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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 181 records · Page 10
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DOE OSTI2023

Operando Electrochemical Liquid-Cell Scanning Transmission Electron Microscopy (EC-STEM) Studies of Evolving Cu Nanocatalysts for CO 2 Electroreduction

The design and synthesis of nanocatalysts with well-defined sizes, compositions, and structures have revolutionized our accessibility to tunable catalyst activity and selectivity for a variety of energy-related electrochemical reactions. Nonetheless, establishing structure-(re)activity correlations requires the understanding of the dynamic evolution of pristine nanocatalysts and the identification of their active states under operating conditions. We previously communicated the operando observation of Cu nanocatalysts evolving into active metallic Cu nanograins for CO 2 electroreduction (Yang et al. Nature 2023, 614, 262–269). Here, we expand our discussion to the technical capabilities and further research applications of operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM), which enables quantitative electrochemistry while tracking dynamic structural evolution of sub-10 nm Cu nanocatalysts. The coexistent H 2 bubbles, often disruptive to operando spectroscopy, are an effective approach to create a thin-liquid layer that significantly improves spatial resolution while remaining electrochemically accessible to Cu nanocatalysts. Operando four-dimensional (4D) STEM in liquids provides insights into the complex structure of active polycrystalline metallic Cu nanograins. With continuous technical developments, we anticipate that operando EC-STEM will evolve into a powerful electroanalytical method to advance our understanding of a variety of nanoscale electrocatalysts at solid/liquid interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Support Effect Studied on Thin-Film Perovskites

Some functional oxides exhibit strong support effects but typically have low surface areas and stabilities that negate the promotional effects. The primary goal of our work in the past three years was to develop high-surface-area versions of these supports by Atomic Layer Deposition onto stable supports, then use these to understand how the oxide supports affect the metal catalytic properties. The primary application targeted for these materials was methane oxidation and related reactions for emissions control. Systems of particular interest were supported, precious metals on thin-film perovskites in order to develop “intelligent” catalysts in which the metal can reversibly ex-solve from perovskite lattices. This following report lists the papers that were published with the support of this DOE grant, together with a brief summary of the results from each paper.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

ALD with Alternative Coreactants: Which Work, Which Do Not, and Why

In this paper, we present a combined experimental and theoretical study that systematically evaluates a series of alcohols (i.e., primary, secondary, and tertiary) as coreactants for trimethylaluminum (TMA)-based atomic layer deposition (ALD) of Al 2 O 3 . We employed in situ quartz crystal microbalance techniques and ex situ X-ray photoelectron spectroscopy to probe growth across a range of temperatures from T = 120 to 285 °C. Dispersion-inclusive hybrid density functional theory was employed to identify potential reaction pathways and compute corresponding Gibbs free-energy barriers and rate coefficients. Experimentally on an Al 2 O 3 surface, sustained thin-film growth, where the rate is constant over many cycles, was only observed with tertiary alcohols (tert-butanol and 2-methyl-2-butanol) at elevated temperatures (e.g., T = 285 °C); for tert-butanol specifically, sustained growth also occurred at T = 240 °C, with no sustained growth at or below T = 210 °C. Growth using primary and secondary alcohols decayed to a negligible value after only 2–3 cycles on an Al 2 O 3 surface at all tested temperatures. Intentional trace additions of H 2 O to anhydrous alcohols restored sustained growth but at reduced deposition rates relative to pure H 2 O. Theoretical analysis supports a bimolecular alkoxy β-H elimination mechanism as the primary reaction pathway: initiated by the formation of a bound alkoxy species, the subsequent β-H elimination step is rate-determining, with a barrier that systematically decreases as the degree of the alcohol coreactant is increased from primary to secondary to tertiary. Computed rate coefficients (k) also indicate a strong temperature dependence (with k increasing by ∼4–5 orders of magnitude from T = 120 to 285 °C) and are consistent with the experimental observation that only tertiary alcohols lead to steady thin-film growth at elevated temperatures. This integrated approach establishes why only certain alcohols can sustain Al 2 O 3 ALD and delivers a predictive framework for identifying effective alcohol coreactants.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Advancing ionomer design to boost interfacial and thin-film proton conductivity via styrene-calix[4]arene-based ionomers

Sub-micrometer-thick ion-conducting polymer (ionomer) layers often suffer from poor ionic conductivity at the substrate/catalyst interface. The weak proton conductivity makes the electrochemical reaction at the cathode of proton-exchange-membrane fuel cells sluggish. To address this, here we report on a class of polystyrene-based ionomers having sub-nanometer-sized, sulfonated macrocyclic calix[4]arene-based pendants (PS-calix). In films with thickness comparable to that of ionomer-based binder layers, the conductivity of PS-calix film (~41 mS/cm) is ~13 times higher than that of the current state-of-the-art ionomer, Nafion. We observe a similar improvement in proton conductivity when PS-calix interfaces with Pt nanoparticles, demonstrating the potential of PS-calix in catalyst ink. Leveraging a favorable interfacial chemical composition, PS-calix enhances proton conduction at the film-substrate interface, a shortcoming of Nafion. Moreover, the water in PS-calix films diffuses faster than bulk water and the water confined in Nafion films, suggesting an important role played by sub-nanometer-sized calix[4]arene cavities in creating unique water/ion transport pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Melt-Processed Halide Perovskite Thin Films from a Two-Dimensional Ruddlesden–Popper Phase Precursor

While halide perovskite thin films have enormous potential for photovoltaics and other optoelectronics, the use of environmentally hazardous solvents during their deposition and processing poses a barrier to their commercialization. In this work, we demonstrated the deposition of melt-processable precursors and subsequent transformation into halide perovskite thin films without using environmentally hazardous solvents. We melted the wide-bandgap layered perovskites [(C 6 H 5 CH(CH 3 )CH 2 NH 3 ) 2 PbI 4 :β-Me-PEA 2 PbI 4 ] at ~210 °C and blade coated them into films. The β-Me-PEA 2 PbI 4 films were subsequently transformed to perovskite-phase methylammonium or formamidinium lead iodide films using a cation-exchange process in an alcohol-based solvent. Lastly, we demonstrate the potential and limitations of a completely solvent-free approach that uses solid-state transformation of a β-Me-PEA 2 PbI 4 film. As a result, this work represents a substantial step toward eliminating environmentally hazardous solvents and enables inexpensive industrial-scale liquid-phase deposition processes that do not require expensive systems for handling and disposing of environmentally hazardous solvents.

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

Hierarchically-Structured Ti/TiO 2 Electrode for Hydrogen Evolution Synthesized via 3D Printing and Anodization

Hierarchically-structured, electro-catalysts consisting of a titanium core with controlled macro-porosity and a thin titania surface-layer with controlled nano-porosity were synthesized via combination of additive manufacturing and in-situ anodization. The electrodes were tested for hydrogen evolution reaction and depicted competitive electro-catalytic activities, with Tafel slopes between 40 and 56 mV dec -1 . The electrodes also depicted competitive onset and over potentials when compared with other electrode alternatives. The synthesis approach for the electro-catalysts reported in this work is being extended to other metal/metal-oxide pairs and applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Revealing nanomechanical deformation at the interface and degradation in all-thin-film inorganic electrochromic devices

Recently, progress in electrochromic (EC) devices has been made in optimizing electrode and device configurations and performance. However, the ion insertion/de-insertion induced charge transfer (CT) nanomechanical effect has remained unexplored, i.e., repetitive electrode size changes at the nanoscale and stress/strain generated during electrochemical cycling, which is the focus of this work due to its intimate correlation with the elastic and plastic deformation at the interface. Considering the intervalence electrons, excellent electrochemical kinetics, and dramatic color changes, tungsten oxide (WO 3 ) and nickel oxide (NiO) films are configured as the EC cathode and anode materials, respectively, within a full device. Upon extended cycles (>10 000), the void generation and delamination that occurred at the interface account for performance decay. Encouraged by the findings, nanoindentation mechanical tests and electrical kelvin probe force microscopy were employed to investigate the CT induced effects at the interface. There is a dramatic increase of up to 45% in the elastic Young's modulus in colored/charged WO 3 at ~40 mC cm -2 . Here, the correlation between CT and synergistic mechanical effect is interpreted by the Lippman equation. Interestingly, despite the charged state (colored; lithiated) with a relatively flat morphology bringing an ~3.4 times higher electrostatic surface potential, the electrical work function unexpectedly decreases, arising from the dominant effect of the dipole layer potential over the chemical potential. The interatomic cohesive energy and equilibrium distance increase bury the seeds for mechanical deformation in the long run. This work provides fundamental insights into electro-chemo mechanics and interdisciplinary concerted interfacial effects at the nano/atomic level. The dependence of surface potential, stress, work function, and cohesive energy on electrochemical kinetics has been interpreted.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Confined Growth of DNA-Assembled Superlattice Films

Here, we study the assembly of DNA-functionalized nanocubes under lateral confinement in microscale square trenches on a DNA-functionalized substrate. Microfocus small-angle X-ray scattering (SAXS) and scanning electron microscopy (SEM) are used to characterize the superlattices (SLs). The results indicate that nanocubes form simple-cubic SLs with square-prism morphology and a (100) out-of-plane orientation to maximize DNA bonding. In-plane, SLs align with the template, exposing their {100} side facets, and the degree of alignment depends on trench size. Interestingly, the distribution of in-plane orientations determined from SAXS and SEM do not agree, indicating that the internal and external structures of the SLs differ. To understand this discrepancy, X-ray ptychography is employed to image the internal structures of the SLs, revealing that SLs which appear to be single-crystalline in SEM may have subsurface grain boundaries, depending on trench size. SEM reveals that the SLs grow via nucleation and growth of randomly oriented domains, which then coalesce; this mechanism explains the observed dependence of alignment and defect structure on size. Interestingly, crystallization occurs via an unusual growth mode, whereby continuous SL layers grow on top of several misoriented islands. Overall, this work elucidates the effect of lateral confinement on the crystallization of DNA-functionalized nanoparticles and shows how X-ray ptychography can be used to gain insight into nanoparticle crystallization.

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

Enhanced positive and negative exchange bias in FeF 2 /Ni with dusted interfaces

An enhanced exchange bias was found in FeF 2 /Ni interfaces by inserting dusting of Pd and Cu atoms. We have used an ultrathin wedge to investigate systematically the effect of a discontinuous nonmagnetic spacer between the antiferromagnetic and ferromagnetic layers. Negative and positive exchange biases are symmetric and maximized for less than two angstroms of the nonmagnetic layer. Moreover, the dusting reduces the field cooling threshold to switch between the negative and the positive exchange bias. This finding demonstrates that nonmagnetic dusted layers can improve the interfacial exchange energy density in antiferromagnetic/ferromagnetic heterostructures and modify the bulk antiferromagnetic domain structure. Other dusting materials such as Ag, Ti, V, and SiO 2 showed no enhancement in FeF 2 /Ni bilayers, which indicates the atomic sensitivity of this effect.

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

Conversion Kinetics and Ionic Conductivity in Na-β”-Alumina + YSZ (Naβ”AY) Sodium Solid Electrolyte via Vapor Phase Conversion Process

Sodium ion batteries have been receiving increasing attention and may see potential revival in the near future, particularly in large-scale grid energy storage coupling with wind and solar power generation, due to the abundant sodium resources, low cost, and sufficiently high energy density. Among the known sodium ion conductors, the Na-β”-alumina electrolyte remains highly attractive because of its high ionic conductivity. This study focuses on the vapor phase synthesis of a Na-β”-Alumina + YSZ (Naβ”AY) composite sodium electrolyte, which has higher mechanical strength and stability than conventional single phase β”-Alumina. The objectives are the measurement of conversion kinetics through a newly developed weight-gain based model and the determination of sodium ionic conductivity in the composite electrolyte. Starting samples contained ~70 vol% α-Alumina and ~30 vol% YSZ (3 mol% Y 2 O 3 stabilized Zirconia) with and without a thin alumina surface layer made by sintering in air at 1600 °C. The sintered samples were placed in a powder of Na-β”-alumina and heat-treated at 1250 °C for various periods. Sample dimensions and weight were measured as a function of heat treatment time. The conversion of α-Alumina in the α-Alumina + YSZ composite into Naβ”AY occurred by coupled diffusion of sodium ions through Na-β”-alumina and of oxygen ions through YSZ, effectively diffusing Na2O. From the analysis of the time dependence of sample mass and dimensions, the effective diffusion coefficient of Na 2 O through the sample, D eff , was estimated to be 1.74 x 10 -7 cm2 s -1 , and the effective interface transfer parameter, k eff , was estimated as 2.33 x 10 -6 cm s -1 . By depositing a thin alumina coating layer on top of the bulk composite, the chemical diffusion coefficient of oxygen through single phase Na-β”-alumina was estimated as 4.35 x 10 -10 cm 2 s -1 . An AC impedance measurement was performed on a fully converted Naβ”AY composite, and the conductivity of the composite electrolyte was 1.3 x 10 -1 S cm -1 at 300 °C and 1.6 x 10 -3 S cm -1 at 25 °C, indicating promising applications in solid state or molten salt batteries at low to intermediate temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Catalytic open-circuit passivation by thin metal oxide films of p-Si anodes in aqueous alkaline electrolytes

Ni and NiO x -based protective thin films are shown to catalyze the oxidation of Si in the presence of O 2 in strongly alkaline KOH(aq) even in the absence of illumination. The O 2 in solution drove the open-circuit potential of the electrode to >0.4 V, which is positive of the Si passivation potential. The elevated electrochemical potential of the surface promoted formation of passive oxides on exposed Si regions of Si/Ni electrodes. Catalytic passivation of Si extended the durability of an np + -Si(100)/NiO x photoanode to >400 h while operating under simulated day/night cycles. In contrast, electrodes without a Ni(O x ) layer and/or without O 2 in solution displayed direct etching of the Si and corrosion pitting during non-illuminated, simulated nighttime episodes of day/night cycling. The O 2 -derived catalyzed passivation of Si using thin films can be generalized to multiple phases of NiO x as well as to materials other than Ni. Finally, relative to operation in aqueous alkaline conditions, decreasing the pH of the electrolyte decreased the dissolution rate of the protective oxide layer formed by the catalyzed passivation process, and consequently increased the durability of the photoanode, but yielded lower photoelectrode fill factors for water oxidation due to the relatively large kinetic overpotentials for the electrocatalyzed oxygen-evolution reaction at near-neutral pH.

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

Intelligent Agents for the Optimization of Atomic Layer Deposition

Atomic layer deposition (ALD) is a highly controllable thin film synthesis approach with applications in computing, energy, and separations. The flexibility of ALD means that it can access a massive chemical catalogue; however, this chemical and process diversity results in significant challenges in determining processing parameters that result in stable and uniform film growth with minimal precursor consumption. In situ measurements of the ALD growth per cycle (GPC) can accelerate process development but it still requires expert intuition and time-consuming trial and error to identify acceptable processing parameters. This procedure is made more difficult by the presence of experimental noise in the GPC values and the complexity of ALD surface chemistries. Here, a need exists for efficient optimization approaches capable of autonomously determining processing conditions resulting in optimal ALD film growth. In this work, we present the development of three optimization strategies and compare their performance in optimizing four simulated ALD processes. Furthermore, the effect of noise in the GPC measurements on optimization convergence is studied.

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

Iridium Surface Oxide Affects the Nafion Interface in Proton-Exchange-Membrane Water Electrolysis

Proton-exchange-membrane water electrolyzer (PEMWE) catalyst layers consist of aggregates of catalyst particles (typically iridium) and ionomer (typically Nafion). Prior work suggests that the oxide form of Ir affects the kinetics of the oxygen-evolution reaction. However, because most catalyst-benchmarking studies are conducted ex situ in liquid electrolytes, it remains unclear how the ionomer is influenced by the catalyst oxide and affects overall cell performance. Using a suite of experimental techniques, we conduct fundamental investigations into model ink (catalyst and ionomer dispersed in solution) and thin-film systems to inform cell-level overpotential analysis as a function of three forms of Ir (metallic Ir m , oxyhydroxide IrOOH, and oxide IrO 2 ). Furthermore, nafion on Ir m has a high degree of phase separation and higher swelling, likely improving the ionic conductivity. Additionally, Nafion binds most strongly to IrOOH, likely yielding reduced kinetic overpotentials. These findings highlight the intricacies of the ionomer/Ir interface and provide insight into all catalyst-layer systems.

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

Millimeter-Scale Exfoliation of hBN with Tunable Flake Thickness for Scalable Encapsulation

As a two-dimensional (2D) dielectric material, hexagonal boron nitride (hBN) is in high demand for applications in photonics, nonlinear optics, and nanoelectronics. Unfortunately, the high-throughput preparation of macroscopic-scale, high-quality hBN flakes with controlled thickness is an ongoing challenge, limiting device fabrication and technological integration. In this report we present a metal thin-film exfoliation method to prepare hBN flakes with millimeter-scale dimension, near-unity yields, and tunable flake thickness distribution from 1-7 layers, a substantial improvement over scotch tape exfoliation. The single crystallinity and high quality of the exfoliated hBN are demonstrated with optical microscopy, atomic force microscopy, Raman spectroscopy, and second harmonic generation. We further explore a possible mechanism for the effectiveness and selectivity based on thin-film residual stress measurements, density functional theory calculations, and transmission electron microscopy imaging of the deposited metal films. We find that the magnitude of the residual tensile stress induced by thin film deposition plays a key role in determining exfoliated flake thickness in a manner which closely resembles 3D semiconductor spalling. Lastly, we demonstrate that our exfoliated, large-area hBN flakes can be readily incorporated as encapsulating layers for other 2D monolayers. Altogether, this method brings us one step closer to the high throughput, mass production of hBN-based 2D photonic, optoelectronic, and quantum devices.

2D materials↗
DOE OSTI2024

Epitaxial Metal Electrodeposition Controlled by Graphene Layer Thickness

Control over material structure and morphology during electrodeposition is necessary for material synthesis and energy applications. One approach to guide crystallite formation is to take advantage of epitaxy on a current collector to facilitate crystallographic control. Single-layer graphene on metal foils can promote “remote epitaxy” during Cu and Zn electrodeposition, resulting in growth of metal that is crystallographically aligned to the substrate beneath graphene. However, the substrate–graphene–deposit interactions that allow for epitaxial electrodeposition are not well understood. Here, we investigate how different graphene layer thicknesses (monolayer, bilayer, trilayer, and graphite) influence the electrodeposition of Zn and Cu. Scanning transmission electron microscopy and electron backscatter diffraction are leveraged to understand metal morphology and structure, demonstrating that remote epitaxy occurs on mono- and bilayer graphene but not trilayer or thicker. Density functional theory (DFT) simulations reveal the spatial electronic interactions through thin graphene that promote remote epitaxy. This work advances our understanding of electrochemical remote epitaxy and provides strategies for improving control over electrodeposition.

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

Superconducting platinum silicide analyzed by x-ray photoelectron spectroscopy

Platinum silicide has garnered increased attention due to its potential applications as a superconductor within silicon technology. In this work, we characterize a superconducting PtSi film using x-ray photoelectron spectroscopy with an Al K α excitation source. Survey spectra, Pt 5s, Pt 4f, Pt 4d, Pt 4p, Pt 4s, Si 2p, Si 2s, O 1s core levels, and the valence band spectrum were measured. In conclusion, this collection of high-quality core level spectra of a superconducting PtSi film provide reference data for this material, which often has a minimal native silicon oxide layer and overlapping Si and Pt core level peaks.

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

Understanding Degradation Mechanisms in SrIrO 3 Oxygen Evolution Electrocatalysts: Chemical and Structural Microscopy at the Nanoscale

Designing acid-stable oxygen evolution reaction electrocatalysts is key to developing sustainable energy technologies such as polymer electrolyte membrane electrolyzers but has proven challenging due to the high applied anodic potentials and corrosive electrolyte. This work showcases advanced nanoscale microscopy techniques supported by complementary structural and chemical characterization to develop a fundamental understanding of stability in promising SrIrO 3 thin film electrocatalyst materials. Cross-sectional high-resolution transmission electron microscopy illustrates atomic-scale bulk and surface structure, while secondary ion mass spectrometry imaging using a helium ion microscope provides the nanoscale lateral elemental distribution at the surface. After accelerated degradation tests under anodic potential, the SrIrO 3 film thins and roughens, but the lateral distribution of Sr and Ir remains homogeneous. A layer-wise dissolution mechanism is hypothesized, wherein anodic potential causes the IrO x -rich surface to dissolve and be regenerated by Sr leaching. Finally, the characterization approaches utilized herein and mechanistic insights into SrIrO 3 are translatable to a wide range of catalyst systems.

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

Colossal Magnetoresistance without Mixed Valence in a Layered Phosphide Crystal

Materials with strong magnetoresistive responses are the backbone of spintronic technology, magnetic sensors, and hard drives. Among them, manganese oxides with a mixed valence and a cubic perovskite structure stand out due to their colossal magnetoresistance (CMR). A double exchange interaction underlies the CMR in manganates, whereby charge transport is enhanced when the spins on neighboring Mn 3+ and Mn 4+ ions are parallel. Prior efforts to find different materials or mechanisms for CMR resulted in a much smaller effect. Here an enormous CMR at low temperatures in EuCd 2 P 2 without manganese, oxygen, mixed valence, or cubic perovskite structure is shown. EuCd 2 P 2 has a layered trigonal lattice and exhibits antiferromagnetic ordering at 11 K. The magnitude of CMR (10(4)%) in as-grown crystals of EuCd 2 P 2 rivals the magnitude in optimized thin films of manganates. In this work, the magnetization, transport, and synchrotron X-ray data suggest that strong magnetic fluctuations are responsible for this phenomenon. The realization of CMR at low temperatures without heterovalency leads to a new regime for materials and technologies related to antiferromagnetic spintronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗