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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 1,477 records · Page 82
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Unveiling the Role of Lithium Iodide in Stabilizing Solid Interfaces in All-Solid-State Li Metal Batteries

A critical challenge in all-solid-state lithium metal batteries (ASSLMBs) is achieving a stable interface between the lithium metal anode and the solid electrolyte. Leveraging its success in Li/I 2 batteries, lithium iodide has garnered significant attentions for its potential to enhance interfacial stability and overall cell performance in ASSLMBs. Here, we elucidate the role of lithium iodide in stabilizing the solid interface in all-solid-state Li metal batteries with a Li argyrodite electrolyte, particularly focusing on its influence on lithium deposition behavior and interfacial evolution. Through in situ optical imaging, we demonstrate more uniform lithium deposition on an iodide-contained argyrodite electrolyte compared to a chloride-based counterpart. Complementary density functional theory calculations attribute improved lithium plating behavior to the enhanced lithiophilicity and better ionic conductivity of lithium iodide at the solid interface, effectively reducing localized current density. In conclusion, these findings provide useful insights into the mechanisms through which lithium iodide enhances the interfacial stability in ASSLMBs.

Anions↗
DOE OSTI2018

Electrolyte Solvation Structure at Solid/Liquid Interface Probed by Nanogap Surface-Enhanced Raman Spectroscopy

Understanding the fundamental factors that drive ion solvation structure and transport is key to design high performance, stable battery electrolytes. Reversible ion solvation and desolvation are critical to the interfacial charge transfer process across the solid-liquid interface as well as the resulting stability of the solid electrolyte interphase (SEI). Here in this paper, we report the first study of Li+ salt solvation structure in aprotic solution in the immediate vicinity (~ 20 nm) of the solid electrode-liquid interface using surface-enhanced Raman spectroscopy (SERS) from a gold nanoparticle (Au NP) monolayer. The plasmonic coupling between Au NPs produces strong electromagnetic field enhancement in the gap region, leading to 5 orders of magnitude increase in Raman intensity for electrolyte components and their mixtures namely, lithium hexafluorophosphate (LiPF6), fluoroethylene carbonate (FEC), ethylene carbonate (EC) and diethyl carbonate (DEC). Further, we estimate and compare the lithium-ion solvation number derived from SERS and Infra-Red (FTIR) spectroscopy experiments to monitor and ascertain the changes in the solvation shell diameter in the confined nanogap region where there is maximum enhancement of the electric field. Our findings provide a new multi-modal spectroscopic approach to gain fundamental insights into the molecular structure of the electrolyte at the solid-liquid interface.

25 ENERGY STORAGE↗
DOE OSTI2020

Probing Heterogeneous Charge Distributions at the α-Al 2 O 3 (0001)/H 2 O Interface

Unlike metal or semiconductor electrodes, the surface charge resulting from the protonation or deprotonation of insulating mineral oxides is highly localized and heterogeneous in nature. In this work the Stark active C≡N stretch of potassium thiocyanate is used as a molecular probe of the heterogeneity of the interfacial electrostatic potential at the α-Al 2 O 3 (0001)/H 2 O interface. Vibrational sum frequency generation (vSFG) measurements performed in the OH stretching region suggest that thiocyanate species organize interfacial water similarly to halide ions. Changes in the electrostatic potential are then tracked via Stark shifts of the vibrational frequency of the thiocyanate stretch. Our vSFG measurements show that we can simultaneously measure the vSFG response of SCN – ions experiencing charged and neutral surface sites. We assign local potentials of +308 and -154 mV to positively and negatively charged aluminol groups that are present at pH = 4 and pH = 10, respectively. Thiocyanate anions at positively charged surface sites and negatively charged surface sites and those participating in contact ion pairing adopt similar orientations and are oppositely oriented relative to thiocyanate ions near neutral surface sites. All four species followed Langmuir adsorption isotherms. Density functional theory–molecular dynamics (DFT-MD) simulations of SCN – near the neutral α-Al 2 O 3 (0001)/H 2 O interface show that the vSFG response in the C≡N stretch region originates from a SCN–H–O–Al complex, suggesting the surface site specificity of these experiments. To our knowledge this is the first spectroscopic measurement of local potentials associated with a heterogeneously charged surface. The ability to probe the evolution of local charges in situ could provide vital insight into many industrial, electrochemical, and geochemically relevant interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electron Inversion and Tunneling at Silicon Thermal Oxide Interfaces for Solar-Driven Molecular Catalysis to Syngas

Semiconductor photoelectrodes are regularly coupled to solid-state heterogeneous catalysts to perform solar-driven reduction of CO 2 . Less frequently, molecular catalysts are employed to better control the reactivity toward desired products, yet the development of robust semiconductor/molecule interfaces has proven challenging. Here, we demonstrate that a 2–3 nm thermal oxide layer on Si exhibits stability in aqueous solution, high photovoltage, and a photocurrent density of ∼10 mA/cm 2 for the solar-driven photoelectrochemical reduction of a homogeneous molecular catalyst, producing syngas with an ∼2:1 H 2 to CO ratio. Because of a low defect density, the oxide interface forms an electron inversion layer with metal-like electron density at cathodic potentials. This inversion layer facilitates electron transfer to redox-active molecules via tunneling even if the molecule’s reduction potential is beyond the semiconductor’s conduction band edge. Using an electrolyte solution composed of a homogeneous cobalt bis(terpyridine) catalyst in a water/organic solvent mixture, stable photoelectrochemistry was observed under 1-sun illumination, exhibiting an ∼30% Faradaic efficiency for CO that was similar to a glassy carbon electrode under comparable conditions. Furthermore, the results demonstrate that an ultrathin thermal oxide interface is a robust platform for development of aqueous-stable, molecule-driven photoelectrocatalysis.

Catalysts↗
DOE OSTI2026

pH-Driven Restructuring of Hydration Layers and Cation Adsorption at the Alumina–Water Interface

Oxide−water interfaces underpin ion separations, catalysis, and electrochemical energy technologies, where the electrical double layer (EDL) controls adsorption, transport, and reactivity. However, the molecular-scale links between pHdependent surface protonation, hydration-layer structure, and counterion adsorption remain poorly defined. Here, we combine in situ crystal truncation rod (CTR) and resonant anomalous X-ray reflectivity (RAXR) with streaming potential measurements and ab initio molecular dynamics (AIMD) simulations to resolve the chemical and structural evolution of the EDL at the single-crystal alumina (012)−water interface in 10 mM Rb + over pH 3−12. CTR measurements reveal two distinct adsorbed water layers at ∼2.2 and ∼3.5 Å above the surface. Each water layer shifts toward the substrate at transition pHs near 6.5 and 10.6, respectively, reflecting changes in primary hydration layer structure in response to the deprotonation of bridging and terminal aluminol groups. RAXR shows a 10-fold increase in Rb + coverage and a decrease in mean adsorption height from ∼3.5 to ∼2.7 Å with increasing pH, indicating enhanced counterion binding accompanied by Stern layer contraction. Streaming potential measurements demonstrate that the zeta potential, i.e., the potential at the hydrodynamic shear plane, is positive at pH 3 and becomes negative at pH ≥ 3.5. The negative charge magnitude increases with increasing pH, consistent with progressive surface deprotonation at higher pH. AIMD identifies inner- and outer-sphere Rb+ complexes whose adsorption heights and coordination geometries depend sensitively on the protonation state of surface oxygens, providing atomistic support for the experimentally inferred trends. These measurements establish two discrete, site-specific pH transitions in hydration-layer structure that track aluminol (de)protonation and quantitatively link them to a pH-driven contraction of the Stern layer (increasing Rb + coverage and decreasing adsorption height). This provides a direct structural basis for connecting surface acid−base chemistry to ion binding distances at an oxide−water interface.

Adsorption↗
DOE OSTI2020

Design and Evaluation of a Tethered, Open Port Sampling Interface for Liquid Extraction-Mass Spectrometry Chemical Analysis

Presented in this work is a tethered, liquid-extraction-sampling interface designed for the mass spectrometric surface sampling/analysis of 3D objects. The tethered, open port sampling interface (TOPSI) incorporates a vacuum line between the sampling probe and ionization source, which enables the ability for an extended, tethered sample transfer line. Herein, several designs of the hand-held TOPSI are presented and evaluated on the basis of the analytical metrics of analyte transport time, peak width, and analyte sensitivity. The best analytical metrics were obtained with capillary flow resistances arranged in a particular order and the vacuum region set at 6.2 kPa. This TOPSI design incorporated a transfer capillary 1 m in length, while retaining a fast analyte transport time (12 s), short signal peak width (5 s baseline-to-baseline), and high analyte signal at 90% of that obtained with a regular open port sampling interface (OPSI). The hand-held TOPSI was demonstrated for the characterization of extracted small molecules and metabolites from the surface of mint and rosemary leaves.

47 OTHER INSTRUMENTATION↗
DOE OSTI2013

Is the Calcite-Water Interface Understood? Direct Comparisons of Molecular Dynamics Simulations with Specular X-ray Reflectivity Data

New insights into the structure of the calcite-water interface are obtained through direct model-independent comparison of multiple classical molecular dynamics (MD) simulations with high-resolution specular X-ray reflectivity (XR) data. This set of comparisons, with four different state-of-the-art force fields (including two non-polarizable, one polarizable, and one reactive force field), reveal new insights into the absolute accuracy of the simulated structures and the uniqueness of the XR-derived structural results. These four simulations, while qualitatively similar, have visibly distinct interfacial structure, and are distinguished through a quantitative comparison of the XR signals calculated from these simulations with experimental XR data. The results demonstrate that the simulated calcite-water interface structures, as a whole, are not consistent with the XR data (i.e., within their precision and accuracy). This disagreement is largely due to the simulation of the calcite lattice. The simulated interfacial water profiles show substantially different levels of agreement with the XR data. Of these, the rigid-ion model (RIM) simulations show the best consistency with the experimental XR data. Further model-dependent comparisons of the structural parameters that describe the interfacial structure (derived from both the MD simulations and the XR data) provide further insight into the sources of differences between these two approaches. Using the new insights from the RIM simulations, new structures of the calcite-water interface consistent with both the experimental data and the simulation are identified and compared to recent results.

Calcite-water interface↗
DOE OSTI2014

Alumina(0001)/Water Interface: Structural Properties and Infrared Spectra from First-Principles Molecular Dynamics Simulations

We investigated the atomic structure and infrared spectra of the alumina(0001)/water interface, using first-principles molecular dynamics simulations based on density functional theory within the generalized gradient approximation. The computed structural properties of the interface are in good agreement with the results of synchrotron X-ray experiments. In this work detailed analyses of the computed infrared spectra revealed two types of water molecules at the hydrophilic oxide/water interface: molecules participating in strong “ice-like” hydrogen bonding with the oxide surface and molecules involved in weaker “liquid-like” hydrogen bonding. Our results provide a molecular interpretation of the “ice-like” and “liquid-like” bands observed in sum-frequency vibrational spectroscopy experiments and underscore the significance of strong hydrogen-bonding interactions in determining the orientation of interfacial water molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Strain-induced phase and oxygen-vacancy stability in ionic interfaces from first-principles calculations

Understanding interfacial chemistry is becoming crucial in materials design for heterointerfaces. Using density functional theory, we elucidate the effect of strained interfaces on phase and oxygen-vacancy stability for CeO2 | ZrO2, ThO2 | ZrO2 and CeO2 | ThO2 interfaces. The calculations show that ZrO2 transforms from cubic fluorite to the orthorhombic columbite under tensile strain providing evidence of a previous experimental speculation of an unrecognized ZrO2 phase. We also show that oxygen vacancies could be preferably stabilized on either side of the interface by manipulating strain. We predict that they are stable in tensile-strain, and unstable in compressivestrained materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Electrical Modulation of the Local Conduction at Oxide Tubular Interfaces

Hetero-interfaces between complex oxides have sparked considerable interest due to their fascinating physical properties and offer new possibilities for next-generation electronic devices. The key to realize practical applications is the control through external stimulus. In this study, we take the self-assembled BiFeO3-CoFe2O4 hetero-interface as a model system to demonstrate the non-volatile electric control of the local conduction at the complex oxide tubular interface. The fundamental mechanism behind this modulation was explored based on static and dynamic conducting atomic force microscopy. We found the movement of oxygen vacancies in the BiFeO3-CoFe2O4 heterostructure is the key to drive this intriguing behavior. This study delivers a possibility of designing new device for next-generation electronic devices.

BFO-CFO↗
DOE OSTI2016

Structural and magnetic depth profiles of magneto-ionic heterostructures beyond the interface limit

Electric field control of magnetism provides a promising route towards ultralow power information storage and sensor technologies. The effects of magneto-ionic motion have been prominently featured in the modification of interface characteristics. Here, we demonstrate magnetoelectric coupling moderated by voltage-driven oxygen migration beyond the interface in relatively thick AlO x /GdO x /Co(15 nm) films. Oxygen migration and Co magnetization are quantitatively mapped with polarized neutron reflectometry under electro-thermal conditioning. The depth-resolved profiles uniquely identify interfacial and bulk behaviours and a semi-reversible control of the magnetization. Magnetometry measurements suggest changes in the microstructure which disrupt long-range ferromagnetic ordering, resulting in an additional magnetically soft phase. X-ray spectroscopy confirms changes in the Co oxidation state, but not in the Gd, suggesting that the GdO x transmits oxygen but does not source or sink it. These results together provide crucial insight into controlling magnetism via magneto-ionic motion, both at interfaces and throughout the bulk of the films.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Promotion of Water-mediated Carbon Removal by Nanostructured Barium Oxide/nickel Interfaces

The existing Ni-yttria-stabilized zirconia anodes in solid oxide fuel cells (SOFCs) perform poorly in carbon-containing fuels because of coking and deactivation at desired operating temperatures. Here we report a new anode with nanostructured barium oxide/nickel (BaO/Ni) interfaces for low-cost SOFCs, demonstrating high power density and stability in C{sub 3}H{sub 8}, CO and gasified carbon fuels at 750 C. Synchrotron-based X-ray analyses and microscopy reveal that nanosized BaO islands grow on the Ni surface, creating numerous nanostructured BaO/Ni interfaces that readily adsorb water and facilitate water-mediated carbon removal reactions. Density functional theory calculations predict that the dissociated OH from H2O on BaO reacts with C on Ni near the BaO/Ni interface to produce CO and H species, which are then electrochemically oxidized at the triple-phase boundaries of the anode. This anode offers potential for ushering in a new generation of SOFCs for efficient, low-emission conversion of readily available fuels to electricity.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2015

Polarization screening-induced magnetic phase gradients at complex oxide interfaces

Thin-film oxide heterostructures show great potential for use in spintronic memories, where electronic charge and spin are coupled to transport information. Here we use a La 0.7 Sr 0.3 MnO 3 (LSMO)/PbZr 0.2 Ti 0.8 O 3 (PZT) model system to explore how local variations in electronic and magnetic phases mediate this coupling. We present direct, local measurements of valence, ferroelectric polarization and magnetization, from which we map the phases at the LSMO/PZT interface. We combine these experimental results with electronic structure calculations to elucidate the microscopic interactions governing the interfacial response of this system. We observe a magnetic asymmetry at the LSMO/PZT interface that depends on the local PZT polarization and gives rise to gradients in local magnetic moments; this is associated with a metal–insulator transition at the interface, which results in significantly different charge-transfer screening lengths. This work establishes a framework to understand the fundamental asymmetries of magnetoelectric coupling in oxide heterostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Liquid interfaces with pH-switchable nanoparticle arrays

Stimuli-responsive 2D nanoscale systems offer intriguing opportunities for creating switchable interfaces. At liquid interfaces, such systems can provide control over interfacial energies, surface structure, and rheological and transport characteristics, which is relevant, for example, to bio- and chemical reactors, microfluidic devices, and soft robotics. We explore the formation of a pH-responsive membrane formed from gold nanoparticles grafted with DNA (DNA–NPs) at a liquid–vapor interface. A DNA–NP 2D hexagonal lattice can be reversibly switched by pH modulation between an expanded state of non-connected nanoparticles at neutral pH and a contracted state of linked nanoparticles at acidic pH due to the AH + –H + A base pairing between A-motifs. Our in situ surface X-ray scattering studies reveal that the reversible lattice contraction can be tuned by the length of pH-activated linkers, with up to ~71% change in surface area.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Tough and circular glass fiber composites via a tailored dynamic boronic ester interface

Glass fiber reinforced polymer (GFRP) composites are valued for their strength and cost-effectiveness. However, traditional GFRPs often face challenges for end-of-life recycling due to their non-depolymerizable thermoset matrices, and long-term performance due to inadequate interfacial adhesion, which can lead to fiber–matrix delamination. Here, in this work, we have designed dynamic fiber–matrix interfaces to allow tough and closed-loop recyclable GFRPs by utilizing a vitrimer, derived from upcycled polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) with boronic ester (S-Bpin) and amine-based diol crosslinker. The boronic ester groups in S-Bpin form dynamic covalent bonds with the naturally present hydroxyl groups on the unsized GF surface, which eliminates the need for fiber sizing and enables facile closed-loop recyclability of both the fibers and the vitrimer matrix. The resulting strong fiber–matrix interface, depicted by the Raman mapping, leads to a 552% increase in-plane shear toughness (6.2 ± 0.3 MJ m -3 ) and 27% ultimate tensile strength (361 ± 89.2 MPa) compared to those of the conventional epoxy-based matrix (0.95 ± 0.05 MJ m -3 and 264 ± 59.7 MPa, respectively). The network rearrangement through dynamic boronic ester exchange enables fast thermoformability and repairability of micro-cracks at elevated temperatures. Additionally, both the matrix and composite demonstrate strong adhesion to various surfaces including steel and glasses exhibiting ≥6 MPa lap shear strength, which expands their suitability for diverse industrial applications. The readily created dynamic interface between boronic ester functionalized vitrimer and neat GFs presents a promising strategy for developing closed-loop recyclable, multifunctional structural materials, offering a sustainable alternative to non-recyclable thermoset GFRPs and contributes to a circular economy in composite materials.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Effect of residual gases in high vacuum on the energy-level alignment at noble metal/organic interfaces

The energy-level alignment at metal/organic interfaces has traditionally been studied using ultraviolet photoelectron spectroscopy (UPS) in ultra-high vacuum (UHV). However, since most devices are fabricated in high vacuum (HV), these studies do not accurately reflect the interfaces in real devices. We demonstrate, using UPS measurements of samples prepared in HV and UHV and current-voltage measurements of devices prepared in HV, that the small amounts of residual gases that are adsorbed on the surface of clean Cu, Ag, and Au (i.e., the noble metals) in HV can significantly alter the energy-level alignment at metal/organic interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Magnetic and electronic properties of the interface between half metallic Fe{sub 3}O{sub 4} and semiconducting ZnO

We have investigated the magnetic depth profile of an epitaxial Fe{sub 3}O{sub 4} thin film grown directly on a semiconducting ZnO substrate by soft x-ray resonant magnetic reflectometry (XRMR) and electron energy loss spectroscopy (EELS). Consistent chemical profiles at the interface between ZnO and Fe{sub 3}O{sub 4} are found from both methods. Valence selective EELS and XRMR reveal independently that the first monolayer of Fe at the interface between ZnO and Fe{sub 3}O{sub 4} contains only Fe{sup 3+} ions. Besides this narrow 2.5 A interface layer, Fe{sub 3}O{sub 4} shows magnetic bulk properties throughout the whole film making highly efficient spin injection in this system feasible.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Enhanced spin pumping at yttrium iron garnet/Au interfaces

Spin injection across the ferrimagnetic insulator yttrium iron garnet (YIG)/normal metal Au interface was studied using ferromagnetic resonance. The spin mixing conductance was determined by comparing the Gilbert damping parameter {alpha} in YIG/Au and YIG/Au/Fe heterostructures. The main purpose of this study was to correlate the spin pumping efficiency with chemical modifications of the YIG film surface using in situ etching and deposition techniques. By means of Ar{sup +} ion beam etching, one is able to increase the spin mixing conductance at the YIG/Au interface by a factor of 5 compared to the untreated YIG/Au interface.

36 MATERIALS SCIENCE↗