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At least 361 records · Page 20

Thermodynamic properties of Gd-Bi alloys determined by emf measurements in LiCl-KCl-GdCl 3 electrolyte

Thermodynamic properties of binary Gd-Bi alloys (mole fraction, x Gd = 0.02–0.35) were determined using electromotive force (emf) measurements in molten LiCl-KCl-GdCl 3 electrolyte in complement with structural, microstructural, and thermal characterization. X-ray diffractometry (XRD) and scanning electron microscopy (SEM) identified the phase constituents of Gd-Bi alloys (x Gd = 0.02–0.35) as Bi matrix and GdBi compound. According to differential scanning calorimetry (DSC) measurements up to 1250 K, a eutectic transition [L = Bi + GdBi] was observed at 543 K but the reported peritectic transition [L + GdBi = GdBi 2 ] was not detected, suggesting the absence of the GdBi 2 compound. Based on structural, microstructural, and thermal characterization of Gd-Bi alloys (x Gd = 0.02–0.35), the GdBi 2 compound was not detected, and its thermodynamic stability is questionable. The emf of Gd-Bi alloy (x Gd = 0.16) at 700–1048 K relative to Gd(s) was measured by electrodepositing pure Gd metal at 25 K increments. Further, the emf values of Gd-Bi alloys were determined via coulometric titration of Gd into liquid Bi using a two-phase [L + GdBi] alloy as a reference electrode at 773–973 K. The solubility of Gd in liquid Bi was also estimated to be 0.50 mol% (773 K), 0.99 mol% (873 K), and 2.21 mol% (973 K) and the excess partial molar Gibbs energy (Δ$\mathrm{\bar{G}^{ex}_{Gd}}$) of liquid Gd-Bi alloys was as low as 65 kJ mol –1 , indicating strong chemical interactions between Gd and Bi.

36 MATERIALS SCIENCE↗

NASA MSFC Electrostatic Levitator (ESL) Rapid Quench System

Electrostatic levitation, a form of containerless processing, is an important tool in materials research. Levitated specimens are free from contact with a container; therefore, heterogeneous nucleation on container walls is not possible. This allows studies of deeply undercooled melts. Furthermore, studies of high‐temperature, highly reactive materials are also possible. Studies of the solidification and crystallization of undercooled melts is vital to the understanding of microstructure development, particularly the formation of alloys with unique properties by rapid solidification. The NASA Marshall Space Flight Center (MSFC) Electrostatic Levitator (ESL) lab has recently been upgraded to allow for rapid quenching of levitated materials. The ESL Rapid Quench System uses a small crucible‐like vessel that can be partially filled with a low melting point material, such as a Gallium alloy, as a quench medium. An undercooled sample can be dropped into the vessel to rapidly quench the sample. A carousel with nine vessels sits below the bottom electrode assembly. This system allows up to nine rapid quenches before having to break vacuum and remove the vessels. This new Rapid Quench System will allow materials science studies of undercooled materials and new materials development. In this presentation, the system is described and initial results are presented.

SanSoucie, Michael P.↗

Catalyst comprising Pt, Ni, and Cr

Catalysts comprising nanostructured elements comprising microstructured whiskers having an outer surface at least partially covered by a catalyst material comprising at least 90 atomic percent collectively Pt, Ni, and Cr, wherein the Pt is present in a range from 32.4 to 35.8 atomic percent, the Ni is present in a range from 57.7 to 63.7 atomic percent, and the Cr is present in a range from 0.5 to 10.0 atomic percent, and wherein the total atomic percent of Pt, Ni, and Cr equals 100. Catalyst described herein are useful, for example, in fuel cell membrane electrode assemblies.

Steinbach, Andrew J. L.↗

Boosting solid oxide fuel cell performance via electrolyte thickness reduction and cathode infiltration

Increasing the power density and reducing the operating temperature of solid oxide fuel cells (SOFCs) is important for improving commercial viability. Here we discuss two strategies for achieving such improvements in Ni–YSZ supported SOFCs – electrolyte thickness reduction and cathode infiltration. Microstructural and electrochemical results are presented showing the effect of reducing YSZ/GDC electrolyte thickness from 8 to 2.5 μm, and the effect of PrO x infiltration into the LSCF–GDC cathode. Both of these measures are effective, particularly at lower temperatures, leading to an increase in the maximum power density at 650 °C from 0.4 to 0.95 W cm –2 , for example. Electrochemical impedance spectroscopy utilizing subtractive analysis shows that PrO x enhances the cathode charge transfer process. Reducing the electrolyte thickness reduces not only the cell ohmic resistance but also the electrode polarization resistance. Furthermore, the latter effect appears to be an artifact associated with a slight increase in the steam partial pressure at the anode due to minor gas leakage across the thinner electrolyte.

25 ENERGY STORAGE↗

Influence of Annealing on Microstructure, Electrochemical, and Magnetic Properties of Co-Doped SrTiO{sub 3} Nanocubes

Effect of annealing on microstructure, electrochemical, and magnetic properties of Co-doped SrTiO{sub 3} nanocubes obtained by the hydrothermal method was studied. X-ray diffraction (XRD) results of all as-prepared and annealed Co-doped SrTiO{sub 3} samples revealed a cubic perovskite structure with the second phases of SrCO{sub 3} and Co{sub 3}O{sub 4}in as-prepared and annealed SrTi{sub 0.90}Co{sub 0.10}O{sub 3} samples, respectively. Agglomerated nanocubes could be clearly observed in all as-prepared and annealed Co-doped samples by scanning electron microscope (SEM) and transmission electron microscope (TEM). X-ray absorption near edge spectroscopy (XANES) results suggested the presence of Co{sup 2+} cations in as-prepared Co-doped SrTiO{sub 3} samples, while both of Co{sup 2+} and Co{sup 3+} cations were found in annealed Co-doped SrTiO{sub 3} samples. The cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) results of as-prepared and annealed SrTi{sub 1-x}Co{sub x}O{sub 3} (x = 0.05, 0.075 and 0.10) electrodes revealed pseudocapacitor behavior of the Faradaic redox reaction type. The specific capacitance (Csc) was affected by the increase of Co content in all as-prepared and annealed Co-doped SrTiO{sub 3} samples with an excellent cycling stability after 200 cycle test of 97.24% and the highest value of 75.28 F g{sup −1} at 1 A g{sup −1} in an annealed SrTi{sub 0.925}Co{sub 0.075}O{sub 3} electrode. Magnetization measurements at room temperature using vibrating sample magnetometer (VSM) revealed diamagnetic behavior of as-prepared SrTiO{sub 3} sample, whereas paramagnetic behavior was observed in all as-prepared Co-doped SrTiO{sub 3} samples. After annealing, undoped sample exhibited paramagnetic behavior, whereas ferromagnetic behavior was observed in all Co-doped SrTiO{sub 3} samples with the increase of saturation magnetization (M{sub s}) at 10 kOe from 0.58 to 1.63 emu/g and the coercive field (H{sub c}) from 43.71 to 123.87 Oe, suggested to originate from the face-center exchange (FCE) mechanism.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A Superior Carbonate Electrolyte for Stable Cycling Li Metal Batteries Using High Ni Cathode

Li metal batteries pairing Li metal anode with high-nickel layer structured oxide cathode are a promising energy storage technology to achieve high energy density. To obtain long cycling life for Li metal batteries, the electrolyte plays a pivotal role in stabilizing both the Li metal anode and the high-nickel cathode upon electrochemical cycling. Herein, we report a carbonate electrolyte that enables a Li||LiNi 0.8 Mn 0.1 Co 0.1 O 2 pouch cell to achieve a high gravimetric energy density of 366 Wh/kg and unprecedented cycling stability with 80% capacity retention after 335 cycles. Here, the 19 F quantitative nuclear magnetic resonance spectroscopy and interface characterization demonstrate that FEC and LiDFOB can reduce the consumption rate of each other and the electrolyte, form a robust LiF-rich SEI on Li metal anode, and improve the microstructure integrity of the high-nickel cathode.

25 ENERGY STORAGE↗

Spatially varying colloidal phase behavior on multi-dimensional energy landscapes

A method is reported to determine equilibrium concentration profiles and local phase behavior for colloids on multi-dimensional energy landscapes. A general expression is derived based on local particle concentration and osmotic pressure differences that are balanced by forces on colloids due to energy landscape gradients. This analysis is applied to colloidal particles in high frequency AC electric fields within octupolar electrodes, where the energy landscape can be shaped in two dimensions. These results are also directly applicable to any particles having induced dipoles in spatially non-uniform electromagnetic fields. Predictions based on modelling colloids with an effective hard disk equation of state indicate inhomogeneous solid and fluid states coexisting on different shaped energy landscapes including multiple minima. Model predictions show excellent agreement with time-averaged Brownian Dynamic simulations at equilibrium. Findings demonstrate a general approach to understand colloidal phase behavior on energy landscapes due to external fields, which could enable control of colloidal microstructure on morphing energy landscapes and the inverse design of fields to assemble hierarchically structured colloidal materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microscopy Studies of the Catalyst Inks for PEM Fuel Cells

The microstructure of the catalyst layer in proton exchange membrane fuel cells (PEMFC) is one of the key factors that determine fuel cell performance. The ink preparation, including dispersion solvent, mixing time, and mixing power, are among the less reported parameters that would influence the ionomer distribution on the catalyst surface and the continuity of the carbon network. In this work, novel characterization approaches have been used to investigate the effect of the Pt/C catalyst ink preparation conditions on the morphology and structures of the catalyst layer. Microscopy analysis revealed that longer mixing time led to better performing electrode structures than shorter mixing time. The longer mixing time enabled improved continuity of the ionomer network and high porosity in the cathode layer that contributes to improved proton conductivity and mass transport. This has been reflected in performance and durability tests, where the electrode made from a 5-day catalyst ink displayed improved performance compared to the one made from a 3-day ink. Durability studies showed 26% and 43% loss of the initial mass activity for 5 days and 3 days mixing, respectively. Finally, in addition, the catalyst layer prepared with ethylene glycol as the dispersion solvent showed better durability than water/1-propanol based solution.

25 ENERGY STORAGE↗

Roll-to-roll production of catalyst coated membranes for low-temperature electrolyzers

Here we demonstrate a roll-to-roll (R2R) process for direct coating of anode catalyst layers on a polymer electrolyte membrane for low-temperature water electrolysis. To develop this process, we studied catalyst ink formulation, ink-membrane interactions, and coating quality. The catalyst inks were a mixture of iridium oxide (IrO2) and Nafion in a water and alcohol dispersion medium. The type of alcohol (methanol, ethanol, propanols) and water-to-alcohol ratio were varied to determine their influence on membrane swelling, dispersion quality, and coatability. Interactions of the ink dispersion medium with the membrane were characterized using sessile-drop contact-angle measurements. These measurements show that the ratio of water to alcohol has a strong influence on how rapidly the dispersion media is absorbed by the membrane. Rheology of the catalyst inks was measured to understand the microstructure of the catalyst particles in the ink. This analysis found that 1-propanol leads to better dispersion of the IrO2 particles than ethanol. Small-scale coating samples were prepared to understand coating uniformity and formation of irregularities. Subsequently, two water/1-propanol ratios (90:10 and 75:25) were down-selected for large-scale R2R slot die coating. The R2R catalyst-coated membrane (CCM) coating process increased catalyst layer production throughput by over 500x compared to our standard lab-scale spray coating. The CCMs obtained from this process were tested as single-cell membrane electrode assemblies. They exhibited a cell voltage of 1.91 V at a current density of 2 A/cm2, which is comparable to spray-coated CCMs. In conclusion, the work presented here demonstrates a continuous, scalable manufacturing process that eliminates the need for the decal transfer step typically used in CCM production.

42 ENGINEERING↗

Phenolic Resin Derived Hard Carbon Anode for Sodium-Ion Batteries: A Review

Sodium-ion batteries are complementary to lithium-ion batteries for grid-scale energy storage applications due to lower cost, safety, and potential for sustainable supply chains. The past decade has witnessed enormous research efforts in developing hard carbon anode materials for sodium-ion batteries. Phenolic resins have received significant attention as hard carbon precursors due to their high carbon yield, highly cross-linked structure, low cost, mature technology, and excellent electrochemical performance of corresponding hard carbon anode. This Review exclusively highlights the state-of-the-art preparation of hard carbon from phenolic resins, and the electrochemical performance in sodium-ion batteries. Cross-linked resins are prepared from three phenolic monomers (phenol, resorcinol, and phloroglucinol) to produce hard carbon. The effects of carbonization temperature on the microstructure, and electrochemical properties of hard carbon have been summarized here. Hard carbon formation, and sodium storage mechanisms have been briefly outlined. Finally, this Review provides an industrial perspective on hard carbon production at scale.

aromatic compounds↗

Insights into the Effect of Heat Treatment and Carbon Coating on the Electrochemical Behaviors of SiO Anodes for Li-Ion Batteries

The use of SiO as an anode material has attracted significant interest due to its high capacity and long cycling life. Many promising approaches, including structural design and carbon coating at high temperatures, effectively improve its intrinsic low electrical conductivity and poor Coulombic efficiency. However, the “heat treatment process-composition and microstructure-electrochemical properties” relationship of the SiO anode is not fundamentally understood. Here the structure and composition evolution in amorphous SiO and graphene-coated SiO is investigated using different heat-treatment conditions. X-ray absorption near-edge structure techniques are also employed to analyze the surface and bulk composition change during the initial lithiation process, supplemented by physical or chemical characterization and electrochemical testing. Here results reveal the structural transition of SiO during heat treatment, from amorphous to disproportionated hierarchical structure, where the as-formed dielectric exterior SiO 2 shell and interior SiO 2 matrix severely polarizes electrodes, hindering the lithiation process. Carbon coating on SiO effectively restricts the growth of the SiO 2 shell and facilitates charge transfer, leading to improved electrochemical performance. A schematic model is proposed to reveal the relationship between the treatments, the resultant structural evolutions, and corresponding electrochemical behaviors.

36 MATERIALS SCIENCE↗

The effect of high-power transient events on tungsten and tungsten coatings used for radio frequency launcher applications

High-temperature plasma-facing material coatings used for radio frequency (RF) launchers need to be robust enough to survive RF breakdown arcing or other transient events from the plasma (e.g., an edge localized mode) without causing a catastrophic failure of the coating. High-power transient effects are being explored by using an RF-induced vacuum arc to determine the robustness of tungsten coatings made by a variety of manufacturing methods. A 1/4-wavelength resonant section of vacuum transmission line terminated with an open circuit electrode structure with a well-defined electric field (30-60 kV/mm) produces repeatable arcing conditions. The initial focus is on tungsten as a plasma-facing material, including sintered tungsten, tungsten coatings on steel produced via physical vapor deposition (PVD), and functionally graded tungsten/steel coatings deposited by low-pressure plasma-spraying (LPPS). Thin PVD coatings (1-2 microns) fail catastrophically from an arc and result in severe delamination of the coating. The arc-induced damage of thicker coatings, such as those made via LPPS, tend to be restricted to the top few microns of the surface. Arcing often initiates on sharp surface microstructures and causes localized melting of tungsten at the surface of all the materials studied and results in resolidified melt pools with surface cracks. The resolidified surface results in a reduction in overall deuterium retention when exposed to typical RF plasma sheath conditions.

Caughman, John [ORNL] (ORCID:0000000206091164)↗

Electrochemical Control of the Morphology and Functional Properties of Hierarchically Structured, Dendritic Cu Surfaces

Electrodeposited dendritic copper foams have been extensively studied as an electrocatalyst for CO 2 reduction reaction (CO 2 RR). Many parameters, such as dendrite size, porosity, pore size, and crystal faceting, define the hierarchical properties of these structures and their subsequent bubble evolution and CO 2 RR capabilities. Herein, the effects the electrodeposition conditions (potential, pH) have on the resulting crystallinity, microstructure, and macroporosity of the copper foam are studied. These morphological differences and the corresponding effects on electrocatalytic activity are characterized. It is shown that the composition of the electrodeposition bath can have significant effects on the mechanics of bubble formation and detachment at the surface during hydrogen evolution reaction in acidic solutions. Similarly, the electrodeposition conditions for the synthesis of the foam affect the product selectivity during CO 2 RR electrocatalysis. As a result, foams deposited in alkaline electrodeposition solutions show high faradaic efficiency and specificity toward C 2 H 6 , an uncommon product of CO 2 RR, at modest applied potentials (−0.8 V versus reversible hydrogen electrode.

14 SOLAR ENERGY↗

Microstructure-Based Degradation Modeling in Solid Oxide Cells

The presentation is intended for a graduate class in Georgia Southern University taught by Dr. Hayri Sezer on electrochemistry, SOFC and Li ion battery. It summaries NETL's recent works on microstructure-based modeling of degradation in solid oxide cells. It covers the degradation mechanism of Ni coarsening, Ni migration and the build-up of oxygen partial pressure inside the electrolyte. The phase-field models developed for Ni coarsening and migration are reviewed and the results are compared to experiments in literature to examine different diffusion mechanisms (Ni self-diffusion, Ni(OH)2 diffusion in pores and Ni(OH) surface diffusion) and driving forces (Ni(OH)x concentration and Ni-YSZ contact angle change). It also demonstrates the developed model for oxygen partial pressure and shows that the predicted oxygen partial pressure can explain the Ni oxidation in the hydrogen electrode and crack growth on the electrolyte-oxygen electrode interface under certain operating conditions.

nickel coarsening↗

Editors’ Choice—Flooded by Success: On the Role of Electrode Wettability in CO 2 Electrolyzers that Generate Liquid Products

Economic operation of carbon dioxide (CO 2 ) electrolyzers generating liquid products will likely require high reactant conversions and product concentrations, conditions anticipated to challenge existing gas diffusion electrodes (GDEs). Notably, electrode wettability will increase as lower surface tension products (e.g., formic acid, alcohols) are introduced into electrolyte streams, potentially leading to flooding. To understand the hydraulically stable operating envelopes in mixed aqueous-organic liquid domains, we connect intrinsic electrode wettability descriptors to operating parameters such as electrolyte flow rate and current. We first measure contact angles of water-organic product dilutions on polytetrafluoroethylene (PTFE) and graphite surfaces as planar analogues for GDE components. We then use material balances around the reactive gas-liquid-solid interface to calculate product mass fractions as functions of water sweep rate and current. Product composition maps visualize the extent to which changes in cell performance influence capillary pressure, a determinant of GDE saturation. Analyses suggest that formic acid mixtures pose little risk for GDE flooding across a wide range of conditions, but effluents containing <30% alcohol by mass may cause flooding. This study reveals opportunities to integrate microstructural features and oleophobic surface treatments into GDEs to repel aqueous-organic mixtures and expand the window of stable operating conditions.

25 ENERGY STORAGE↗

Multifunctional Utilization of Pitch-Coated Carbon Fibers in Lithium-Based Rechargeable Batteries

This work reports carbon fibers as an electrode material and current collector for dual-carbon and lithium-ion batteries. Here, fully graphitic and semigraphitic carbon fibers undergo anion intercalation beyond 4.5 V versus Li/Li + . Symmetric dual-carbon full cells using a pitch-coated fully graphitic carbon fiber mat as both cathode and anode delivers an energy-density of 276 and 322 Wh kg -1 at 342 W kg -1 power density in the voltage range of 3.0–5.0 and 3.0–5.2 V, respectively. On the other hand, nongraphitic carbon fibers do not exhibit anion intercalation up to 5.2 V and can be used as a current collector. They also possess a larger number of Li + storage sites in their randomly oriented microstructure when used as an anode. A lithium-ion full cell with double carbon-coated C-LiFePO 4 loaded on nongraphitic carbon fiber as a cathode and pitch-coated nongraphitic carbon fiber as an anode exhibits 202.6 and 75.2 Wh kg -1 energy density at power densities of 46.75 W kg -1 and 11.7 kW kg -1 , respectively in 2.0–3.5 V range. This pitch-coated carbon fiber-based battery configuration eliminates the need for metal foils and costly fluorinated binders, lowers overall weight of the cell, and is capable of sustaining mechanical stress and thermal shock.

PF6− intercalation↗

Transition characteristics and electron kinetics in microhollow cathode discharges

We demonstrate the transition characteristics and electron kinetics of microdischarges in a microgap with a cathode having microstructures using two-dimensional particle-in-cell/Monte Carlo collision (2d3v) simulations. It is found that the microdischarge is inside the hollow cavity at lower pressures, forming microhollow cathode discharges (MHCDs), while the dominant discharge moves outside the cavity at higher pressures, locating above the cathode rectangular protrusion tip. The spatial distributions of the microdischarge parameters (e.g., electric potential and electron density) are presented by capturing the transition characteristics. The electron kinetics of the microdischarges are examined based on the moment analysis of the electron Boltzmann equation. The collisional and non-collisional components of the electron power absorption are decomposed, which were seldomly investigated for microdischarges previously. The results provide fundamental insights into MHCD formation with a structured electrode at varying pressure conditions, which could be beneficial for the design and fabrication of microplasma devices in practical applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Control of Ionomer Distribution in Roll-to-Roll Coated Fuel Cell Catalyst Layers

Fuel cell catalyst layers are a complex mixture of catalyst particles and ion-conducting polymers. The performance of catalyst layers is highly dependent on microstructure, which must balance proton and electron conduction with gas transport. As fuel cells transition from the laboratory to industrial production for vehicles and other applications, there is a need to understand how manufacturing processes impact the microstructure and, ultimately, the performance of catalyst layers. In this work, we have focused on the roll-to-roll coating of catalyst layers for proton exchange membrane fuel cells. The catalyst layers are responsible for the electrochemical reactions that enable power production. In these devices the catalyst is commonly a Pt nanoparticle supported on porous carbon blacks. The ion conducting polymer, or ionomer, is typically a perfluorosulfonic acid. The most common being Nafion. To fabricate the catalyst layer, the catalyst particles are dispersed in an ink with the ionomer and cast to form the catalyst layer. Commonly, laboratory samples are prepared using spray coating or hand painting, which effectively coat many thin layers to achieve the desired catalyst layer thickness. This creates catalyst layers with uniform distributions of materials throughout the thickness of the full catalyst layer. In contrast, roll-to-roll methods, like slot die, gravure or screen printing, coat the catalyst layer as a single wet film. As the film dries, ink constituents are able to segregate, leading to a heterogeneous distribution of materials through the thickness of the layer. It is also known that the choice of solvent and drying rate can affect the morphology of the catalyst layer. Thus, there is a need to understand how ink formulation and the drying process influence the distribution of materials and catalyst layer morphology. Here, we have explored the influence of solvent and drying rate on morphology of roll-to-roll coated catalyst layers. We show the development of the Kelvin probe method as a rapid screening technique for qualitative analysis of ionomer distribution. We also utilize nano X-ray computed tomography to visualize electrode structure and to quantify particle-size and pore-size distributions, thickness-dependent ionomer distribution, tortuosity, and effective transport properties. We find that solvent has a strong influence on ionomer distribution, with less of an effect on porosity. Conversely, drying temperature has a strong influence on porosity, but less influence on ionomer distribution. Finally, we utilize in situ fuel cell performance testing and other advanced diagnostics to quantify the impact of catalyst layer properties on fuel cell performance and demonstrate that roll-to-roll coating is capable of coating high performance catalyst layers in multi-meter lengths.

14 SOLAR ENERGY↗