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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 595 records · Page 33
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Magnetism in Mixed Valence, Defect, Cubic Perovskites: BaIn 1– x Fe x O 2.5+δ , x = 0.25, 0.50, and 0.75. Local and Average Structures

The series BaIn 1–x Fe x O 2.5+δ , x = 0.25, 0.50, and 0.75, has been prepared under air-fired and argon-fired conditions and studied using X-ray diffraction, d.c. and a.c. susceptibility, Mössbauer spectroscopy, neutron diffraction, X-ray near edge absorption spectroscopy (XANES), and X-ray pair distribution (PDF) methods. While Ba 2 In 2 O 5 (BaInO 2.5 ) crystallizes in an ordered brownmillerite structure, Ibm2, and Ba 2 Fe 2 O 5 (BaFeO 2.5 ) crystallizes in a complex monoclinic structure, P2 1 /c, showing seven Fe 3+ sites with tetrahedral, square planar, and octahedral environments, all phases studied here crystallize in the cubic perovskite structure, Pm$\bar{}3}$m, with long-range disorder on the small cation and oxygen sites. 57 Fe Mössbauer studies indicate a mixed valency, Fe 4+ /Fe 3+ , for both the air-fired and argon-fired samples. The increased Fe 3+ content for the argon-fired samples is reflected in increased cubic cell constants and in the increased Mössbauer fraction. It appears that the Pm$\bar{}3}$m phases are only metastable when fired in argon. From a slightly modified percolation theory for a primitive cubic lattice (taking into account the presence of random O atom vacancies), long-range spin order is permitted for the x = 0.50 and 0.75 phases. Instead, the d.c. susceptibility shows only zero-field-cooled (ZFC) and field-cooled (FC) divergences at ~6 K [5 K] for x = 0.50 and at ~22 K [21 K] for x = 0.75, with values for the argon-fired samples in [ ]. Neutron diffraction data for the air-fired samples confirm the absence of long-range magnetic order at any studied temperature. For the air-fired x = 0.50, a.c. susceptibility data show a frequency-dependent χ'(max) and spin glass behavior, while for x = 0.75, χ'(max) is invariant with frequency, ruling out either a spin glass or a superparamagnetic ground state. These behaviors are discussed in terms of competing Fe 3+ –Fe 3+ antiferromagnetic exchange and ferromagnetic Fe 3+ –Fe 4+ exchange. The PDF and 57 Fe Mössbauer data indicate a local structure at short interatomic distances, which deviates strongly from the average Pm$\bar{}3}$m model. Fe Mössbauer, PDF, and XANES data show a systematic dependence on x and indicate that the Fe 3+ sites are largely fourfold-coordinated and Fe 4+ sites are fivefold- or sixfold-coordinated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Solution-Processed Layered Gallium Telluride Thin-Film Photodetectors

Using scalable solution processing, layered gallium telluride (GaTe) nanoflake dispersions are produced in surfactant-free, low-boiling-point, water–ethanol cosolvent mixtures. During exfoliation, chemical degradation of the ambient-reactive GaTe crystals is minimized by using deoxygenated solvents in a sealed tip ultrasonication system. The structural and chemical integrity of the solution-processed GaTe nanoflakes is subsequently confirmed with a comprehensive suite of microscopic and spectroscopic analyses. Furthermore, field-effect transistors and phototransistors based on individual solution-processed GaTe nanoflakes show electronic and optoelectronic properties, respectively, that are comparable to micromechanically exfoliated GaTe. Minimal solution-processing residues from the surfactant-free, low-boiling-point cosolvent dispersion medium coupled with the high intrinsic hole doping of GaTe produces the highest electrical conductivity among solution-processed layered nanoflake thin films without post-treatment. Large-area photodetectors based on these electrically percolating thin films of solution-processed GaTe nanoflakes show a positive correlation between responsivity and illumination intensity, with a high photoconversion gain that is explained by a combination of defect-mediated optical processes and photothermal effects. Finally, overall, this study establishes solution-processed layered GaTe nanoflakes as a leading candidate for high-performance, large-area, thin-film photodetectors.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Shear Response of Ionizable Polymer Melts at the Crossover from Ionomers to Polyelectrolytes

Nonlinear shear response of polymers is affected by inherent barriers for diffusive motion, including entanglements and topology. In ionizable polymers, ionic clusters further constrain the intrinsic dynamics of the polymers, significantly enhancing their viscosity. Here, using fully atomistic molecular dynamics simulations, the nonlinear shear response of ionizable polymers is presented, across the transition from the ionomer regime where distinctive clusters dominate the structure to the polyelectrolyte regime where clusters percolate, in polystyrene randomly sulfonated with fractions of SO 3 − groups of f = 0.20 and 0.35, in pristine and tetrahydrofuran (THF) swollen polyelectrolyte melts. For f = 0.20, the ionic clusters first fracture into smaller clusters followed by splitting into individual ionic groups and eventually reform. At higher f, the clusters morph in shape but do not break under high shear. At very high shear rates, all of the chains stretch and recoil rapidly. As the shear rate is reduced, some chains stretch and recoil, while others remain largely unaffected by the shear. Macroscopically, for all systems, the shear viscosity displays initially an elastic response, followed by nonlinear shear stress overshoot and, eventually, a steady state. The evolution of viscosity with time and shear reflects that of the ionizable domains.

cluster chemistry↗
DOE OSTI2015

Charge Transport at Ti-Doped Hematite (001)/Aqueous Interfaces

Solid-state transport and electrochemical properties of Ti-doped hematite (001) epitaxial thin films (6.0, 8.3, and 16.6 at% Ti) were probed to achieve a better understanding of doped hematite for photoelectrochemical (PEC) applications. Room temperature resistivity measurements predict a resistivity minimum near 10 at% Ti doping, which can be rationalized as maximizing charge compensating Fe2+ concentration and Fe3+ electron accepting percolation pathways simultaneously. Temperature dependent resistivity data are consistent with small polaron hopping, revealing an activation energy that is Ti concentration dependent and commensurate with previously reported values (≈ 0.11 eV). In contact with inert electrolyte, linear Mott-Schottky data at various pH values indicate that there is predominantly a single donor for Ti-doped hematite at 6.0 at% Ti and 16.6 at% Ti concentrations. Two slope Mott-Schottky data at pH extremes indicate the presence of a second donor or surface state in the 8.3 at% Ti-doped film, with an energy level ≈ 0.7 eV below the Fermi level. Mott-Schottky plots indicate pH and Ti concentration dependent flatband potentials of -0.4 to -1.1 V vs. Ag/AgCl, commensurate with previously reported data. Flatband potentials exhibited super-Nernstian pH dependence ranging from -69.1 to -101.0 mV/pH. Carrier concentration data indicate that the Fermi energy of the Ti-doped system is Ti concentration dependent, with a minimum of 0.15 eV near 10 at% Ti. These energy level data allow us to construct an energy band diagram for Ti-doped hematite electrode/electrolyte interfaces, and to determine a Ti-doping concentration t

Environmental Molecular Sciences Laboratory↗
DOE OSTI2015

Structural and Chemical Evolution of Li- and Mn-rich Layered Cathode Material

Lithium (Li)- and manganese-rich (LMR) layered-structure materials are very promising cathodes for high energy density lithium-ion batteries. However, their voltage fading mechanism and its relationships with fundamental structural changes are far from being sufficiently understood. Here we report the detailed phase transformation pathway in the LMR cathode (Li[Li0.2Ni0.2Mn0.6]O2) during cycling for the samples prepared by hydro-thermal assistant method. It is found the transformation pathway of LMR cathode is closely correlated to its initial structure and preparation conditions. The results reveal that LMR cathode prepared by HA approach experiences a phase transformation from the layered structure to a LT-LiCoO2 type defect spinel-like structure (Fd-3m space group) and then to a disordered rock-salt structure (Fm-3m space group). The voltage fade can be well correlated with the Li ion insertion into octahedral sites, rather than tetrahedral sites, in both defect spinel-like structure and disordered rock-salt structure. The reversible Li insertion/removal into/from the disordered rock-salt structure is ascribed to the Li excess environment that can satisfy the Li percolating in the disordered rock-salt structure despite the increased kinetic barrier. Meanwhile, because of the presence of a great amount of oxygen vacancies, a significant decrease of Mn valence is detected in the cycled particle, which is below that anticipated for a potentially damaging Jahn-Teller distortion (+3.5). Clarification of the phase transformation pathway, cation redistribution, oxygen vacancy and Mn valence change undoubtedly provides insights into a profound understanding on the voltage fade, and capacity degradation of LMR cathode. The results also inspire us to further enhance the reversibility of LMR cathode via improving its surface structural stability.

Cation redistribution↗
DOE OSTI2025

Local Cation-Ordered Superlattice Stabilizing Ni-Rich Single-Crystalline Cathodes

Ni-rich single-crystalline cathodes are pivotal for advancing lithium-ion battery technology due to their high energy density and mechanical stability. However, Ni-rich single-crystalline particles face intrinsic structural heterogeneity due to excessively high sintering temperature required to shape micron-sized morphologies─typically over 150 °C above the polycrystalline optimum, leading to rapid electrochemical decay and unsatisfied rate performance that hinder their practical application. Here, in this work, we propose a lithium-deficient presintering strategy to synthesize cation-ordered single-crystalline LiNi 0.83 Co 0.12 Mn 0.05 O 2 (S-NCM83), effectively minimizing lattice chemical heterogeneity and defect formation. The resulting cation-ordered percolation network enhances the structural stability of the bulk, reduces the energy barrier for Li + migration, and stabilizes Li + diffusion pathways. Consequently, S-NCM83 demonstrates significantly improved cycling stability across various operating temperatures and achieves exceptional rate performance, delivering 206 mAh g –1 at 0.1 C and 170 mAh g –1 at 5 C, without requiring surface coatings or doping. This work introduces a universal strategy to address the long-standing structural instability issues in single-crystalline cathodes, paving the way for simplified and scalable approaches to long-life and high-energy lithium-ion batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Multiprincipal Component P2-Na 0.6 (Ti 0.2 Mn 0.2 Co 0.2 Ni 0.2 Ru 0.2 )O 2 as a High-Rate Cathode for Sodium-Ion Batteries

Mixing transition metal cations in nearly equiatomic proportions in layered oxide cathode materials is a new strategy for improving the performances of Na-ion batteries. The mixing of cations not only offers entropic stabilization of the crystal structure but also benefits the diffusion of Na ions with tuned diffusion activation energy barriers. In light of this strategy, a high-rate Na 0.6 (Ti 0.2 Mn 0.2 Co 0.2 Ni 0.2 Ru 0.2 )O 2 cathode was designed, synthesized, and investigated, combining graph-based deep learning calculations and complementary experimental characterizations. This new cathode material delivers high discharge capacities of 164 mA g –1 at 0.1 C and 68 mAh g –1 at a very high rate of 86 C, demonstrating an outstanding high rate capability. Ex situ and operando synchrotron X-ray diffraction were used to reveal the detailed structural evolution of the cathode upon cycling. Using the climbing-image nudged elastic-band calculation and Ab initio molecular dynamics simulations, we show that the optimal transition metal composition enables a percolating network of low barrier pathways for fast, macroscopic Na diffusion, resulting in the observed high rate performance.

25 ENERGY STORAGE↗
DOE OSTI2019

Linking structural and transport properties in three-dimensional fracture networks

Here, we investigate large scale particle motion and solute breakthrough in sparse three-dimensional discrete fracture networks (DFN) characterized by power-law distributed fracture lengths. The three networks we consider have the same fracture intensity values but exhibit different percolation densities, geometric properties and topological structures. We considered two different average transport models to predict solute breakthrough, a streamtube model and a Bernoulli CTRW model, both of which provide insights into the flow fields within the networks. The streamtube model provides acceptable predictions at short distances in two of the networks, but fails in all cases to predict breakthrough times at the outlet plane, which indicates that particle motion in such fracture networks cannot be characterized by a constant velocity between the inlet and control plane at which the breakthrough curve is detected. Rather the structure of the network requires that frequent velocity transitions be made as particles move through the system. Despite the relatively broad distribution of fracture radii and relatively small number of independent velocity transitions, the CTRW approach conditioned on the initial velocity distribution provides reasonable predictions for the breakthrough curves at different distances from the inlet. The application of these averaged transport models provides a richer understanding of the link from the fracture network structure to ow and transport properties.

58 GEOSCIENCES↗
DOE OSTI2019

Impact of Confining Stress on Capillary Pressure Behavior During Drainage Through Rough Fractures

In this work we study, numerically, the behavior of capillary pressure $(P_c)$ during slow immiscible displacement in a rough fracture as a function of the degree of fracture aperture heterogeneity that results from two distinct mechanisms: normal confining stress and fracture surface correlation. We generate synthetic self-affine rough fractures at different correlation scales, solve the elastic contact problem to model the effect of confining stress, and simulate slow immiscible displacement of a wetting fluid by a nonwetting one using a modified invasion percolation model that accounts for in-plane curvature of the fluid-fluid interface. Our modeling results indicate that the power spectral density, $S(f)$, of $P_c$, can be used to qualitatively characterize fracture aperture heterogeneity. We show that the distribution of forward avalanche sizes follows a power law $N_f (S_f)$ ∝ $S^{-a}_f$ , with exponent $α$ = 2, in agreement with previously reported values for porous media and equal to the expected theoretical exponent for a self-organized criticality process.

58 GEOSCIENCES↗
DOE OSTI2019

Robust Predictive Design of Field Measurements for Evapotranspiration Barriers Using Universal Multiple linear Regression

Surface barriers are normally installed to reduce downward water movement into contaminated zones. Specifically, evapotranspiration (ET) barriers are used to store water and release it, via ET, before it can percolate into an underlying waste zone. To assess the effectiveness of a surface barrier, we used an existing data set, model-simulated data, and a dimensionality reduction approach called universal multiple linear regression (uMLR) to optimize the required number of sensors in a 2-m thick surface barrier. To understand the usefulness of implementing predictive uMLR to accommodate multiple monitoring objectives, we compare several network designs, selected based on down-sampling of existing data, with a recommended sensor design based on model simulations performed without consideration of existing data. We further added consideration of “fuzzy” design, which allows more practical guidelines for field implementation of uMLR. We discovered that uMLR, combined with robust decision-making, provides a simple, flexible, and high-quality network design for monitoring the total water stored in a surface barrier across multiple uncertain conditions.

58 GEOSCIENCES↗
DOE OSTI2021

Numerical and Analytical Modeling of Flow Partitioning in Partially Saturated Fracture Networks

Infiltration processes in fractured-porous media remain a crucial, yet not very well understood component of recharge and vulnerability assessment. Under partially-saturated conditions flows in fractures, percolating fracture networks, and fault zones contribute to the fastest spectrum of infiltration velocities via preferential pathways. Specifically, the partitioning dynamics at fracture intersections determine the magnitude of flow fragmentation into vertical and horizontal components and hence the bulk flow velocity and dispersion of fracture networks. In this work, we derive an approximate analytical solution for the partitioning process and validate it using smoothed particle hydrodynamics simulations. The developed transfer function is conceptually based on simulation results and laboratory experiments carried out in previous works. It allows to efficiently simulate flow through fracture networks with simple cubic structure and arbitrary number of fractures and aperture sizes via linear response theory and convolution of a given input signal. We derive a non-dimensional bulk flow velocity ($\widetilde{v}$) and dispersion coefficient ($\widetilde{D}$) to characterize fracture networks in terms of dimensionless horizontal and vertical time scales $\tau_m$ and $\tau_0$. The dispersion coefficient is shown to strongly depend on the horizontal time scale and converges towards a constant value of $0.08$ within reasonable fluid and geometrical parameter ranges, while the non-dimensional velocity exhibits a characteristic $\widetilde{v} \sim \tau_m^{-1/2}$ scaling. Given that hydraulic information is often only available at limited places within (fractured-porous) aquifer system, such as boreholes or springs, our study intends to provide a rudimentary analytical concept to potentially reconstruct internal fracture network geometries from external boundary information, e.g., the dispersive properties of discharge (groundwater level fluctuations).

42 ENGINEERING↗
DOE OSTI2021

Characterizing the Effect of Capillary Heterogeneity on Multiphase Flow Pulsation in an Intermediate–Scale Beadpack Experiment using Time Series Clustering and Frequency Analysis

An intermediate-scale beadpack drainage experiment was conducted to investigate how simple layered lamination heterogeneity affects CO 2 flow. Two simple layers of capillary barriers are manually packed in the tank and slow drainage was carried out using analog fluids to mimic the capillary- and gravity-dominated CO 2 upward migration process in deep saline aquifers. Nonwetting phase saturation time series clustering analysis and frequency analysis have been conducted on the experimental data. Additionally, modified invasion percolation numerical simulations were done on a digital model of the beadpack to compare to experimental results. Results show that capillary barriers can lead to strong pulsation behavior, which in turn can cause unexpected early breaching through other barriers. The inlet pressure is found to be able to respond to saturation changes in far regions of the domain, indicating that the wetting phase can transmit pressure changes from the other phase. Although static simulations were not able to capture all the dynamic behavior observed in the experiment, Monte Carlo composite simulation results combining many different realizations can better illustrate how the nonwetting phase will behave in the heterogeneous domain. Furthermore, our results suggest the need for CO 2 storage site selection with preference given to aquifers with more capillary barriers with finer grain sizes to avoid flow pulsation and to retard plume upward migration.

58 GEOSCIENCES↗
DOE OSTI2022

Quantifying the Impact of Lagged Hydrological Responses on the Effectiveness of Groundwater Conservation

Many irrigated agricultural areas seek to prolong the lifetime of their groundwater resources by reducing pumping. However, it is unclear how lagged responses, such as reduced groundwater recharge caused by more efficient irrigation, may impact the long-term effectiveness of conservation initiatives. Here, we use a variably saturated, simplified surrogate groundwater model to: 1) analyze aquifer responses to pumping reductions, 2) quantify time lags between reductions and groundwater level responses, and 3) identify the physical controls on lagged responses. We explore a range of plausible model parameters for an area of the High Plains Aquifer (USA) where stakeholder-driven conservation has slowed groundwater depletion. We identify two types of lagged responses that reduce the long-term effectiveness of groundwater conservation, recharge-dominated and lateral-flow-dominated, with vertical hydraulic conductivity (K Z ) the major controlling variable. When high K z allows percolation to reach the aquifer, more efficient irrigation reduces groundwater recharge. By contrast, when low K z impedes vertical flow, short term changes in recharge are negligible, but pumping reductions alter the lateral flow between the groundwater conservation area and the surrounding regions (lateral-flow-dominated response). For the modeled area, we found that a pumping reduction of 30% resulted in median usable lifetime extensions of 20 or 25 years, depending on the dominant lagged response mechanism (recharge- vs. lateral-flow-dominated). These estimates are far shorter than estimates that do not account for lagged responses. To conclude, results indicate that conservation-based pumping reductions can extend aquifer lifetimes, but lagged responses can create a sizable difference between the initially perceived and actual long-term effectiveness.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Predicting Flow in Fracture Networks With Quantum Algorithms

Uncertainty quantification plays a crucial role in the modeling of subsurface flow. For instance, uncertainties in the properties of geologic fracture networks significantly impact flow, requiring numerous simulations to accurately estimate quantities of interest. However, each simulation is computationally expensive because it requires solving a large linear system to capture features that involve both small and large fractures. An example is in percolation, where the interaction of many small fractures (which cumulatively can have a large surface area) with the rock matrix must be modeled precisely. Quantum computing is an emerging tool with the potential to address this issue. Quantum algorithms offer a significant speedup in solving linear systems, achieving efficiencies that are challenging to match with classical approaches. These classical approaches include direct solvers, such as LU decomposition, and iterative methods, notably preconditioned conjugate gradient, commonly used in subsurface modeling to solve large sparse systems. However, applying quantum algorithms to geologic fracture flow requires careful attention to algorithmic and problem-specific constraints to fully realize this quantum advantage. In this work we describe a quantum algorithm for generalized Monte Carlo applications with a quadratic speedup over the classical approaches which can be combined with the quantum speedup, currently under investigation, for solving quantum linear systems for subsurface flow. We show that for quantum algorithms the computational cost of estimating a quantity of interest for a statistical ensemble of networks is roughly the same as that of a single realization, essentially implying that one can get uncertainty quantification for free.

58 GEOSCIENCES↗
DOE OSTI2017

Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials

Recent progress in the understanding of percolation theory points to cation-disordered lithium-excess transition metal oxides as high-capacity lithium-ion cathode materials. Nevertheless, the oxygen redox processes required for these materials to deliver high capacity can trigger oxygen loss, which leads to the formation of resistive surface layers on the cathode particles. Here, we demonstrate here that, somewhat surprisingly, fluorine can be incorporated into the bulk of disordered lithium nickel titanium molybdenum oxides using a standard solid-state method to increase the nickel content, and that this compositional modification is very effective in reducing oxygen loss, improving energy density, average voltage, and rate performance. We argue that the valence reduction on the anion site, offered by fluorine incorporation, opens up significant opportunities for the design of high-capacity cation-disordered cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2022

Folded network and structural transition in molten tin

The fundamental relationships between the structure and properties of liquids are far from being well understood. For instance, the structural origins of many liquid anomalies still remain unclear, but liquid-liquid transitions (LLT) are believed to hold a key. However, experimental demonstrations of LLTs have been rather challenging. Here, we report experimental and theoretical evidence of a second-order-like LLT in molten tin, one which favors a percolating covalent bond network at high temperatures. The observed structural transition originates from the fluctuating metallic/covalent behavior of atomic bonding, and consequently a new paradigm of liquid structure emerges. The liquid structure, described in the form of a folded network, bridges two well-established structural models for disordered systems, i.e., the random packing of hard-spheres and a continuous random network, offering a large structural midground for liquids and glasses. Our findings provide an unparalleled physical picture of the atomic arrangement for a plethora of liquids, shedding light on the thermodynamic and dynamic anomalies of liquids but also entailing far-reaching implications for studying liquid polyamorphism and dynamical transitions in liquids.

36 MATERIALS SCIENCE↗