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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Solid 3D Li–S Battery Design via Stacking 2D Conductive Microporous Coordination Polymers and Amorphous Li–S Layers

To make a lithium-sulfur (Li-S) battery practical, not only high gravimetric energy capacity is important, but also high volumetric energy capacity will be required. The currently explored Li-S cathode designs often deploy systems with liquid electrolyte infiltration, hence with relatively low volumetric capacity. In the current study, we theoretically test a compact solid three-dimensional (3D) design (more like a Li-ion battery cathode than a conventional Li-S cathode) consisted of a sandwich structure alternating between the two-dimensional (2D) Mn-hexaaminobenzene-based coordination polymer (2D Mn-HAB-CP) layer and the amorphous Li-S layer. We study the theoretical limits for both its gravimetric and volumetric energy capacity, as well as its structural stability and Li diffusion within the cathode system. To study the Li diffusion within an amorphous system, we also develop a pull-atom molecular dynamics (PA-MD) to calculate the barrier heights of such disordered systems. We reveal the mechanism that determines the Li diffusion in the amorphous layer of the system. Overall, we find such a 3D solid Li-S cathode can be practical, with sufficient large gravimetric and volumetric energy capacity, as well as the Li diffusion constant. It also solves many other common Li-S cathode problems, from Li polysulfide dissolution to electrical insulating, and structure instabilities.

25 ENERGY STORAGE↗
DOE OSTI2020

Amorphous Pd-Loaded Ti 4 O 7 Electrode for Direct Anodic Destruction of Perfluorooctanoic Acid

In this work we present a novel Ti 4 O 7 -based electrode loaded with amorphous Pd clusters that achieve efficient anodic destruction of perfluorooctanoic acid (PFOA), a persistent water pollutant with significant environmental and human health concerns. These amorphous Pd clusters were characterized by the disordered, noncrystalline arrangement of Pd single atoms in close proximity, in contrast to crystalline Pd nanoparticles that have been often employed to tailor the electronic properties of an electrode. We found that the Ti 4 O 7 electrode loaded with amorphous Pd clusters significantly outperformed the Ti 4 O 7 electrode loaded with crystalline Pd particles due to enhanced electron transfer through dominant Pd–O bonds. Combined with the efficient binding of PFOA and its degradation intermediates to the fluorinated electrode surface, this electrode was capable of mineralizing PFOA and releasing fluoride as F – . The reaction pathway was found to proceed without involving reactive oxygen species and therefore was not quenched by common anions in complex natural water systems such as chloride ions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

An Ab Initio -Derived Force Field for Amorphous Silica Interfaces for Use in Molecular Dynamics Simulations

Here, we present a classical interatomic force field, silica-DDEC, to describe the interactions of amorphous and crystalline silica surfaces, parametrized using density functional theory-based charges. Charge schemes for silica surfaces were developed using the density-derived electrostatic and chemical (DDEC) method, which reproduces atomic charges of the periodic models as well as the electrostatic potential away from the atom sites. Lennard–Jones parameters were determined by requiring the correct description of (i) the amorphous silica density, coordination defects, and local coordination geometry, relative to experimental measurements, and (ii) water-silica interatomic distances compared with ab initio results. Deprotonated surface silanol sites are also described within the model based on DDEC charges. The result is a general electronic structure-derived model for describing fully flexible amorphous and crystalline silica surfaces and interactions of liquids with silica surfaces of varying structure and protonation state.

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

Machine-Learning-Guided Insights into Solid-Electrolyte Interphase Conductivity: Are Amorphous Lithium Fluorophosphates the Key?

Despite decades of study, the identity of the dominant Li + -conducting phase within the inorganic SEI of Li-ion batteries remains unresolved. While the mosaic model describes LiF/Li 2 O/Li 2 CO 3 nanocrystallites within a disordered matrix, these crystalline phases inherently offer limited ionic conductivity. Growing evidence suggests that interfaces, grain boundaries, and amorphous phases may instead host the primary fast-ion pathways. Using diffusion-based generative structure prediction and machine-learning interatomic potentials (MLIPs), we investigate lithium difluorophosphate (LiPO 2 F 2 ), a key mixed-anion decomposition product of phosphorus- and fluorine-containing electrolytes. We identify a stable crystalline polymorph and demonstrate that the amorphous counterpart is conductive, with projected room-temperature σ ≈ 0.18 mS cm –1 and E a ≈ 0.40 eV. Here, this enhancement stems from structural disorder flattening the Li site-energy landscape and a low formation energy for Li-interstitial defects, which supplies additional mobile carriers. We propose amorphous mixed-anion Li-P-O-F phases as a promising conducting medium in the SEI, offering a specific target for engineering improved battery interfaces.

Zhong, Peichen [University of California, Berkeley↗
DOE OSTI2026

Amorphous ZrCl 4 -Based Superionic Conductor as a Cost-Effective Solid Electrolyte for Batteries

Developing highly conductive and cost-effective solid electrolytes is essential for the commercialization of all-solid-state batteries (ASSBs). Zr-based halide electrolytes hold great promise due to their low estimated cost and high oxidation stability. However, the ionic conductivities of most of them are not high enough to enable moderate- and high-rate cycling of ASSBs. Here, fast ion transport is achieved in a group of cost-effective ZrCl 4 -based electrolytes via a design strategy to create highly disordered amorphous structures. Amorphous Li 0.8 ZrCl 4 (SO 4 ) 0.4 , with a low estimated cost of $21 kg –1 , achieves an ionic conductivity of 1.86 mS cm –1 at 25 °C. It also shows a high oxidation limit of 4.5 V vs Li/Li + and good compatibility with high-voltage cathodes, as demonstrated by the stable cycling of ASSBs (73.7% capacity retention after 1000 cycles at 1 C). Synchrotron X-ray diffraction, pair distribution function analysis, and electrochemical impedance spectroscopy reveal that the outstanding conductivity of these amorphous electrolytes is closely related to their short-range and medium-range ordering, revealing new insights for designing high-performance, cost-effective solid electrolytes.

Zhang, Guangxing [Georgia Institute of Technology,↗
DOE OSTI2020

Amorphization and Plasticity of Olivine During Low-Temperature Micropillar Deformation Experiments

Experimentally quantifying the viscoplastic rheology of olivine at the high stresses and low temperatures of the shallow lithosphere is challenging due to olivine's propensity to deform by brittle mechanisms at these conditions. In this study, we use microscale uniaxial compression tests to investigate the rheology of an olivine single crystal at room pressure and temperature. Pillars with nominal diameters of 1.25 μm were prepared using a focused ion beam milling technique and were subjected to sustained axial stresses of several gigapascal. The majority of the pillars failed after dwell times ranging from several seconds to a few hours. However, several pillars exhibited clear evidence of plastic deformation without failure after 4–8 hr under load. The corresponding creep strain rates are estimated to be on the order of 10-6 to 10 -7 s -1 . The uniaxial stresses required to achieve this deformation (4.1–4.4 GPa) are in excellent agreement with complementary data obtained using nanoindentation techniques. Scanning transmission electron microscopy observations indicate that deformation occurred along amorphous shear bands within the deformed pillars. Electron energy loss spectroscopy measurements revealed that the bands are enriched in Fe and depleted in Mg. We propose that inhomogeneities in the cation distribution in olivine concentrate stress and promote the amorphization of the Fe-rich regions. Finally, the time dependence of catastrophic failure events suggests that the amorphous bands must grow to some critical length scale to generate an unstable defect, such as a shear crack.

58 GEOSCIENCES↗
DOE OSTI2026

Constraining the Hydration of Clay Minerals and Abundances of Amorphous Phases in Gale Crater, Mars

Both water and organic matter are required for the development and persistence of life. Phyllosilicates (clay minerals) have high surface areas that easily sorb water and organic matter. The Curiosity rover has investigated several hundred meters of stratigraphy in Gale crater, including where clays were detected from orbit. Previous results have suggested that subsurface hydration is greatest in units with the most abundant clays, suggesting that these minerals may be hydrated. Organics have also been found throughout Gale crater. Smectites are the most common and abundant phyllosilicates in Gale crater samples and can expand and sorb water and organics in interlayer sites. The most common organic sorption processes on Earth typically involve water or hydroxyl, so hydrated phyllosilicates are good candidates for organic preservation. Using newly derived subsurface hydration results with previously published mineralogy and geochemistry, we derived modeled constraints on the abundances of hydrated amorphous phases, “excess” water, and “excess” cations. These “excess” phases are not accounted for by published crystalline phase abundances or by amorphous phases constrained here. We found correlations between smectites and both “excess” water and “excess” cation abundances, indicating that smectites in Gale crater are hydrated and that cation bridging could be a mechanism for sorption of organics. Our results also show the persistence of amorphous sulfates, opal-A, and volcanic or impact glass, which indicate low water-rock interactions. Increased abundances of sulfates and glass in stratigraphically higher samples may indicate lower water availability and environmental aridification during the time these units were being deposited.

58 GEOSCIENCES↗
DOE OSTI2021

Distilling nanoscale heterogeneity of amorphous silicon using tip-enhanced Raman spectroscopy (TERS) via multiresolution manifold learning

Abstract Accurately identifying the local structural heterogeneity of complex, disordered amorphous materials such as amorphous silicon is crucial for accelerating technology development. However, short-range atomic ordering quantification and nanoscale spatial resolution over a large area on a-Si have remained major challenges and practically unexplored. We resolve phonon vibrational modes of a-Si at a lateral resolution of <60 nm by tip-enhanced Raman spectroscopy. To project the high dimensional TERS imaging to a two-dimensional manifold space and categorize amorphous silicon structure, we developed a multiresolution manifold learning algorithm. It allows for quantifying average Si-Si distortion angle and the strain free energy at nanoscale without a human-specified physical threshold. The multiresolution feature of the multiresolution manifold learning allows for distilling local defects of ultra-low abundance (< 0.3%), presenting a new Raman mode at finer resolution grids. This work promises a general paradigm of resolving nanoscale structural heterogeneity and updating domain knowledge for highly disordered materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Accelerating amorphous polymer electrolyte screening by learning to reduce errors in molecular dynamics simulated properties

Polymer electrolytes are promising candidates for the next generation lithium-ion battery technology. Large scale screening of polymer electrolytes is hindered by the significant cost of molecular dynamics (MD) simulation in amorphous systems: the amorphous structure of polymers requires multiple, repeated sampling to reduce noise and the slow relaxation requires long simulation time for convergence. Here, we accelerate the screening with a multi-task graph neural network that learns from a large amount of noisy, unconverged, short MD data and a small number of converged, long MD data. We achieve accurate predictions of 4 different converged properties and screen a space of 6247 polymers that is orders of magnitude larger than previous computational studies. Further, we extract several design principles for polymer electrolytes and provide an open dataset for the community. Our approach could be applicable to a broad class of material discovery problems that involve the simulation of complex, amorphous materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Total X-ray scattering and big-box modeling of pressure-induced local disorder and partial amorphization in CsPbBr 3

The mechanisms governing pressure-induced amorphization and its reversibility in halide perovskites are not yet fully understood, particularly the contribution of local disorder. We performed high-pressure synchrotron total X-ray scattering and reverse Monte Carlo (RMC) big-box modeling using CsPbBr 3 as a model system to investigate short-range structural evolution in both the ordered and partially amorphous phases. While diffraction data indicate that long-range order persists up to 2 GPa, pair distribution function (PDF) analysis reveals significant local distortions, including PbBr 6 octahedral tilting and Cs displacement, which influence the bandgap through a complex interplay between bond compression and angular tilting. Beyond 2 GPa, CsPbBr 3 undergoes partial amorphization, with significant disordering of Cs and Br, while the Pb sublattice remains preserved, allowing for structural recovery upon decompression. Our work, accounting for both short- and long-range structural evolution through RMC modeling, successfully captures how disorder shapes the structural response of halide perovskites under pressure.

critical phenomena↗
DOE OSTI2023

Ab initio structural dynamics of pure and nitrogen-containing amorphous carbon

Abstract Amorphous carbon (a-C) has attracted considerable interest due to its desirable properties, which are strongly dependent on its structure, density and impurities. Using ab initio molecular dynamics simulations we show that the sp 2 /sp 3 content and underlying structural order of a-C produced via liquid quenching evolve at high temperatures and pressures on sub-nanosecond timescales. Graphite-like densities ( $$\lesssim$$ ≲ 2.7 g/cc) favor the formation of layered arrangements characterized by sp 2 disordered bonding resembling recently synthesized monolayer amorphous carbon (MAC), while at diamond-like densities ( $$\gtrsim$$ ≳ 3.3 g/cc) the resulting structures are dominated by disordered tetrahedral sp 3 hybridization typical of diamond-like amorphous carbon (DLC). At intermediate densities the system is a highly compressible mixture of coexisting sp 2 and sp 3 regions that continue to segregate over 10’s of picoseconds. The addition of nitrogen (20.3%) (a-CN) generates major system features similar with those of a-C, but has the unexpected effect of reinforcing the thermodynamically disfavored carbon structural motifs at low and high densities, while inhibiting phase separation in the intermediate region. At the same time, no nitrogen elimination from the carbon framework is observed above $$\simeq$$ ≃ 2.8 g/cc, suggesting that nitrogen impurities are likely to remain embedded in the carbon structures during fast temperature quenches at high pressures.

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

Alternating-bias assisted annealing of amorphous oxide tunnel junctions

Superconducting quantum bits (qubits) rely on ultra-thin, amorphous oxide tunneling barriers that can have significant inhomogeneities and defects as grown. This can result in relatively large uncertainties and deleterious effects in the circuits, limiting the scalability. Finding a robust solution to the junction reproducibility problem has been a long-standing goal in the field. Here, we demonstrate a transformational technique for controllably tuning the electrical properties of aluminum-oxide tunnel junctions. This is accomplished using a low-voltage, alternating-bias applied individually to the tunnel junctions, with which resistance tuning by more than 70% can be achieved. The data indicates an improvement of coherence and reduction of two-level system defects. Transmission electron microscopy shows that the treated junctions are predominantly amorphous, albeit with a more uniform distribution of alumina coordination across the barrier. This technique is expected to be useful for other devices based on ionic amorphous materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Ultrathin quasi-2D amorphous carbon dielectric prepared from solution precursor for nanoelectronics

Abstract Materials keeping thickness in atomic scale but extending primarily in lateral dimensions offer properties attractive for many emerging applications. However, compared to crystalline counterparts, synthesis of atomically thin films in the highly disordered amorphous form, which avoids nonuniformity and defects associated with grain boundaries, is challenging due to their metastable nature. Here we present a scalable and solution-based strategy to prepare large-area, freestanding quasi-2D amorphous carbon nanomembranes with predominant sp 2 bonding and thickness down to 1–2 atomic layers, from coal-derived carbon dots as precursors. These atomically thin amorphous carbon films are mechanically strong with modulus of 400 ± 100 GPa and demonstrate robust dielectric properties with high dielectric strength above 20 MV cm −1 and low leakage current density below 10 −4 A cm −2 through a scaled thickness of three-atomic layers. They can be implemented as solution-deposited ultrathin gate dielectrics in transistors or ion-transport media in memristors, enabling exceptional device performance and spatiotemporal uniformity.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Localized electronic and vibrational states in amorphous diamond

Amorphous diamond structures are generated by quenching high-density high-temperature liquid carbon using tight-binding molecular-dynamics simulations. We show that the generated amorphous diamond structures are predominated by strong tetrahedral bonds with the sp 3 bonding fraction as high as 97%, thus exhibit an ultra-high incompressibility and a wide band gap close to those of crystalline diamond. A small amount of sp 2 bonding defects in the amorphous sample contributes to localized electronic states in the band gap while large local strain gives rise to localization of vibrational modes at both high and low frequency regimes.

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

Importance of multimodal characterization and influence of residual Li 2 S impurity in amorphous Li 3 PS 4 inorganic electrolytes

Amorphous Li 3 PS 4 (LPS) solid-state electrolytes are promising for energy-dense lithium metal batteries. LPS glass, synthesized from a 3:1 mol ratio of Li 2 S and P 2 S 5 , has high ionic conductivity and can be synthesized by ball milling or solution processing. Ball milling has been attractive because it provides the easiest route to access amorphous LPS with a conductivity of 3.5 × 10 –4 S cm –1 (20 °C). However, achieving the complete reaction of precursors via ball milling can be difficult, and most literature reports use X-ray diffraction (XRD) or Raman spectroscopy to confirm sample purity, both of which have limitations. Furthermore, the effect of residual precursors on ionic conductivity and lithium metal cycling is unknown. In this work, we illustrate the importance of multimodal characterization to determine LPS phase and chemical purity. To determine the residual Li 2 S content in LPS, we show that (1) XRD and 31 P solid state nuclear magnetic resonance (ssNMR) are insufficient and (2) Raman loses sensitivity at concentrations below 12 mol% Li 2 S. Most importantly, we show that 7 Li ssNMR is highly sensitive. Using 7 Li ssNMR, we investigate the effect of ball milling parameters and develop a robust and highly reproducible procedure for pure LPS synthesis. We find that as the residual Li 2 S precursor content increases, LPS conductivity decreases and lithium metal batteries exhibit higher overpotentials and poor cycle life. Furthermore, our work reveals the importance of multimodal characterization techniques for amorphous solid-state electrolyte characterization and will enable better synthetic strategies for highly conductive electrolytes for efficient energy-dense solid-state lithium metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Structural water in amorphous carbonate minerals: ab initio molecular dynamics simulations of X-ray pair distribution experiments

Water is known to play a controlling role in directing mineralization pathways and stabilizing metastable amorphous intermediates in hydrous carbonate mineral MCO 3 ·nH 2 O systems, where M 2+ is a divalent metal cation. Despite this recognition, the nature of the controls on crystallization is poorly understood, largely owing to the difficulty in characterizing the dynamically disordered structures of amorphous intermediates at the atomic scale. Here, we present a series of atomistic models, derived from ab initio molecular dynamics simulation, across a range of experimentally relevant cations (M = Ca, Mg, Sr) and hydration levels (0 ≤ n ≤ 2). Theoretical simulations of the dependence of the X-ray pair distribution function on the hydration level n show good agreement with available experimental data and thus provide further evidence for a lack of significant nanoscale structure in amorphous carbonates. Upon dehydration, the metal coordination number does not change significantly, but the relative extent of water dissociation increases, indicating that a thermodynamic driving force exists for water dissociation to accompany dehydration. Mg strongly favors monodentate conformation of carbonate ligands and shows a marked preference to exchange monodentate carbonate O for water O upon hydration, whereas Ca and Sr exchange mono- and bidentate carbonate ligands with comparable frequency. Finally, water forms an extensive hydrogen bond network among both water and carbonate groups that exhibits frequent proton transfers for all three cations considered suggesting that proton mobility is likely predominantly due to water dissociation and proton transfer reactions rather than molecular water diffusion.

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

Elucidating the reversible exsolution–dissolution behaviour of high-entropy oxides in crystalline and amorphous phases

High-entropy oxides (HEOs), as a subclass of high-entropy materials (HEMs), offer a versatile platform for catalysis by leveraging entropy-stabilized solid solutions with tunable compositions, lattice structures, and electronic properties. While exsolution–dissolution of metal species in crystalline HEOs has emerged as a promising strategy for reversible active sites regeneration, the dynamic behaviour of HEOs possessing amorphous nature remains under-explored, particularly the difference with crystalline counterparts. In this work, we systematically investigate the architecture-dependent exsolution–dissolution behavior of HEOs by comparing a crystalline-phase HEO (c-HEO) and an amorphous-phase HEO (a-HEO), both comprising Ni, Mg, Cu, Zn, and Co as principal metal elements. Using a combination of in situ variable-temperature X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron microscopy, and in situ CO diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS), the structural evolution of the two HEO phases under redox conditions was elucidated. Both materials exhibit reversible exsolution of metallic species or alloys in reducing environments, followed by re-incorporation into the host lattice upon oxidation. Remarkably, the a-HEO demonstrates more facile and dynamic self-healing behavior, with alloy exsolution and dissolution occurring under milder conditions because of its enhanced reducibility and structural disorder. This study provides critical insights into the design of next-generation regenerable catalysts based on amorphous HEOs, highlighting the role of phase structure in governing reversible metal-site formation dynamics and catalytic performance.

Wang, Qingju [Univ. of Tennessee, Knoxville, TN (U↗