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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

The Effect of Mechanical State on the Equilibrium Potential of Alkali Metal/Ceramic Single–Ion Conductor Systems

The relationship between mechanical stress states and interfacial electrochemical thermodynamics of Li metal/Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 and Na metal/ Na-β”-Al 2 O 3 systems are examined in two experimental configurations with an applied uniaxial load; the solid electrolytes are pellets and the metal electrodes high-aspect-ratio electrodes. The experimental results demonstrate that 1) the change in equilibrium potential at the metal/electrolyte interface, when stress is applied to the metal electrode, is linearly proportional to the molar volume of the metal electrode, and 2) the mechanical stress in the electrolyte has a negligible effect on the equilibrium potential for an experimental setup in which the electrolyte is stressed and the electrode is left unstressed. Solid mechanics modeling of a metal electrode on a solid electrolyte pellet indicates that pressure and normal stress are within ≈0.5 MPa of each other for the high aspect ratio (≈1:100 thickness:diameter in our study) Li metal electrodes under loads that exceed yield conditions. Furthermore, this work should aid in advancing the quantitative understanding of alkali metal dendrite formation within incipient cracks and their subsequent growth, and pore formation upon stripping, both situations where properly accounting for the impact of mechanical state on the equilibrium potential is of critical importance for calculating the current distribution.

25 ENERGY STORAGE↗
DOE OSTI2025

Electrolyte-driven interphase stabilization in high-voltage sodium-ion full cells

Sodium-ion batteries with a high-voltage O3-type layered oxide cathode paired with a hard carbon anode can offer high energy density; however, significant interfacial instabilities driven by electrode/electrolyte reactions limit a broader industrial adoption. Localized high concentration electrolytes (LHCEs) are a rational choice as they promote salt decomposition over solvent, forming stable, inorganic-rich electrode-electrolyte interphases (EEIs). We present here a comparison of high-voltage (4.2 V) hard carbon | NaNi 1/3 Fe 1/3 Mn 1/3 O 2 pouch cells in LHCEs and in a standard carbonate-based electrolyte by (i) examining the influence of diluent choice on the electrochemical performance of LHCEs and (ii) investigating how the electrolyte chemistry affects the composition and structure of EEIs formed. Importantly, LHCEs demonstrate superior electrochemical performance, achieving 37% higher capacity after 200 cycles (119 vs. 87 mA h g -1 ) compared to the carbonate-based electrolyte. The enhanced stabilization provided by LHCEs at the interface with high-voltage sodium layered oxide cathode is revealed by gas evolution measurements obtained through online electrochemical mass spectrometry (OEMS). Time-of-flight secondary ion mass spectrometry paired with focused ion beam and advanced statistical analyses reveal that the superior performance of LHCE stems from a robust, thin cathode electrolyte interphase formed on the sodium layered oxide cathode and a homogeneous solid electrolyte interphase formation on the hard carbon anode. Furthermore, this study highlights the critical importance of electrolyte design in interphase stabilization, which plays a key role in advancing sodium-ion batteries toward commercial viability.

25 ENERGY STORAGE↗
DOE OSTI2025

Micro-structural features and material properties impact on adhesive metal joints via computational modeling and machine learning

The quality of structural bonding in practical applications depends on various factors arising from materials, pre-processing conditions, and manufacturing. Understanding how these factors influence bonding performance and determining their relative importance are of significant interest. Thus, this study evaluates the effects of microstructural features and material properties on the structural strength of adhesively-bonded metal joints at the submillimeter scale, utilizing a combination of Finite Element Modeling (FEM) and Machine Learning (ML) with Gradient Boosting Regression (GBR). The microstructural features include adhesive thickness, internal voids within the adhesive, adherend-adhesive interfacial voids, void size and volume fraction, and surface roughness. The material properties include the constitutive behavior of the adhesive, as well as the adherend-adhesive interfacial strength and fracture energy. The changes in structural strength and morphologies of the bonded metal structures with respect to different microstructural features and material properties were clarified by FEM. By further leveraging ML-GBR, the sequence of importance of these factors affecting bonding performance across various scenarios was summarized. This work provides valuable insights into the development of improved structural bonding for adhesive joints in industries such as automotive , aerospace, and beyond.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Trace LiBF 4 Enabling Robust LiF-Rich Interphase for Durable Low-Temperature Lithium-Ion Pouch Cells

Lithium-ion batteries (LIBs) with electrolytes containing lithium tetrafluoroborate (LiBF 4 ) can achieve large capacity retention under low temperature, but the accompanying rapid capacity decay inhibits commercialization. Here, in this study, the impact of LiBF 4 as a supplemental salt to LiPF 6 is systematically investigated using low ethylene carbonate (EC)-content electrolytes, along with a low-melting-point cosolvent. It is found that rational adjustment of the amount of LiBF 4 could not only regulate the interactions of anions and solvents in Li + solvation sheaths but also tune the composition and morphology of solid electrolyte interphase (SEI). It is worth noting that electrolytes with trace amount of LiBF 4 (0.05 M) show synergetic interaction between PF 6 - and Li + and decreased interaction between EC and Li + , achieving a dense and LiF-rich SEI, which enables a 200 mAh pouch cell with less gas generation, long-lived cycling, and higher low-temperature capacity, simultaneously. This work provides new insight into utilizing trace LiBF 4 for stable interface construction of durable low-temperature LIBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Criteria for electronic growth of Au on layered semiconductors

An electronic growth mode has been reported to occur in several noble metals on MoS2 but has not been observed on other layered semiconductors. In this work, the experiments show that Au(111) islands initially follow an electronic growth mode on WS2, matching the quantization seen in Au/MoS2. However, while epitaxial nanostructures with similar features are observed on WSe2, there is no sign of electronic growth. Binding energy calculations show that multiple bonding sites have nearly the same energy on both WS2 and MoS2, while Au strongly prefers a single bonding site on WSe2. Having multiple sites with the same energy gives flexibility in interfacial bonding that can alleviate strain from the 9+% lattice mismatch in these systems, which would, otherwise, easily suppress quantum size effects from electronic growth modes. These results should be useful in predicting which systems undergo quantized electronic growth on layered semiconductors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Thin film design of amorphous hafnium oxide nanocomposites enabling strong interfacial resistive switching uniformity

A design concept of phase-separated amorphous nanocomposite thin films is presented that realizes interfacial resistive switching (RS) in hafnium-oxide-based devices. The films are formed by incorporating an average of 7% Ba into hafnium oxide during pulsed laser deposition at temperatures ≤400°C. The added Ba prevents the films from crystallizing and leads to ~20-nm-thin films consisting of an amorphous HfO x host matrix interspersed with ~2-nm-wide, ~5-to-10-nm-pitch Ba-rich amorphous nanocolumns penetrating approximately two-thirds through the films. This restricts the RS to an interfacial Schottky-like energy barrier whose magnitude is tuned by ionic migration under an applied electric field. Resulting devices achieve stable cycle-to-cycle, device-to-device, and sample-to-sample reproducibility with a measured switching endurance of ≥10 4 cycles for a memory window ≥10 at switching voltages of ±2 V. Each device can be set to multiple intermediate resistance states, which enables synaptic spike-timing–dependent plasticity. The presented concept unlocks additional design variables for RS devices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Accelerated beta radiation aging of interlayer titanium nitride in gallium nitride contacts

Currently, there is no good way to determine the influence of the radiation on the aging of betavoltaic electrical contacts. Here, this work tested a method to accelerate the aging of the contacts inside a betavoltaic by enhancing energy deposition within the interfacial region of interest. An electrical contact of gold-titanium on gallium nitride was aged by exposure to tritium betas and electrons in a beamline. The interface stoichiometry was compared to the electrical performance of the contact. The method to age the betavoltaic component could help predict lifetime performance of the internal electrical contacts and provide assurance of deployment reliability.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Accelerated Beta Radiation Aging of Interlayer Titanium Nitride in Gallium Nitride Contacts

Research conducted under the Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory, a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy. An NNSS author co-authored this paper, and portions of this work were supported by the Mission Support and Test Services, LLC, under Contract No. DE-NA0003624 with the U.S. Department of Energy, National Nuclear Security Administration, NA-10 USDOE NA Office of Defense Programs (NA-10). PNNL-SA-163618 Currently, there is no good way to determine the influence of radiation on the aging of betavoltaic electrical contacts. This work tested a method to accelerate the aging of the contacts inside a betavoltaic by enhancing energy deposition within the interfacial region of interest. An electrical contact of gold-titanium on gallium nitride was aged by exposure to tritium betas and electrons in a beamline. The interface stoichiometry was compared to the electrical performance of the contact. The method to age the betavoltaic component could help predict the lifetime performance of the internal electrical contacts and provide assurance of deployment reliability.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Self-Propulsion by Directed Explosive Emulsification

An active droplet system, programmed to repeatedly move autonomously at a specific velocity in a well-defined direction, is demonstrated. Coulombic energy is stored in oversaturated interfacial assemblies of charged nanoparticle-surfactants by an applied DC electric field and can be released on demand. Spontaneous emulsification is suppressed by an increase in the stiffness of the oversaturated assemblies. Rapidly removing the field releases the stored energy in an explosive event that propels the droplet, where thousands of charged microdroplets are ballistically ejected from the surface of the parent droplet. The ejection is made directional by a symmetry breaking of the interfacial assembly, and the combined interaction force of the microdroplet plume on one side of the droplet propels the droplet distances tens of times its size, making the droplet active. The propulsion is autonomous, repeatable, and agnostic to the chemical composition of the nanoparticles. The symmetry-breaking in the nanoparticle assembly controls the microdroplet velocity and direction of propulsion. Finally, this mechanism of droplet propulsion will advance soft micro-robotics, establishes a new type of active matter, and introduces new vehicles for compartmentalized delivery.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Insights into solvent and surface charge effects on Volmer step kinetics on Pt (111)

Abstract The mechanism of pH-dependent hydrogen oxidation and evolution kinetics is still a matter of significant debate. To make progress, we study the Volmer step kinetics on platinum (111) using classical molecular dynamics simulations with an embedded Anderson-Newns Hamiltonian for the redox process and constant potential electrodes. We investigate how negative electrode electrostatic potential affects Volmer step kinetics. We find that the redox solvent reorganization energy is insensitive to changes in interfacial field strength. The negatively charged surface attracts adsorbed H as well as H + , increasing hydrogen binding energy, but also trapping H + in the double layer. While more negative electrostatic potential in the double layer accelerates the oxidation charge transfer, it becomes difficult for the proton to move to the bulk. Conversely, reduction becomes more difficult because the transition state occurs farther from equilibrium solvation polarization. Our results help to clarify how the charged surface plays a role in hydrogen electrocatalysis kinetics.

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

Understanding the Dissolution and Passivation of an Aluminum Electrode during Electrocoagulation of Groundwater Using Neutron and X-ray Reflectometry

An aluminum (Al)-based electrocoagulation (EC) system can effectively remove dissolved silica and hardness in groundwater. The effectiveness of Al-EC in terms of pollutant removal, Faradaic efficiency, and energy consumption depends on the interfacial electrolysis or passivation of the electrode in water. Thus, understanding the electrolysis reaction at the liquid/electrode interface during operation is important for sustainable EC deployment. Here, a continuous flow-through Al-EC system was tested with various groundwater simulants, i.e., chloride (Cl – )-based, sulfate (SO 4 2– )-based, and mixed solutions. High pollutant removal with low energy consumption was observed in Cl – -based groundwater treatment, while low pollutant removal with high energy consumption was observed in SO 4 2– -based groundwater. For example, the required energy per unit mass of Al dosing in SO 4 2– -based groundwater is three times higher than that in Cl – -based groundwater at 10 mA/cm 2 . However, increasing the Cl – concentration significantly reduces this energy demand. In SO 4 2– -based groundwater, the silicate removal efficiency drops from 85.1% to 24.0% compared to that for Cl – -based groundwater, while Mg 2+ and Ca 2+ removal efficiencies decrease to 0.6% from 15.8% and 5.7% from 44.8%, respectively. To better understand this EC performance, we used in situ neutron reflectometry (NR) to examine the interfacial dynamics of Al dissolution and passivation at a 100 nm scale occurring on the surface of the sacrificial Al electrodes during EC. Ex situ X-ray reflectometry (XRR) was also used to support the in situ NR results. Both NR and XRR results revealed that Al dissolution is influenced by the presence of Cl – in the simulants, while a passivating layer forms on the electrode in a SO 4 2– -based solution. In the Cl – -based solution, anodic Al dissolution occurred locally and inhomogeneously across the surface of the Al anode film, resulting in a localized thickness reduction over time. In the SO 4 2– -based solution, no apparent dissolution of the Al anode was identified. Instead, Al underwent oxidation, forming an amorphous Al 2 O 3 surface layer within the Al electrode film that increased in thickness over time. In the mixed solution, both anodic Al dissolution and surface Al 2 O 3 layer formation occurred, indicating that Al dissolution and surface Al 2 O 3 layer formation are attributable to the Cl – and SO 4 2– ions, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Phase-Transition Interlayer Enables High-Performance Solid-State Sodium Batteries with Sulfide Solid Electrolyte

All-solid-state sodium (Na) batteries (ASSSBs) using sulfide-based solid electrolytes (SEs) have attracted intensive attention due to their superior safety, high energy density and low cost. However, interfacial issue is one of the biggest challenges to achieve high-performance sulfide-based ASSSBs due to the serious reactions between active Na metal and sulfide SEs at the interface. To address the interfacial challenges, we propose in this paper a simple and efficient approach by introducing a polymer electrolyte as an interlayer to stabilize the interface. Na 3 SbS 4 as a model sulfide SE is used to demonstrate the interlayer strategy to stabilize the interface by preventing the detrimental reactions and inhibiting Na dendrites. As a result, stable Na plating/stripping was observed in Na symmetric cells under the current density of 0.1 mA cm –2 . Moreover, ASSSBs with Na metal and TiS 2 electrode delivered long-term stability over 300 cycles remaining a specific capacity above 100 mAh g –1 , and FeS 2 ||Na cells exhibited an impressive specific capacity of up to 200 mAh g –1 after the 20th cycles. This work demonstrates an efficient strategy to address interfacial challenges between sulfide SEs and Na metal, which contributes to the development of ASSSBs in next-generation energy storage systems.

25 ENERGY STORAGE↗
DOE OSTI2023

All-polymer nanocomposites having superior strength, toughness and ultralow energy dissipation

Toughening polymers has attracted significant interest. Traditionally, polymer toughness is enhanced by constructing polymer networks or introducing sacrificial bonds into the chains between crosslink points. These strategies, though, introduce pronounced energy dissipation and associated heat, both of which are undesirable under long-term cyclic loading, for example at the interface of implants in the human body. By incorporating single-chain nanoparticles (SCNPs) into linear polymer chains to generate all-polymer nanocomposites (APNCs), we have been able to achieve high strength, high toughness with low energy dissipation. Using a combination of simulation and experimental results, we are advancing a “SCNPs effect” where tightly cross-linked SCNPs produce a modulus contrast to achieve strengthening and toughening. Benefitting from the soft interface, the penetrable and deformable SCNPs cause the surrounding polymer chains to move in concert, significantly reducing the interfacial friction to achieve low energy dissipation. The intramolecular cross-linking of the SCNPs and adhesion between the SCNPs and polymer matrix are critical for realizing such high-performance systems. Based on a Gaussian regression model and back propagation (BP) neural network, the mechanical strength can be predicted and is supported by simulations. Finally, the APNC concept described can be applied to elastomers and gels, broadening its utilization in high-cycle and low-dissipation applications, like soft robots, flexible sensors and cartilage replacements, and artificial heart valves.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Stable CdTe Photoanodes with Energetics Matching Those of a Coating Intermediate Band

Here, a TiO 2 coating was grown on a CdTe absorber by atomic layer deposition for stabilization against its photocorrosion during photoelectrochemical water splitting. Under simulated sunlight (AM 1.5G, 100 mW cm –2 ), this multilayer CdS/CdTe/TiO 2 /Ni/NiO x photoanode produced a light-limited photocurrent density of 24.5 ± 0.5 mA cm –2 and a photovoltage of 780 ± 20 mV. This record energy-conversion performance was comparable to those of baseline CdS/CdTe solar cells and was achieved only after the development of proper CdTe surface treatments prior to coating the stabilization layer. The TiO 2 coating, with its in-gap charge-transport intermediate band, facilitates hole transport as light exits the CdTe/TiO 2 interface. With proper interfacial chemistry, the electrochemical potential energy of the coating intermediate band matched that of the CdTe valence band. Moreover, the stabilized CdS/CdTe/TiO 2 /Ni/NiO x photoanodes showed 100 h stability for water oxidation under light-on/light-off cycles. This study provides insightful guidance for designing stabilization contacts for efficient and stable light-driven water oxidation.

14 SOLAR ENERGY↗
DOE OSTI2020

The dependence of aluminum lattice orientation on semiconductor lattice parameter in planar InAs/Al hybrid heterostructures

We present a detailed study of 7-nm thick Al layers epitaxially grown on In x Al 1-x As or Al 1-x Ga x Sb y As 1-y (0 0 1) semiconductors using high-resolution transmission electron microscopy (HRTEM) and synchrotron X-ray diffraction (XRD). These techniques provide high spatial and high reciprocal space resolution information about Al lattice orientations and interfacial structure, highlighting the existence of a strong correlation between the surface lattice parameter of the semiconductor and the normal orientation of the aluminum film. The normal orientation of Al layers is found to be [1 1 1] when the in-plane semiconductor surface lattice parameter, a S , is smaller than 5.98 Å, and is [1 1 0] when aS is larger than this value. In the transition between these lattice parameters where one orientation is preferred, both orientations may be observed. Concomitant with the change in normal orientation is an inversion in the strain state of the aluminum film. When the normal orientation is [1 1 1], the Al film is compressively strained; while for [1 1 0] normal orientations, the Al in-plane strain is tensile. An energy balance model, accounting for surface, interfacial, side-face, and strain energy, and the registry of lattice planes across the semiconductor/aluminum interface provide explanations for the observed normal orientation and strain inversion.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Electrolyte Organization Leads to Potential-Dependence in Thermochemical Catalysis of Nonpolar Reactions

Electrochemical polarization is now known to play a key role in thermochemical catalysis at solid–liquid interfaces. However, existing frameworks cannot account for why even nonpolar, nonfaradaic reactions are sensitive to interfacial polarization. In order to uncover the molecular basis of this phenomenon, we herein study the potential-dependent reaction kinetics of ethylene and trans-2-butene hydrogenation at Pt–liquid interfaces. Measurements were performed in aqueous and ortho-difluorobenzene (o-DFB) solutions, spontaneously polarizing the Pt–liquid interfaces by, respectively, varying the pH or dissolving distinct metallocene redox buffers into solution. Here, we find that at comparable mechanistic regimes, the rates of both ethylene and trans-2-butene hydrogenation are maximized near the same electrochemical potential, E. Moreover, the potential-dependence, defined as $\frac{∂ln 𝑟}{∂𝐸}$, of trans-2-butene hydrogenation is approximately 2.2× greater than that of ethylene hydrogenation across the full potential range studied. These observations are all consistent with a model in which polarization of the Pt surface away from the local potential of zero free charge (E PZFC ) induces electrostatic organization of the polar solvent and charged ions near the interface, which impedes olefin adsorption and surface reaction because these surface reactions induce electrolyte displacement. Accordingly, interfacial polarization alters the free energy landscape and thus the rate of nonpolar heterogeneous catalysis by controlling the degree of electrostatic organization of polar and charged spectators at the interface, which do not in general need to be specifically chemisorbed onto the surface but could simply be close enough to the surface to be perturbed by the olefin adsorption. These results point toward electrochemical design handles, namely, the electrolyte, catalyst potential, and local E PZFC of the catalyst, with which to tune interfacial catalysis of thermochemical organic transformations.

adsorption↗