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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 1,081 records · Page 60
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Perspective—Enhancing Active Anode Material Performance for Lithium-Ion Batteries via Manipulation of Interfacial Chemistry

Over the past decade, conversion-type anodes have been viewed as an attractive frontrunner for use in the next-generation of high-capacity battery materials. However, many technological limitations exist in the stability and long-term reliability of these anodes for the commercialization of these electrodes. This perspective studies how interfacial interactions between different components of the electrode can help elucidate the key physical and chemical properties needed for the development of high-capacity materials for battery applications.

25 ENERGY STORAGE↗
NASA NTRS1991

Structure and functions of water-membrane interfaces and their role in proto-biological evolution

Among the most important developments in proto-biological evolution was the emergence of membrane-like structures. These are formed by spontaneous association of relatively simple amphiphilic molecules that would have been readily available in the primordial environment. The resulting interfacial regions between water and nonpolar interior of the membrane have several properties which made them uniquely suitable for promoting subsequent evolution. They can (1) selectively attract organic material and mediate its transport, (2) serve as simple catalysts for chemical reactions, and (3) promote the formation of trans-membrane electrical and chemical gradients which could provide energy sources for proto-cells. Understanding the structure of interfaces, their interactions with organic molecules and molecular mechanisms of their functions is an essential step to understanding proto-biological evolution. In our computer simulation studies, we showed that the structure of water at interfaces with nonpolar media is significantly different from that in the bulk. In particular, the average surface dipole density points from the vapor to the liquid. As a result, negative ions can approach the interface more easily than positive ions. Amphiphilic molecules composed of hydrocarbon conjugated rings and polar substituents (e.g., phenol) assume at the interface rigid orientations in which polar groups are buried in water while hydrocarbon parts are located in the nonpolar environment. These orientational differences are of special interest in connection with the ability of some of these molecules to efficiently absorb photons. Flexible molecules with polar substituents often adopt at interfaces conformations different from those in the bulk aquaeous solution and in the gas phase. As a result, in many instances both specificity and kinetics of chemical reactions in which these molecules can participate is modified by the presence of surfaces. Of special interest is the mechanism by which polar molecules are transferred across interface between water and a nonpolar medium. Our recent study showed that simple ionophores bind ions by the same mechanisms as ion channels and carriers from modern cells.

Pohorille, A.↗
DOE OSTI2025

Structure and Sulfur: Tuning the Viscoelastic and Surface Properties of Natural Keratin Fibers

Natural keratin fibers, such as wool, possess a complex hierarchical structure that governs their mechanical properties and surface energy. However, the extent to which these characteristics are influenced by combined contributions of structural variations (e.g., fiber diameter, intermediate filament (IF) packing) and chemical composition (e.g., disulfide bond density) remains poorly understood. In this study, we investigate wool fibers from five sheep breeds (Merino, Polwarth, Cheviot, Eider, and Devon) to elucidate how these factors influence viscoelasticity and surface interactions. Using a multimodal approach integrating interfacial and bulk characterization methods, including inverse gas chromatography (IGC), atomic force microscopy-infrared spectroscopy (AFM-IR), X-ray photoelectron spectroscopy (XPS), uniaxial tensile testing, and synchrotron small-angle X-ray scattering (SAXS), we show that the nanometer-thick 18-methyleicosanoic acid (18-MEA) layer is consistently present across all wool types and plays a key role in governing hydrophobicity and surface heterogeneity. A controlled isothermal treatment at 200 °C, designed to cleave disulfide bonds, results in a nearly 40% reduction in specific surface area across all fiber types, accompanied by a significant decrease in tensile strength and 80% reduction in elongation at break for Merino and Devon wool, but limited influence on the mechanical properties of Eider fibers. Furthermore, rate-dependent tensile testing within the elastic regime reveals distinct viscoelastic responses among the fiber types, suggesting that the sulfur-rich protein matrix surrounding IFs and its structure contribute actively to stress partitioning. Altogether, when combined with conclusions from SAXS measurements of IF spacing, our work offers compelling insights into the role of the keratin-associated protein (KAP) matrix in shaping wool fiber mechanics. Differences in mechanical behavior among wool types, despite similar IF spacing or sulfur content, highlight the importance of matrix composition and cross-linking density, suggesting that the molecular architecture of the KAP network may be a dominant factor in determining fiber performance.

X-ray scattering↗
DOE OSTI2024

A Highly Efficient and Affordable Hybrid System for Hydrogen and Electricity Production (Final Project)

The pursuit of clean, secure, and sustainable energy has sparked significant interest in fuel cells for power generation and electrolyzer cells for hydrogen production. Among all types of fuel and electrolyzer cells, solid oxide cells (SOCs) have emerged as promising candidates due to their high efficiency and versatility. However, conventional oxygen-ion conductive SOCs face several challenges related to their performance and durability associated with their high-temperature operation (≥ 800 ºC). This has led to a growing interest in intermediate-temperature (≤ 650 ºC) proton-conducting solid oxide cells (p-SOCs) as potential alternatives. In collaboration between Phillips 66 and Georgia Tech, this project aims to achieve a 1 kW p-SOCs system to demonstrate the commercial viability of efficient SOC systems. This report addresses four primary areas and key challenges we overcame: (1) development of efficient and durable proton-conducting electrolyte (e.g., BaHf 0.1 Ce 0.7 Yb 0.2 O 3-δ ) and electrode/catalyst materials, (2) large area cell fabrication (10 x 10 cm 2 ), (3) scalable stack design and building (250 W and 1 kW), and (4) demonstration of a 1 kW prototype system. Notably, significant challenges faced during the large area cell fabrication process were addressed by achieving cell flatness, improving fabrication yield, and ensuring electrode/electrolyte interfacial adhesion. Stack designs were also developed, focusing on reducing contact resistance and optimizing stack components (e.g., sealants). These efforts resulted in the achievement of high performance and durability with promising outputs of 250 W and 1 kW. Furthermore, the integration of these stacks into a fuel-powered system was explored, with refinements made to heat management, as well as to pressure and heating conditions. The results demonstrated the potential applicability of our p-SOC technology in commercial energy storage and power generation systems. Additionally, the report discusses techno-economic analysis and a market transformation plan, aiming to evaluate and advance the commercial feasibility of this technology.

25 ENERGY STORAGE↗
DOE OSTI2024

Role of Heterointerface in Lithium-Induced Phase Transition in T d -WTe 2 Nanoflakes

A new polytype of WTe 2 with a bandgap has been recently discovered through the intercalation of lithium into the van der Waals gaps of T d -WTe 2 . Here, we report the effects of reduced thicknesses and heterointerfaces on the intercalation-induced phase transition in WTe 2 . Using in situ Raman spectroscopy during the electrochemical lithiation of WTe 2 flakes as a function of flake thickness, we observe that additional electrochemical energy is required for the phase transition of WTe 2 from the T d phase to the new lithiated T d ' phase, going from 0.8 V of the applied electrochemical voltage for a thick flake to 0.5 V and 0.3 V for 7- and 5-layered samples, respectively. We ascribe this suppression of the phase transition to the interfacial interaction between the nanoflake and SiO 2 /Si substrate, which plays an increasing role as the sample thickness is reduced. The suppressed kinetics of the phase transition can be mitigated by placing the WTe 2 flake on a hexagonal boron nitride (hBN) flake, which facilitates the release of the in-plane strain induced by the phase transition. Importantly, our study underscores the significance of interfacial effects in modulating phase transitions in two-dimensional (2D) materials, suggesting heterogeneous transition pathways, as well as interfacial engineering to control these phase transitions.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Stripping away ion hydration shells in electrical double-layer formation: Water networks matter

Significance For centuries the double layer at the solid/electrolyte interface has been a central concept in electrochemistry. Today, it is still crucial for virtually all renewable energy storage and conversion technologies. Here, the double-layer formation is probed by THz spectroscopy with ultrabright synchrotron light as a source. Our results capture the molecular details of double-layer formation at positively/negatively charged Au electrodes for an NaCl electrolyte. We reveal a contrasting response applying positive versus negative bias, which is dictated by the interfacial water network and rationalized by accompanying molecular dynamics simulations and electronic-structure calculations. While Na + is directly attracted toward the negatively charged electrode, stripping of the Cl − hydration shell is observed only at larger potential values.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Antiferromagnetic domain switching modulated by an ultrathin Co interlayer in the Fe/Co/CoO/MgO(001) system

Using a combination of hysteresis loop, Kerr microscope, and x-ray magnetic circular dichroism measurements, in this study we investigated the antiferromagnetic (AFM) domain switching process modulated by the sub-nm thick Co inserting layer in a single crystalline Fe/Co/CoO/MgO(001). The CoO AFM domain switching occurs at lower temperature for the thicker Co interlayer, and the activation energy barrier of CoO AFM domain switching decreases as the Co interlayer thickness increases. The exchange coupling strength between the AFM spins in CoO layer and the ferromagnetic spins in the Fe/Co bilayer is found to be independent of the Co layer thickness. Our results suggest an approach to modulate the dynamic properties of AFM domains with an interfacial modification.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Validating first-principles molecular dynamics calculations of oxide/water interfaces with x-ray reflectivity data

Metal oxide/water interfaces play a crucial role in many electrochemical and photocatalytic processes, such as photoelectrochemical water splitting, the creation of fuel from sunlight, and electrochemical CO 2 reduction. First-principles electronic structure calculations can reveal unique insights into these processes, such as the role of the alignment of the oxide electronic energy levels with those of liquid water. An essential prerequisite for the success of such calculations is the ability to predict accurate structural models of these interfaces, which in turn requires careful experimental validation. Here we report a general, quantitative validation protocol for first-principles molecular dynamics simulations of oxide/aqueous interfaces. The approach makes direct comparisons of interfacial x-ray reflectivity (XR) signals from experimental measurements and those obtained from ab initio simulations with semilocal and van der Waals functionals. The protocol is demonstrated here for the case of the Al 2 O 3 (001)/water interface, one of the simplest oxide/water interfaces. We discuss the technical requirements needed for validation, including the choice of the density functional, the simulation cell size, and the optimal choice of the thermodynamic ensemble. Our results establish a general paradigm for the validation of structural models and interactions at solid/water interfaces derived from first-principles simulations. Furthermore, while there is qualitative agreement between the simulated structures and the experimental best-fit structure, direct comparisons of simulated and measured XR intensities show quantitative discrepancies that derive from both bulk regions (i.e., alumina and water) as well as the interfacial region, highlighting the need for accurate density functionals to properly describe interfacial interactions. Our results show that XR data are sensitive not only to the atomic structure (i.e., the atom locations) but also to the electron-density distributions in both the substrate and at the interface.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Emerging investigator series: ion diffusivities in nanoconfined interfacial water films contribute to mineral carbonation thresholds

The dynamics and reactivity of nanoconfined fluids play critical roles across a wide range of environmental and technological systems, though reaction mechanisms and kinetics are not well understood. Here, the carbonation kinetics of forsterite (Mg 2 SiO 4 ) exposed to 90 atm supercritical carbon dioxide at 35–65 °C and 85–100% relative humidity (RH) was monitored with in situ X-ray diffraction, and partner molecular dynamics simulations were used to describe the free energy landscape of Mg 2+ adsorption and diffusion on forsterite surfaces covered in water films 3–10 monolayers thick. The collective findings reveal how decreasing the water film thickness by ~1.4 monolayers, from ~0.92 to ~0.64 nm, inhibited reaction rates by up to 97%, promoted anhydrous Mg-carbonate (magnesite, MgCO 3 ) precipitation, and more than doubled the apparent activation energy of carbonation. The transport simulations suggest that four monolayers are required to enable sufficiently facile Mg 2+ diffusion, helping explain previously observed water film thickness-dependent reactivity thresholds.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Interconnected cathode-electrolyte double-layer enabling continuous Li-ion conduction throughout solid-state Li-S battery

All-solid-state lithium (Li) batteries with high energy density are a promising solution for the next-generation energy storage systems in large-scale devices. To simultaneously overcome the challenges of poor ionic conduction of solid electrolytes and shuttling of active materials, here we introduce a functional electrolyte-cathode bilayer framework with interconnected LLAZO channels from the electrolyte into the cathode for advanced solid-state Li-S batteries. Differing from the traditional solid-state batteries with separated layer compositions, the introduced bilayer framework provides ultrafast and continuous ion/electron conduction. Instead of transferring Li+ across the polymer and garnet phases which involve huge interfacial resistance, Li+ is directly conducted through the LLAZO channels created continuously from the cathode layer to the solid electrolyte layer, significantly shortening the diffusion distance and facilitating the redox reaction of sulfur and sulfides. A stable cycle life is demonstrated in the prototype Li-S solid-state batteries assembled with the introduced LLAZO-LLAZO@CNF interconnected bilayer framework. High capacity is obtained at room temperature, indicating the superior electrochemical properties of the bilayer framework that result from the unique design of the interconnected LLAZO garnet phase.

25 ENERGY STORAGE↗
DOE OSTI2022

Molecular simulation of the structural and thermodynamic properties of n-alkane/brine interfacial systems with nonionic surfactants

All-atom molecular dynamics (MD) simulations are used to study the structural and thermodynamic properties of water + n-heptane interfacial systems in the presence of salinity (NaCl, NaI, KCl, and KI) and two different nonionic surfactants. Excellent qualitative and quantitative agreement with interfacial tension experimental data is obtained, but this requires applying a charge scaling factor to the ionic species, suggesting the likely role of polarizability effects. Tensoactive behavior is observed for the NaI and KI systems, coinciding with layering of the iodide species near the interface. Further, there are significant interaction differences between the surfactants and the different ionic species, but the structural and thermodynamic behavior of the surfactant molecules is relatively unaffected by the specific salt species. Our analysis suggest that the surfactant-surfactant interactions play a critical role in determining the interfacial behavior, with a much smaller impact associated with the composition of the brine phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

The effect of original and initial saturation on residual nonwetting phase capillary trapping efficiency

Injection of supercritical carbon dioxide (CO 2 ) into geological formations is a strategy for both atmospheric greenhouse gas reduction (climate change mitigation) and enhanced oil recovery. To understand CO 2 trapping efficiency, the capillary trapping behaviors that immobilize subsurface fluids were analyzed at the pore-scale using pairs of proxy fluids representing the range of in situ nonwetting and wetting fluid properties encountered in geologic storage reservoirs. The pairs of fluids were cycled through imbibition and drainage processes using a flow cell apparatus containing a sintered glass bead column. Computed x-ray microtomography (microCT) was used to identify immobilized nonwetting fluid after imbibition and drainage events. From microCT images, the trapped residual (post-secondary imbibition) nonwetting phase was spatially correlated to both the original (post-primary imbibition) and the initial (post-primary drainage) nonwetting phase; this relationship is referred to here as the original saturation dependence (SO-dependence) and initial saturation dependence (SI-dependence), respectively. Significant trends of decreasing SO- and SI-dependence with increasing wetting and nonwetting fluid phase viscosities were observed. This finding implies that the amount of CO 2 injected and ultimately trapped is dependent on the nonwetting phase (e.g. oil or gas) already present in the formation, as well as on the manner in which supercritical CO 2 is initially injected, which are factors not considered in current trapping models. To explore the potential effect that varying viscosity and interfacial tension (IFT) might have on this process, we report on a variety of fluid pairs with different viscosities and IFT.

42 ENGINEERING↗
DOE OSTI2024

Epitaxial heterointerfacial electron bridge synchronizes oxygen evolution activity and stability on a layered double hydroxide surface

Scalable green hydrogen production via electrocatalytic water splitting is largely restricted by the insufficient activity and stability of oxygen evolution reaction (OER) catalysts at the anode. As a class of the most active OER catalysts in alkaline electrolyzers, the application of layered double hydroxides (LDHs) remains a main challenge owing to the unstable lattice oxygen dissolution due to the dominant lattice oxygen-involving OER mechanism during long-term operation. Herein, we found that using an epitaxial hetero-interfacing nickel hydroxide (namely Ni(OH) 2 ) as an electron bridge between an active FeCo LDH and Ni foam support to form an LDH*/NFO catalyst, the electronic storage capacity around the Fermi level (-0.5 to +0.5 eV, e-D FE ) sharply increases from 0.93 per cell to 1.51 per cell. Subsequently, we demonstrate that this high e-D FE enables ceaseless and fast power injection into the kinetic process of intermediate species conversion and inhibits lattice oxygen dissolution in the active FeCo LDH. Consequently, it demonstrated a low OER overpotential of 246 mV at a current density of 100 mA cm -2 and ultrahigh stability for up to 3500 hours with an ultraslow overpotential increase rate of 9.4 × 10 -3 mV h -1 . Therefore, we developed an epitaxial hetero-interfacial electron bridging strategy to synchronize the activity and stability of available catalysts for scalable green hydrogen production via electrocatalytic water splitting.

25 ENERGY STORAGE↗
DOE OSTI2025

Enhancing Acidic Oxygen Evolution Activity by Controlling Oxidation State of Iridium

Iridium oxides with high oxidation states have been reported to be effective in enhancing the acidic oxygen evolution reaction (OER) performance. In this work, we develop ultrasmall IrO x nanoparticles (NPs) over titanium nitride (TiN), which undergoes surface oxidation under oxidative conditions to form oxygen‐modified TiN (oxi‐TiN), enabling the formation of highly oxidized Ir δ+ (δ > 4). This IrO x /oxi‐TiN catalyst delivers higher Ir mass activity than commercial IrO 2 , while comparable stability is maintained. The superior OER activity of IrO x /oxi‐TiN is further demonstrated in a proton exchange membrane water electrolyzer (PEMWE), requiring only 1.88 V to reach 3 A cm −2 , achieving the U.S. Department of Energy 2025 target (1.90 V at 3 A cm −2 ). In situ X‐ray absorption spectroscopy (XAS) confirms that the superior OER activity of IrO x /oxi‐TiN originates from highly oxidized Ir δ+ under OER conditions. Density functional theory (DFT) calculations reveal a general correlation between the oxidation state of Ir and OER overpotential. Specifically, the introduction of interfacial oxygen at the Ir/TiN interface increases the oxidation state of deposited Ir δ+ from δ < 4 to δ > 4, decreasing the OER overpotential. This study highlights the critical role of high oxidation states of Ir δ+ in enhancing OER activity, providing guidance for the development of advanced acidic OER catalysts.

58 GEOSCIENCES↗
DOE OSTI2024

Enhanced rare earth element recovery with cross-linked glutaraldehyde-lanthanide binding peptides in foam-based separations

Lanthanide Binding Tag (LBT) peptides that coordinate selectively with lanthanide ions can be used to replace the energy intensive processes used for the separation of rare earth elements (REEs). These surface-active biomolecules, once selectively complexed with the trivalent REE cations, can adsorb to air/aqueous interfaces of bubbles for foam-based REEs recovery. Glutaraldehyde, an organic compound that is a homobifunctional crosslinker for proteins and peptides, can be used to enhance the adsorption and interfacial stabilization of lanthanide-bound peptides films. The stability of the interfacial cross-linked films was tested by measuring their dilational and shear surface rheological properties. Surface activity of the adsorbed species was analyzed using pendant drop tensiometry, while surface density and molecular arrangement were determined using x-ray reflectivity and x-ray fluorescence near total reflection. Glutaraldehyde cross-linked REE-peptide complexes enhance the adsorption of lanthanides to air-water interfaces, resulting in thicker interfacial structures. Subsequently, these thicker layers enhance the dilational and shear interfacial rheological properties. The interfacial film stabilization and REEs extraction promoted by the cross-linker presented in this work provides an approach to integrate glutaraldehyde as a substitute of common foam stabilizers such as polymers, surfactants, and particles to optimize the recovery of REEs when using biomolecules as extractants.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Reactive force fields for aqueous and interfacial magnesium carbonate formation

Here we develop Mg/C/O/H ReaxFF parameter sets for two environments: an aqueous force field for magnesium ions in solution and an interfacial force field for minerals and mineral–water interfaces. Since magnesium is highly ionic, we choose to fix the magnesium charge and model its interaction with C/O/H through Coulomb, Lennard-Jones, and Buckingham potentials. We parameterize the forcefields against several crystal structures, including brucite, magnesite, magnesia, magnesium hydride, and magnesium carbide, as well as Mg 2+ water binding energies for the aqueous forcefield. Then, we test the forcefield for other magnesium-containing crystals, solvent separated and contact ion-pairs and single-molecule/multilayer water adsorption energies on mineral surfaces. We also apply the forcefield to the forsterite–water and brucite–water interface that contains a bicarbonate ion. We observe that a long-range proton transfer mechanism deprotonates the bicarbonate ion to carbonate at the interface. Free energy calculations show that carbonate can attach to the magnesium surface with an energy barrier of about 0.22 eV, consistent with the free energy required for aqueous Mg–CO 3 ion pairing. Also, the diffusion constant of the hydroxide ions in the water layers formed on the forsterite surface are shown to be anisotropic and heterogeneous. These findings can help explain the experimentally observed fast nucleation and growth of magnesite at low temperature at the mineral–water–CO 2 interface in water-poor conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗