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Results for “surface stability”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

First-principles study of the surface properties of uranium carbides

Uranium carbides have attracted renewed interest as advanced nuclear fuels for Generation IV reactors. As an important property required for gas bubble modeling in nuclear fuels, the surface energy of uranium carbides is scarce in literature. In this work, we study the surface properties of uranium carbides by first-principles density functional theory calculations. Surface orientations with maximum Miller index up to 3, 2 and 2 are investigated for UC, U 2 C 3 and α-UC 2 , respectively. By studying the effects of surface termination and chemical potential on surface energy, we identify the factors that determines the surface stability. From the calculated surface energies, the surface properties of uranium carbide single crystals are obtained from Wulff construction, including equilibrium morphology, dominant surface orientation and area weighted surface energy.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Chemical stabilization of graphite surfaces

Embodiments of a device, or a component of a device, including a stabilized graphite surface, methods of stabilizing graphite surfaces, and uses for the devices or components are disclosed. The device or component includes a surface comprising graphite, and a plurality of haloaryl ions and/or haloalkyl ions bound to at least a portion of the graphite. The ions may be perhaloaryl ions and/or perhaloalkyl ions. In certain embodiments, the ions are perfluorobenzenesulfonate anions. Embodiments of the device or component including stabilized graphite surfaces may maintain a steady-state oxidation or reduction surface current density after being exposed to continuous oxidation conditions for a period of at least 1-100 hours. The device or component is prepared by exposing a graphite-containing surface to an acidic aqueous solution of the ions under oxidizing conditions. The device or component can be exposed in situ to the solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Fundamental Factors Impacting the Stability of Phosphonate-Derivatized Ruthenium Polypyridyl Sensitizers Adsorbed on Metal Oxide Surfaces

A series of 18 ruthenium(II) polypyridyl complexes were synthesized and evaluated under electrochemically oxidative conditions, which generates the Ru(III) oxidation state and mimics the harsh conditions experienced during the kinetically limited regime that can occur in dye-sensitized solar cells (DSSCs) and dye-sensitized photo-electrosynthesis cells, to further develop fundamental insights into the factors governing molecular sensitizer surface stability in aqueous 0.1 M HClO 4 . Both desorption and oxidatively induced ligand substitution were observed on planar fluorine-doped tin oxide (FTO) electrodes, with a dependence on the E 1/2 Ru(III/II) redox potential dictating the comparative ratios of the processes. Complexes such as RuP4OMe ( E 1/2 = 0.91 vs Ag/AgCl) displayed virtually only desorption, while complexes such as RuPbpz ( E 1/2 > 1.62 V vs Ag/AgCl) displayed only chemical decomposition. Comparing isomers of 4,4'- and 5,5'-disubstituted-2,2'-bipyridine ancillary ligands, a dramatic increase in the rate of desorption of the Ru(III) complexes was observed for the 5,5'-ligands. Nanoscopic indium-doped tin oxide thin films (nanoITO) were also sensitized and analyzed with cyclic voltammetry, UV–vis absorption spectroscopy, and X-ray photoelectron spectroscopy, allowing for further distinction of desorption versus ligand-substitution processes. Desorption loss to bulk solution associated with the planar surface of FTO is essentially non-existent on nanoITO, where both desorption and ligand substitution are shut down with RuP4OMe. Finally, these results revealed that minimizing time spent in the oxidized form, incorporating electron-donating groups, maximizing hydrophobicity, and minimizing molecular bulk near the adsorbed ligand are critical to optimizing the performance of ruthenium(II) polypyridyl complexes in dye-sensitized devices.

14 SOLAR ENERGY↗
DOE OSTI2019

Phase Control on Surface for the Stabilization of High Energy Cathode Materials of Lithium Ion Batteries

The development of high energy electrode materials for lithium ion batteries is challenged by their inherent instabilities, which become more aggravated as the energy densities continue to climb, accordingly causing increasing concerns on battery safety and reliability. Here, taking the high voltage cathode of LiNi 0.5 Mn 1.5 O 4 as an example, we demonstrate a protocol to stabilize this cathode through a systematic phase modulating on its particle surface. We are able to transfer the spinel surface into a 30 nm shell composed of two functional phases including a rock-salt one and a layered one. The former is electrochemically inert for surface stabilization while the latter is designated to provide necessary electrochemical activity. The precise synthesis control enables us to tune the ratio of these two phases, and achieve an optimized balance between improved stability against structural degradation without sacrificing its capacity. This study highlights the critical importance of well-tailored surface phase property for the cathode stabilization of high energy lithium ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2019

Study of Chemical Etching and Chemo-Mechanical Polishing on CdZnTe Nuclear Detectors

Cadmium zinc telluride (CdZnTe) semiconductor has applications in the detection of Xrays and gamma-rays at room temperature without having to use a cooling system. Chemical etching and chemo-mechanical polishing are processes used to smoothen CdZnTe wafer during detector device fabrication. These processes reduce surface damages left after polishing the wafers. In this paper, we compare the effects of etching and chemo-mechanical polishing on CdZnTe nuclear detectors, using a solution of hydrogen bromide in hydrogen peroxide and ethylene glycol mixture. X-ray photoelectron spectroscopy (XPS) was used to monitor TeO 2 on the wafer surfaces. Current-voltage and detector-response measurements were made to study the electrical properties and energy resolution. XPS results showed that the chemical etching process resulted in the formation of more TeO 2 on the detector surfaces compared to chemo-mechanical polishing. The electrical resistivity of the detector is of the order of 10 10 Ω-cm. The chemo-mechanical polishing process increased the leakage current more that chemical etching. For freshly treated surfaces, the etching process is more detrimental to the energy resolution more than chemo-mechanically polishing. The energy resolutions of the CdZnTe wafers are expected to improve as the surfaces stabilize and result in reduced surface currents.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Single-crystal based studies for correlating the properties and high-voltage performance of Li[Ni x Mn y Co 1₋x₋y ]O 2 cathodes

Safe and stable cycling of lithium-ion battery cathodes at high voltages is essential for meeting next-generation energy storage demands, yet the lack of fundamental understanding of the correlation of a material's properties and reactivities largely hinders current progress. Here, we demonstrate how single-crystal samples with well-controlled physical characteristics can be used to unambiguously establish the relationships among specific properties, surface chemistry and electrochemical performance, enabling rational design of better performing cathode materials. Layered Li[Ni x Mn y Co 1₋x₋y ]O 2 (NMC) crystals, with four different particle shapes of an octahedron (Oct), truncated octahedron (T-Oct), polyhedron (Poly) and platelet (Plate), were prepared to vary the presence of (104), (001) and (012) family facets on the surface. This represents the first experimental verification of NMC morphologies that were theoretically calculated in the past. Systematic studies on the impact of isolated physical properties reveal the important roles of the Ni content, particle size and facet on surface stability and electrochemical performance. We show that compared to (012) surface dominated samples, high-voltage cycling stability was much improved on the (001) dominated Plate sample, suggesting that replacing the (012) surface with lower energy (001) and/or (104) surfaces can be effective in stabilizing NMCs during high energy applications. Our study moreover provides insights into how tailoring a material's surface properties can be used as an important route in balancing cathode capacity and stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Determining the oxidation stability of SnSe under atmospheric exposure

Abstract Understanding surface stability becomes critical as 2D materials like SnSe are developed for piezoelectric and optical applications. SnSe thin films deposited by molecular beam epitaxy showed no structural changes after a two-year exposure to atmosphere, as confirmed by X-ray diffraction and Raman spectroscopy. X-ray photoelectron spectroscopy and reflectivity show a stable 3.5 nm surface oxide layer, indicating a self-arresting oxidative process. Resistivity measurements show an electrical response dominated by SnSe post-exposure. This work shows that SnSe films can be used in ambient conditions with minimal risk of long-term degradation, which is critical for the development of piezoelectric or photovoltaic devices. Graphical Abstract

Chin, Jonathan R. (ORCID:0000000273205678)↗
DOE OSTI2017

A comparative study of surface energies and water adsorption on Ce-bastnäsite, La-bastnäsite, and calcite via density functional theory and water adsorption calorimetry

Bastnäsite, a fluoro-carbonate mineral, is the single largest mineral source of light rare earth elements (REE), La, Ce and Nd. Enhancing the efficiency of separation of the mineral from gangue through froth flotation is the first step towards meeting an ever increasing demand for REE. To design and evaluate collector molecules that selectively bind to bastnäsite, a fundamental understanding of the structure and surface properties of bastnäsite is essential. In our earlier work (J Phys Chem C, 2016, 120, 16767), we carried out an extensive study of the structure, surface stability and water adsorption energies of La-bastnäsite. Here in this work, we make a comparative study of the surface properties of Ce-bastnäsite, La-bastnäsite, and calcite using a combination of density functional theory (DFT) and water adsorption calorimetry. Spin polarized DFT+U calculations show that the exchange interaction between the electrons in Ce 4f orbitals is negligible and that these orbitals do not participate in bonding with the oxygen atom of the adsorbed water molecule. In agreement with calorimetry, DFT calculations predict larger surface energies and stronger water adsorption energies on Ce-bastnäsite than on La-bastnäsite. The order of stabilities for stoichiometric surfaces is as follows: [100] > [101] > [102] > [0001] > [112] > [104] and the most favorable adsorption sites for water molecules are the same as for La-bastnäsite. In agreement with water adsorption calorimetry, at low coverage water molecules are strongly stabilized via coordination to the surface Ce3+ ions, whereas at higher coverage they are adsorbed less strongly via hydrogen bonding interaction with the surface anions. Lastly, due to similar water adsorption energies on bastnäsite [101] and calcite [104] surfaces, the design of collector molecules that selectively bind to bastnäsite over calcite must exploit the structural differences in the predominantly exposed facets of these minerals.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Enhancing the Ion Transport in LiMn 1.5 Ni 0.5 O 4 by Altering the Particle Wulff Shape via Anisotropic Surface Segregation

Spontaneous and anisotropic surface segregation of W cations in LiMn 1.5 Ni 0.5 O 4 particles can alter the Wulff shape and improve surface stability, thereby significantly improving the electrochemical performance. An Auger electron nanoprobe was employed to identify the anisotropic surface segregation, whereby W cations prefer to segregate to {110} surface facets to decrease its relative surface energy according to Gibbs adsorption theory and subsequently increase its surface area according to Wulff theory. Consequently, the rate performance is improved (e.g., by ∼5-fold at a high rate of 25C) because the {110} facets have more open channels for fast lithium ion diffusion. Furthermore, X-ray photoelectron spectroscopy (XPS) depth profiling suggested that the surface segregation and partial reduction of W cation inhibit the formation of Mn 3+ on surfaces to improve cycling stability via enhancing the cathode electrolyte interphase (CEI) stability at high charging voltages. Here, this is the first report of using anisotropic surface segregation to thermodynamically control the particle morphology as well as enhancing CEI stability as a facile, and potentially general, method to significantly improve the electrochemical performance of battery electrodes. Combining neutron diffraction, an Auger electron nanoprobe, XPS, and other characterizations, we depict the underlying mechanisms of improved ionic transport and CEI stability in high-voltage LiMn 1.5 Ni 0.5 O 4 spinel materials.

Wulff shape↗
DOE OSTI2016

Geometric stabilization of the electrostatic ion-temperature-gradient driven instability. I. Nearly axisymmetric systems

The effects of a non-axisymmetric (3D) equilibrium magnetic field on the linear ion-temperature-gradient (ITG) driven mode are investigated. We consider the strongly driven, toroidal branch of the instability in a global (on the magnetic surface) setting. Previous studies have focused on particular features of non-axisymmetric systems, such as strong local shear or magnetic ripple, that introduce inhomogeneity in the coordinate along the magnetic field. In contrast, here we include non-axisymmetry explicitly via the dependence of the magnetic drift on the field line label α, i.e., across the magnetic field, but within the magnetic flux surface. We consider the limit where this variation occurs on a scale much larger than that of the ITG mode, and also the case where these scales are similar. Close to axisymmetry, we find that an averaging effect of the magnetic drift on the flux surface causes global (on the surface) stabilization, as compared to the most unstable local mode. In the absence of scale separation, we find destabilization is also possible, but only if a particular resonance occurs between the magnetic drift and the mode, and finite Larmor radius effects are neglected. We discuss the relative importance of surface global effects and known radially global effects.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

In situ ambient pressure XPS study of Pt/Cu(111) single-atom alloy in catalytically relevant reaction conditions

The presence of multiple reactant gases as well as reaction intermediates in a heterogeneous catalytic reaction results in a complex interaction between different components of the catalyst with each gas, which can alter the surface and chemical state of the catalyst differently than in the presence of an individual gas alone. In this study, we used in situ ambient pressure x-ray photoelectron spectroscopy to study the surface state of Pt/Cu(111) single-atom alloy model system in two catalytically relevant reaction conditions: CO 2 hydrogenation and CO oxidation. We found that the activation of CO 2 results in the formation of CO, which adsorbs on Pt sites at up to 400 K. In the presence of CO 2 and H 2 , Pt catalyzes the reverse water–gas shift reaction, which produces more CO and further stabilizes surface Pt atoms at 450 K. On the other hand, in CO oxidation condition, the presence of O 2 results in the formation of a thick Cu 2 O layer at higher temperatures, and Pt atoms are no longer detected in the surface and subsurface layers. When O 2 is introduced to the sample before CO, the formation of a complete Cu 2 O layer that covers all Pt atoms occurs immediately at room temperature. Finally, however, when CO is introduced at room temperature before O 2 , the presence of adsorbed CO on Pt sites stabilizes the surface Pt atoms and prevents the formation of a complete Cu 2 O layer, thus exposing the Pt atoms in 'holes' in the Cu 2 O layer.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Dopant Distribution in Co-Free High-Energy Layered Cathode Materials

The practical implementation of Co-free, LiNiO 2 -derived cathodes has been prohibited by their poor cycle life and thermal stability, concluded from the structural instability, phase transformations, reactive surfaces, and chemomechanical breakdown. With the hierarchical distribution of Mg/Ti dual dopants in LiNiO 2 , we report a Co-free layered oxide that exhibits enhanced bulk and surface stability. Ti shows a gradient distribution and is enriched at the surface, whereas Mg distributes homogeneously throughout the primary particles. The resulting Mg/Ti codoped LiNiO 2 delivers a material-level specific energy of ~780 W h/kg at C/10 with 96% retention after 50 cycles. The specific energy reaches ~680 W h/kg at 1C with 77% retention after 300 cycles. Furthermore, the Mg/Ti dual dopants improve the rate capability, thermal stability, and self-discharge resistance of LiNiO 2 . Our synchrotron X-ray, electron, and electrochemical diagnostics reveal that the Mg/Ti dual dopants mitigate phase transformations, reduce nickel dissolution, and stabilize the cathode–electrolyte interface, thus leading to the favorable battery performance in lithium metal and graphite cells. The current study suggests that engineering the dopant distribution in cathodes may provide an effective path toward lower cost, safer, and higher energy density Co-free lithium batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Dual‐Gradient Construction on Li‐Rich Cathodes for High Stability Lithium Battery

Abstract The practical applications of high‐energy Li‐rich layered oxides (LLOs) have been hindered by the severe performance degradation including voltage decay and capacity fading. The gradient construction toward high‐activity interior and high‐stability exterior, typically realized by gradually changed transition metal (TM) gradient in LLOs, can alleviate the performance degradation to certain degrees. In this study, a gradient design of Al/Mg dopants is demonstrated for the TM‐gradient LLOs to further harmonize the high‐activity interior and high‐stability exterior, thereby forming the dual (TM and doping) gradient. As a result, superior capacity retention of 86% and a minor voltage decay of 0.54 mV cycle −1 are achieved at 1 C after 300 cycles. The improved electrochemical stability of the dual‐gradient LLO is attributed to the enhanced surface stability and suppressed bulk structure degeneration of LLOs upon electrochemical cycling. The dual‐gradient design serves as an important approach to fabricate high‐performance bulk LLOs toward applications.

Wu, Tianhao↗
DOE OSTI2025

Derivation of physical equations for high-speed laser welding using large language models

It is challenging to formulate complex physical phenomena that occur in a manufacturing process, particularly when the available data are limited, rendering conventional data-driven approaches ineffective. This study aims to predict humping onset in high-speed laser welding by introducing a novel framework, namely text-to-equations generative pre-trained transformer (T2EGPT). This method leverages the capabilities of large language models (LLMs), in combination with sparse experimental data and enriched literature data, to derive an interpretable and generalizable equation for predicting humping initiation. By capturing key correlations among physical parameters, T2EGPT generates a compact and dimensionless expression that accurately predicts hump formation. The equation reveals that humping arises from the interplay between inertia-driven backward melt flow and capillary-driven surface stabilization, where inertial forces drive molten metal backward and capillary forces resist surface deformation. Furthermore, compared to traditional data-driven models, T2EGPT demonstrates enhanced predictive accuracy and cross-material transferability. More broadly, this study highlights the potential of LLMs to integrate textual information with data-driven discovery, enabling the extraction of physical laws in data-scarce scientific domains.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Crossing the bridge from molecular catalysis to a heterogenous electrode in electrocatalytic water oxidation

Significant progress has been made in designing single-site molecular Ru(II)-polypyridyl-aqua catalysts for homogenous catalytic water oxidation. Surface binding and transfer of the catalytic reactivity onto conductive substrates provides a basis for heterogeneous applications in electrolytic cells and dye-sensitized photoelectrosynthesis cells (DSPECs). Earlier efforts have focused on phosphonic acid (-PO 3 H 2 ) or carboxylic acid (-CO 2 H) bindings on oxide surfaces. However, issues remain with limited surface stabilities, especially in aqueous solutions at higher pH under conditions that favor water oxidation by reducing the thermodynamic barrier and accelerating the catalytic rate using atom-proton transfer (APT) pathways. Here, we address the problem by combining silane surface functionalization and surface reductive electropolymerization on mesoporous, nanofilms of indium tin oxide (ITO) on fluorine-doped tin oxide (FTO) substrates (FTO| nano ITO). FTO| nano ITO electrodes were functionalized with vinyltrimethoxysilane (VTMS) to introduce vinyl groups on the electrode surfaces by silane attachment, followed by surface electropolymerization of the vinyl-derivatized complex, [Ru II (Mebimpy)(dvbpy)(OH 2 )] 2+ (1 2+ ; Mebimpy: 2,6-bis(1-methyl-1 H -benzo[ d ]imidazol-2-yl)pyridine; dvbpy: 5,5'-divinyl-2,2'-bipyridine), in a mechanism dominated by a grafting-through method. The surface coverage of catalyst 1 2+ was controlled by the number of electropolymerization cycles. The combined silane attachment/cross-linked polymer network stabilized 1 2+ on the electrode surface under a variety of conditions especially at pH > ~6. Surface-grafted poly1 2+ was stable toward redox cycling at pH ~ 7.5 over an ~4-h period. Finally, sustained heterogeneous electrocatalytic water oxidation by the electrode gave steady-state currents for at least ~6 h with a Faradaic efficiency of ~68% for O 2 production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Balancing the Hydrogen Evolution Reaction, Surface Energetics, and Stability of Metallic MoS 2 Nanosheets via Covalent Functionalization

We modify the fundamental electronic properties of metallic (1T phase) nanosheets of molybdenum disulfide (MoS 2 ) through covalent chemical functionalization, and thereby directly influence the kinetics of the hydrogen evolution reaction (HER), surface energetics, and stability. Chemically exfoliated, metallic MoS 2 nanosheets are functionalized with organic phenyl rings containing electron donating or withdrawing groups. We find that MoS 2 functionalized with the most electron donating functional group (p-(CH 3 CH 2 ) 2 NPh-MoS 2 ) is the most efficient catalyst for HER in this series, with initial activity that is slightly worse compared to the pristine metallic phase of MoS 2 . The p-(CH 3 CH 2 ) 2 NPh-MoS 2 is more stable than unfunctionalized metallic MoS 2 and outperforms unfunctionalized metallic MoS 2 for continuous H 2 evolution within 10 min under the same conditions. With regards to the entire studied series, the overpotential and Tafel slope for catalytic HER are both directly correlated with the electron donating strength of the functional group. The results are consistent with a mechanism involving ground-state electron donation or withdrawal to/from the MoS 2 nanosheets, which modifies the electron transfer kinetics and catalytic activity of the MoS 2 nanosheet. The functional groups preserve the metallic nature of the MoS 2 nanosheets, inhibiting conversion to the thermodynamically stable semiconducting state (2H) when mildly annealed in a nitrogen atmosphere. We propose that the electron density and, therefore, reactivity of the MoS 2 nanosheets are controlled by the attached functional groups. Functionalizing nanosheets of MoS 2 and other transition metal dichalcogenides provides a synthetic chemical route for controlling the electronic properties and stability within the traditionally thermally unstable metallic state.

08 HYDROGEN↗