High Performance Perovskite Solar Cells

Abstract Crystallinity and crystal orientation have a predominant impact on a materials’ semiconducting properties, thus it is essential to manipulate the microstructure arrangements for desired semiconducting device performance. Here, ultra‐uniform hole‐transporting material (HTM) by self‐assembling COOH‐functionalized P3HT (P3HT‐COOH) is fabricated, on which near single crystal quality perovskite thin film can be grown. In particular, the self‐assembly approach facilitates the P3HT‐COOH molecules to form an ordered and homogeneous monolayer on top of the indium tin oxide (ITO) electrode facilitate the perovskite crystalline film growth with high quality and preferred orientations. After detailed spectroscopy and device characterizations, it is found that the carboxylic acid anchoring groups can down‐shift the work function and passivate the ITO surface, retarding the interface carrier recombination. As a result, the device made with the self‐assembled HTM show high open‐circuit voltage over 1.10 V and extend the lifetime over 4,300 h when storing at 30% relative humidity. Moreover, the cell works efficiently under much reduced light power, making it useful as power source under dim‐light conditions. The demonstration suggests a new facile way of fabricating monolayer HTM for high efficiency perovskite devices, as well as the interconnecting layer needed for tandem cell.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Self-adhesive ionomers for durable low-temperature anion exchange membrane electrolysis

Low-temperature water electrolysis using an anion conductive polymer electrolyte has several potential advantages over other technologies, however, the fabrication of durable alkaline electrodes remains a challenge. Detachment of catalysts results in the loss of electrochemical surface area. Simple mixtures of ionomer and catalyst can suffer from poor catalyst adhesion because only physical adhesion is used to bind the components together. A family of chemically bonded, self-adherent, hydroxide conducting ionomers were synthesized and tested under alkaline electrolysis conditions with nickel ferrite anode electrocatalysts and platinum-nickel cathode catalyst. The ionomers are based on hydroxide conducting poly(norbornene) polymers used as the solid polymer electrolyte in alkaline fuel cells and electrolyzers. The synthesized terpolymer ionomers have been functionalized to provide pendant sites for covalent chemical bonding of bis(phenyl)-A-diglycidyl ether to the ionomer, catalyst, and porous transport layer. The electrodes show excellent adhesion between the catalyst particles, porous transport layer and ionomer, as determined by adhesion measurements and electrolysis performance. As a result, the AEM electrolyzer had stable voltage performance under high current density (1 A/ cm 2 at 1.83 V (67% voltage efficiency)) for extended time periods (>600 h) without degradation.

08 HYDROGEN↗

Conductivity effects in high-voltage spacecraft insulating materials

Laboratory measurements were performed to assess the influence of various external parameters on the conductivity properties of several typical and potential spacecraft insulating materials in a simulated space environment. The materials tested include Kapton, Teflon, quartz, and polyvinylidene fluoride. The parameters measured comprise sample thickness, temperature, applied voltage, illumination intensity and wavelength, and electron beam energy and current density. All tests were conducted in a vacuum chamber at a pressure of about one millionth Torr both with conventional optically-transparent gold front-surface electrodes and with the front surfaces of the test samples exposed directly to an electron beam. The data presented illustrate some of the complexities in electrical characteristics exhibited by the materials as a result of interactions with various conditions of their environment.

Adamo, R. C.↗