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At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Water Interplays during Dysprosium Electrodeposition in Pyrrolidinium Ionic Liquid: Deconvoluting the Pros and Cons for Rare Earth Metallization

The electrochemical production of rare earth metals (REMs) in ionic liquids (ILs) has received much attention as a promising, sustainable and replacement to the molten salt electrolysis. Water additives have been recently suggested as a strategy to overcome the limitations of the ionic liquid process, but without complete assessment of its overall viability for the REMs production. In this regard, a full investigation of water impact on dysprosium (Dy) electrodeposition in pyrrolidinium triflate (BMPyOTf) ionic liquid was carried out. Water introduction was revealed to involve an interplay of implications on the electrodeposition process, including coordination, speciation, reduction pathways, interfacial dynamics, nucleation and metal stability and purity. In highly dry conditions, the reduction occurs at very negative potentials (-3.3V) in a consecutive pathway, resulting in negligible metal electrodeposition (low rate and efficiency) at the electrode surface. Initial water introduction (<30% molar fraction) leads to partitioning of the Dy complex between water and IL coordinated speciation, giving rise to an additional wave at more positive potentials (-2.4V). Probing and quantification of the heterogeneous Dy speciation by spectroscopic analyses enabled the uncovering of the reduction mechanism and accurate evaluation of the mass transport properties. While lowering the reduction thermodynamics, water addition also improved the nucleation, deposition rate and faradaic efficiency. In spite of these benefits, stripping voltammetric analysis also indicated substantial chemical reactivity of the deposited Dy metal with water additives and/or electrolyte components, under extended timescales. Surface characterization of the obtained product confirmed limited Dy metal stability (mostly oxidized/fluorinated) and purity (~60%) in the studied system. Moreover, high water introduction (>30% molar fraction) was shown to trigger a fast hydrogen evolution reaction (HER), downgrading the robustness of system efficiency. We report the overall impact of water additives seems to engender both promoting and mitigating effects on the Dy electrodeposition process, making the case for more innovative strategies to be sought.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Chemical Compensation Challenges in Processing Antiferroelectric PbZrO 3 Thin Films

The electric field-induced antipolar-to-polar phase transition in antiferroelectric materials is accompanied by large changes in the structural and functional response, making them attractive for many applications ranging from pulsed energy capacitors to high-strain-high (blocking-)force actuators, solid-state heating and cooling systems, and optoelectronic devices. PbZrO 3 , as an end member of the PZT, (x)PbZr 1–x Ti x O 3 , solid solution, has been the subject of many studies. However, processing of perovskite PbZrO 3 is extremely challenging due to phase instabilities induced by Pb loss at the temperatures necessary for perovskite crystallization. Here, we discuss the challenges associated with Pb loss, as well as its compensation through bulk Pb overstoichiometry and interfacial PbO additions, in chemical solution processed, highly oriented PbZrO 3 thin films. For both 042 o - and 001 o -oriented (o-orthorhombic distortion) PbZrO 3 thin films, the crystallization interfaces are the most important contributors to Pb loss and off-stoichiometric outcomes, and no single approach was sufficient to address these challenges. Pb-rich and Pb-deficient nonperovskite phases including ZrO x were only observable through microscopic characterization, and X-ray diffraction alone could not rule out the presence of such secondary phases. “Ideal” macroscopic antiferroelectric polarization-electric field double hysteresis curves were observed despite (at times) the large presence of secondary phases. However, reduced saturation polarization and increased phase transition electric fields were observed concomitantly with the presence of secondary phase(s) and tentatively assigned to the voltage drop across the ZrO x nanocrystals. Based on these results, it is imperative that the presence of secondary phases always be addressed (beyond X-ray diffraction spectra) in order to correctly evaluate the properties of antiferroelectric films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1978

Effects of ultrathin oxides in conducting MIS structures on GaAs

Schottky barrier-type GaAs baseline devices (semiconductor surface etched and then immediately metalized) and GaAs conducting metal oxide-semiconductor devices are fabricated and characterized. The baseline surfaces (no purposeful oxide) are prepared by a basic or an acidic etch, while the surface for the MIS devices are prepared by oxidizing after the etch step. The metallizations used are thin-film Au, Ag, Pd, and Al. It is shown that the introduction of purposeful oxide into these Schottky barrier-type structures examined on n-type GaAs modifies the barrier formation, and that thin interfacial layers can modify barrier formation through trapping and perhaps chemical reactions. For Au- and Pd-devices, enhanced photovoltaic performance of the MIS configuration is due to increased barrier height.

Childs, R. B.↗
NASA NTRS1995

Thermoelastic Theory for the Response of Materials Functionally Graded in Two Directions with Applications to the Free-Edge Problem

A recently developed micromechanical theory for the thermoelastic response of functionally graded composites with nonuniform fiber spacing in the through-thickness direction is further extended to enable analysis of material architectures characterized by arbitrarily nonuniform fiber spacing in two directions. In contrast to currently employed micromechanical approaches applied to functionally graded materials, which decouple the local and global effects by assuming the existence of a representative volume element at every point within the composite, the new theory explicitly couples the local and global effects. The analytical development is based on volumetric averaging of the various field quantities, together with imposition of boundary and interfacial conditions in an average sense. Results are presented that illustrate the capability of the derived theory to capture local stress gradients at the free edge of a laminated composite plate due to the application of a uniform temperature change. It is further shown that it is possible to reduce the magnitude of these stress concentrations by a proper management of the microstructure of the composite plies near the free edge. Thus by an appropriate tailoring of the microstructure it is possible to reduce or prevent the likelihood of delamination at free edges of standard composite laminates.

Aboudi, Jacob↗
DOE OSTI2022

Relation between interfacial shear and friction force in 2D materials

Understanding the interfacial properties between an atomic layer and its substrate is of key interest at both the fundamental and technological levels. From Fermi level pinning to strain engineering and superlubricity, the interaction between a single atomic layer and its substrate governs electronic, mechanical and chemical properties. Here, we measure the hardly accessible interfacial transverse shear modulus of an atomic layer on a substrate. By performing measurements on bulk graphite, and on epitaxial graphene films on SiC with different stacking orders and twisting, as well as in the presence of intercalated hydrogen, we find that the interfacial transverse shear modulus is critically controlled by the stacking order and the atomic layer–substrate interaction. Importantly, we demonstrate that this modulus is a pivotal measurable property to control and predict sliding friction in supported two-dimensional materials. The experiments demonstrate a reciprocal relationship between friction force per unit contact area and interfacial shear modulus. As a result, the same relationship emerges from simulations with simple friction models, where the atomic layer– substrate interaction controls the shear stiffness and therefore the resulting friction dissipation.

36 MATERIALS SCIENCE↗
NASA NTRS1989

The application of electrochemical impedance spectroscopy for characterizing the degradation of Ni(OH)2/NiOOH electrodes

Electrochemical impedance spectra of rolled and bonded and sintered porous nickel battery electrodes were recorded periodically during charge/discharge cycling in concentrated KOH solution at various temperatures. A transmission line model (TLM) was adopted to represent the impedance of the porous electrodes, and various model parameters were adjusted in a curve fitting routine to reproduce the experimental impedances. Degradation processes for rolled and bonded electrodes were deduced from changes in model parameters with electrode cycling time. In developing the TLM, impedance spectra of planar (non-porous) electrodes were used to represent the pore wall and backing plate interfacial impedances. These data were measured over a range of potentials and temperatures, and an equivalent circuit model was adopted to represent the planar electrode data. Cyclic voltammetry was used to study the characteristics of the oxygen evolution reaction on planar nickel electrodes during charging, since oxygen evolution can affect battery electrode charging efficiency and ultimately electrode cycle life if the overpotential for oxygen evolution is sufficiently low. Transmission line modeling results suggest that porous rolled and bonded nickel electrodes undergo restructuring during charge/discharge cycling prior to failure.

Macdonald, D. D.↗
DOE OSTI2025

Evaluating the bond strength and fracture mechanisms of cold-sprayed zinc coating on AZ91 magnesium substrate via a combined experimental and computational approach

Magnesium (Mg) alloys are ideal candidates for automotive applications due to their high strength to weight ratio, castability, recyclability etc., however, they lack corrosion and oxidation resistance. Solid-state deposition techniques, such as cold spray, have been demonstrated to enhance their corrosion resistance as it relies on the severe plastic deformation of powder particles upon impact with the substrate to form a metallurgical bond with the substrate and within the coating. At cold sprayed interfaces, a heterogeneous microstructure is formed that includes some porosity, oxides and intermetallics which can significantly affect coating performance. Thus, establishing a direct correlation between the interface microstructure and its properties can aid in designing optimal cold spray parameters. In this study, we investigated the microstructure and mechanical properties of a zinc (Zn) coating deposited on a high pressure die cast (HPDC) AZ91 Mg substrate via high resolution scanning transmission electron microscopy, in situ micro-tensile testing, and finite element method (FEM) modeling. Micro-tensile pillars fabricated using the plasma focused ion beam (PFIB) successfully isolates the coating-substrate interface within the gauge length. The average bond strength of Zn-Mg interface was determined to be ∼140 MPa with failure occurring partially at the interface and mostly into the coatings. A detailed microstructural characterization revealed evidence of a strong metallurgical bonding at the Zn-Mg interface and formation of the C14 MgZn 2 laves phase interlayer resulting in a mixed mode of fracture during the micro-tensile experiments. FEM modeling reveals the stress distribution along the interfaces and suggests that a MgZn 2 layer thickness between 200–400 nm is optimum to increase the bond strength and minimize the triaxiality. Such a site-specific interfacial analysis with correlative computational modeling provides crucial insight into the overall performance of cold spray interfaces.

Bond strength↗
DOE OSTI2020

A transmission electron microscopy study of dislocation propagation and filtering in highly mismatched GaSb/GaAs heteroepitaxy

Monolithic integration of lattice-mismatched semiconductor materials opens up access to a wide range of bandgaps and new device functionalities. However, it is inevitably accompanied by defect formation. A thorough analysis of how these defects propagate and interact with interfaces is critical to understanding their effects on device parameters. In this study, we present a comprehensive study of dislocation networks in the GaSb/GaAs heteroepitaxial system using transmission electron microscopy (TEM). Specifically, the sample analyzed is a GaSb film grown on GaAs using dislocation–reduction strategies such as interfacial misfit array formation and introduction of a dislocation filtering layer. Using various TEM techniques, it is shown that such an analysis can reveal important information on the dislocation behavior including filtering mechanism, types of dislocation reactions, and other interactions with interfaces. A novel method that enables plan-view imaging of deeply embedded interfaces using TEM and a demonstration of independent imaging of different dislocation types are also presented. While clearly effective in characterizing dislocation behavior in GaSb/GaAs, we believe that the methods outlined in this article can be extended to study other heteroepitaxial material systems.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Moisture Stability of Sulfide Solid-State Electrolytes

In this report we detail a comprehensive study on the moisture stability of sulfide solid-state electrolytes in dry room environments. Although sulfide SSEs have many favorable attributes, this class of materials suffers from poor stability with water. Sulfide SSEs react with water to form gaseous H 2 S and a variety of solid byproducts like Li 3 PO 4 and LiOH, which go on to increase the interfacial impedance of solid-state batteries. Lab-scale research typically utilizes gloveboxes with <1 ppm water, however, the large-scale manufacturing of Li-ion batteries occurs in –40°C dewpoint dry rooms with around 126 ppm water. Consequently, the moisture stability of sulfide SSEs must be addressed if the manufacture of solid-state batteries based on sulfide SSEs is to be scaled up. Here, we are the first to characterize the moisture stability of sulfide SSEs according to both H 2 S and the degradation of ionic conductivity at different moisture setpoints ranging from –76°C to –40°C dewpoint. A variety of different SSE compositions are studied; namely, (Li 2 S) 75 (P 2 S 5 ) 25 , (Li 2 S) 70 (P 2 S 5 ) 30 , (Li 2 O) 7 (Li 2 S) 68 (P 2 S 5 ) 25 , (Li 2 O) 7 (Li 2 S) 63 (P 2 S 5 ) 30 , and (Li 2 S) 75 (P 2 S 5 ) 25 + 20 mol% LiI. We find that moisture stability improves with 75 mol% Li2S modifier content and the introduction of a Li 2 O co-modifier. After a 30 min exposure in a –40°C dewpoint dry room environment we found that (Li 2 S) 75 (P 2 S 5 ) 25 + 20 mol% LiI powder generated 0.1 cc/g H 2 S and its ionic conductivity decreased by over 50%. However, when SSE powder was exposed as a slurry in a dodecane carrier the same SSE composition generated 0 cc/g H 2 S and its ionic conductivity only dropped by 14%. Our results show that sulfide SSEs have acceptable moisture stability when appropriately processed in a dry room environment.

25 ENERGY STORAGE↗
NASA NTRS1990

Thermal buoyancy and Marangoni convection in a two fluid layered system - A numerical study

Thermal buoyancy and surface tension driven convection is numerically investigated in a system with two, immiscible fluids. The geometry investigated, has an open cavity configuration with the lighter fluid situated on top of the heavier fluid, forming a stable layered system. The upper fluid meniscus and the interface are assumed to be flat and undeformable in the calculations. The governing equations and boundary/interface conditions are solved by a control volume based finite difference scheme for two pairs of immiscible fluids; the water-hexadecane system and a so called generic system. The steady state calculations show, that dramatically different flows are predicted when the interfacial tension effects are included or excluded from the system model. These differences are particularly appreciable in surface tension dominated flows, that are typical of microgravity situations. Complex flow patterns, with induced secondary flows are noticed in both the fluids. In general, the overall system heat transfer is found to increase with increases in the thermal buoyancy and surface tension effects, but the behavior of the system flow and thermal fields is not easy to characterize, when different combinations of these forces are considered.

Ramachandran, N.↗
DOE OSTI2023

Bimetallic-Derived Catalytic Structures for CO 2 -Assisted Ethane Activation

In recent years, the simultaneous upgrading of CO 2 and ethane has emerged as a promising approach for generating valuable gaseous (CO, H 2 , and ethylene) and liquid (aromatics and C 3 oxygenates) chemicals from the greenhouse gas CO 2 and large-reserved shale gas. The key challenges for controlling product selectivity lie in the selective C-H and C-C bond cleavage of ethane with the assistance of CO 2 . Bimetallic-derived catalysts likely undergo alloying or oxygen-induced segregation under reaction conditions, thus providing diverse types of interfacial sites, e.g., metal/support (M/M'O x ) interface and metal oxide/metal (M'O x /M) inverse interface, that are beneficial for selective CO 2 -assisted ethane upgrading. The alloying extent can be initially predicted by cohesive energy and atomic radius (or Wigner-Seitz radius), while the preference for segregation to form the on-top suboxide can be approximated using the work function, electronegativity, and binding strength of adsorbed oxygen. Furthermore, bimetallic-derived catalysts are typically supported on high surface area oxides. Modifying the reducibility and acidity/basicity of the oxide supports and introducing surface defects facilitate CO 2 activation and oxygen supplies for ethane activation. Using in situ synchrotron characterization and density functional theory (DFT) calculations, we found that the electronic properties of oxygen species influence the selective cleavage of C-H/C-C bonds in ethane, with electron-deficient oxygen over the metal (or alloy) surface promoting nonselective bond scission to produce syngas and electron-enriched oxygen over the metal oxide/metal interface enhancing selective C-H scission to yield ethylene. Here, we further demonstrate that the preferred structures of the catalyst surfaces, either alloy surfaces or metal oxide/metal inverse interfaces, can be controlled through the appropriate choice of metal combinations and their atomic ratios. Through a comprehensive comparison of experimental results and DFT calculations, the selectivity of C-C/C-H bond scission is correlated with the thermodynamically favorable bimetallic-derived structures (i.e., alloy surfaces or metal oxide/metal inverse interfaces) under reaction conditions over a wide range of bimetallic catalysts. These findings not only offer structural and mechanistic insights into bimetallic-derived catalysts but also provide design principles for selective catalysts for CO 2 -assisted activation of ethane and other light alkanes. This Account concludes by discussing challenges and opportunities in designing advanced bimetallic-derived catalysts, incorporating new reaction chemistries for other products, employing precise synthesis strategies for well-defined structures with optimized site densities, and leveraging time/spatial/energy-resolved in situ spectroscopy/scattering/microscopy techniques for comprehensive structural analysis. The research methodologies established here are helpful for the investigation of dynamic alloy and interfacial structures and should inspire more efforts toward the simultaneous upgrading of CO 2 and shale gas.

03 NATURAL GAS↗
DOE OSTI2020

New Synthesis Strategies to Improve Co-Free LiNi0.5Mn0.5O2 Cathodes: Early Transition Metal d0 Dopants and Manganese Pyrophosphate Coating

In this work, we report solution-based doping and coating strategies to improve the electrochemical performance of the Co-free layered oxide cathode LiNi0.5Mn0.5O2 (LNMO). Small amounts of d0 dopants (e.g., Mo6+and Ti4+, 0.5-1 at. %) increase the cathode’s specific capacity, cycling stability, and rate capability. More specifically, a Mo-doped cathode with the nominal composition LiNi0.495Mn0.495Mo0.01O2 achieves a high reversible capacity of 180 mAh/g at 20 mA/g with good retention at higher rates (e.g., 120 mAh/g at 100 mA/g). Effects of 1 at.% Mo dopant on the cathode structure were studied using a suite of characterization tools including X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy (TEM). These measurements demonstrate that Mo6+ reduces Li+/Ni2+cation mixing and mitigates undesirable phase transformations near the cathode surface during cycling. This work also reports the use of an inorganic Mn2P2O7 coating which enhances cycling stability, presumably through formation of a stable cathode electrolyte interphase (CEI) layer. Overall, the synthesis approaches reported herein are quite general and can potentially be expanded to other high voltage LIB cathodes.

Co-free cathodes, d0 cation, pyrophosphate coating↗
DOE OSTI2022

Emergent phenomena at oxide interfaces studied with standing-wave photoelectron spectroscopy

Emergent phenomena at complex-oxide interfaces have become a vibrant field of study in the past two decades due to the rich physics and a wide range of possibilities for creating new states of matter and novel functionalities for potential devices. The electronic-structural characterization of such phenomena presents a unique challenge due to the lack of direct yet nondestructive techniques for probing buried layers and interfaces with the required Ångstrom-level resolution, as well as element and orbital specificity. In this Review, we survey several recent studies wherein soft x-ray standing-wave photoelectron spectroscopy—a relatively newly developed technique—is used to investigate buried oxide interfaces exhibiting emergent phenomena such as metal-insulator transition, interfacial ferromagnetism, and two-dimensional electron gas. The advantages, challenges, and future applications of this methodology are also discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Direct quantification of ion composition and mobility in organic mixed ionic-electronic conductors

Ion transport in organic mixed ionic-electronic conductors (OMIECs) is crucial due to its direct impact on device response time and operating mechanisms but is often assessed indirectly or necessitates extra assumptions. Operando x-ray fluorescence (XRF) is a powerful, direct probe for elemental characterization of bulk OMIECs and was used to directly quantify ion composition and mobility in a model OMIEC, poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS), during device operation. The first cycle revealed slow electrowetting and cation-proton exchange. Subsequent cycles showed rapid response with minor cation fluctuation (~5%). Comparison with optical-tracked electrochromic fronts revealed mesoscale structure–dependent proton transport. The calculated effective ion mobility demonstrated thickness-dependent behavior, emphasizing an interfacial ion transport pathway with a higher mobile ion density. The decoupling of interfacial effects on bulk ion mobility and the decoupling of cation and proton migration elucidate ion transport in conventional and emerging OMIEC-based devices and has broader implications for other ionic conductors writ large.

42 ENGINEERING↗
DOE OSTI2022

Comprehensive Characterization of Multi-Phase Sulfurized Polyacrylonitrile Cathodes for Lithium-Sulfur Batteries

Sulfurized polyacrylonitrile (SPAN) is considered one of the most promising cathode materials to overcome the operational challenges that plague lithium-sulfur (Li-S) batteries. However, material properties and electrochemical performance implications of SPAN prepared under different synthesis conditions are not yet fully investigated. In this study, we show the impacts of different synthesis conditions on the formation of sulfur to PAN bonds and redox reaction mechanisms of multi-phase SPAN via comprehensive material and electrochemical characterizations. In-situ Raman analysis was first applied to study the multi-phase SPAN-based Li-S cells. We found that both elemental sulfur and chemically bonded sulfur are present under the synthesis condition of 300 degree C/3 h along with unreacted PAN. The incompletely sulfurized, multi-phase SPAN exhibited an unusually rapid capacity degradation in the resultant Li-S cells, which is attributed to polysulfide formation and continuously growing interfacial impedance in the Li-S cells. On the other hand, SPAN samples prepared under the synthesis condition of 350 degree C/3 h are found completely sulfurized with chemically bonded sulfur to the PAN backbone without the presence of free elemental sulfur. Complete sulfurization of SPAN led to exceptionally stable cycle performance due to excellent reversible redox processes of chemically bonded sulfur with Li+ in the Li-S cells.

DIRECT ENERGY CONVERSION,ENERGY STORAGE↗
DOE OSTI2023

Potential induced degradation in c-Si glass-glass modules after extended damp heat stress

Traditional Glass-Backsheet (GB) photovoltaic (PV) modules have been the industry standard for a long time, but the Glass-Glass (GG) modules are quickly rising in popularity. PV modules installed in hot-humid climates with high string voltages can undergo potential induced degradation (PID). So far, to the best of our knowledge, only fresh modules with strong interfacial adhesion have been investigated for PID. However, in reality, the PV modules have weak interfacial adhesion after a few years of field exposure. Therefore, it is essential to evaluate PV modules with weakened interfaces. In this study, we investigated the PID susceptibility of PV modules with weakened interfaces after subjecting them to 2000 hours of damp heat (DH2000) at 85°C/85% relative humidity (RH) in an accelerated environmental chamber. Fresh GG modules were also stressed for PID to compare with PID degradation of DH-stressed modules. Pre- and post-characterization tests were done before, between, and after each stress method to determine the changes in electrical performance, cell metallization properties, and hotspot properties. It is observed that fresh GG modules showed little/no degradation (less than 1%) in maximum power (Pmax), whereas the GG modules that underwent sequential DH and PID degraded by 11% to 12%. Potential mechanisms for these degradations are also presented. Furthermore, the results presented in this study are critical for the industry, considering that the bifacial modules with GG construction will be dominant in the next 10 years.

14 SOLAR ENERGY↗
DOE OSTI2022

Unusual flat and extended morphology of intercalated Cu under MoS 2

We report a general method was developed to intercalate metals under layered materials through a controlled density of sputtered defects. The method has already been applied to study a range of metals intercalated under graphite, and different types of morphologies were realized. In the current work, we extend the method to the study of intercalation under MoS 2 , noting that work on this system is rather limited. We use Cu as the prototype metal for comparison with Cu intercalation under graphite. Although the growth conditions needed for intercalation under graphite and MoS 2 are similar, the type of intercalated phases is very different. Each Cu island that nucleates on top of MoS 2 during Cu deposition provides material that is transferred below MoS 2 through sputtered defects under the island base; this transfer results in a uniform intercalated Cu “carpet” morphology that extends over the mesoscale. On the contrary, Cu intercalation under graphite results in well separated, compact islands formed by monomer detachment from small Cu islands on top and transfer below through defects far from the islands. The structural techniques (scanning electron microscopy and atomic force microscopy) and spectroscopic techniques (x-ray photoelectron spectroscopy and energy-dispersive spectroscopy) are used for the characterization of the intercalated Cu layer.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗