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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 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Efficient Scalable Parallel Higher Order Direct MoM-SIE Method With Hierarchically Semiseparable Structures for 3-D Scattering

A novel fast scalable parallel algorithm is proposed for the solution of large 3-D scattering problems based on: 1) the double (geometrical and current-approximation) higher order (DHO) method of moments (MoM) in the surface integral equation (SIE) formulation and 2) a direct solver for dense linear systems utilizing hierarchically semiseparable (HSS) structures. Namely, an HSS matrix representation is used for compression, factorization, and solution of the system matrix. In addition, a rank-revealing QR decomposition for memory compression is used, with a stopping criterion in terms of the relative rank tolerance value. One method for geometrical preprocessing of the scatterers based on the cobblestone distance sorting technique is employed in order to enhance the HSS algorithm accuracy and parallelization. Numerical examples show how the accuracy of the DHO HSS-MoM-SIE method is easily controllable by using the relative tolerance for the matrix compression. Furthermore, the examples demonstrate low memory consumption, as well as much faster simulation time, when compared to the direct LU decomposition. The method enables dramatically faster monostatic scattering computations than iterative solvers and reduced number of unknowns when compared to low-order discretizations. Finally, great scalability of the algorithm is demonstrated on more than one thousand processes.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2019

Scission of the Five-Membered Ring in 1- H -Inden-1-one C 9 H 6 O and Indenyl C 9 H 7 in the Reactions with H and O Atoms

Quantum chemical G3(MP2,CC)//B3LYP/6-311G(d,p) calculations of the C 9 H 7 O potential energy surface were utilized to investigate the mechanism of the 1-H-inden-1-one (C 9 H 6 O) + H and indenyl (C 9 H 7 ) + O reactions and were combined with Rice–Ramsperger–Kassel–Marcus Master Equation (RRKM-ME) calculations to predict temperature- and pressure-dependent reaction rate constants and product branching ratios. The most favorable reaction pathways for C 9 H 6 O + H lead to the bimolecular C 8 H 7 + CO products, which are slightly endothermic with respect to the reactants. The reaction begins with H addition to the ortho or meta C atoms in the five-membered ring, C 9 H 6 O + H → w2/w3, and then proceeds by isomerization to w1, (w3 →) w2 → w1. From thereon, the w1 → w9 → w8 → p1 and w2 → w8 → p1 pathways lead to ortho-vinyl phenyl + CO, whereas w1 → w10 → w11 → p2 and C 9 H 6 O + H → w10 → w11 → p2 produce styrenyl + CO. The results of the RRKM-ME calculations showed that only the well-skipping C 9 H 6 O + H → C 8 H 7 (p1/p2) + CO mechanism is relevant under combustion conditions. A comparison with a smaller prototype 2,4-cyclopentadienone + H → C 4 H 5 + CO reaction demonstrated that the H atom is a less efficient destroyer of a cyclopentadienone-like moiety when this moiety is linked to an aromatic or a PAH structure. The C 9 H 7 + O reaction begins with highly exothermic barrierless addition of the oxygen atom to the radical site in the five-membered ring of indenyl producing w1 and then, the reaction mostly proceeds by β-scission in the five-membered ring, which may be preceded by H migration to w2 or w10, and completes by the CO loss forming the highly exothermic C 8 H 7 radical products. Modified Arrhenius expressions for the rate constants of all reactions pertinent to the formation of C 8 H 7 + CO from C 9 H 6 O + H, C 9 H 7 + H, and unimolecular decomposition of benzopyranyl have been generated and suggested for combustion kinetic modeling. Furthermore, it is concluded that the oxidation reactions of a five-membered ring with atomic oxygen remain fast in the presence of attached or surrounding six-membered rings.

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

Nonmonotonic-potential description of polarization effects, fusion, and nuclear rainbows in elastic scattering of 6 Li + 12 C at 4.5–600 MeV

The experimental differential cross-section (CS) and analyzing power (AP) data of the 6 Li + 12 C elastic scattering over a wide laboratory energy scale (4.5MeV≤𝐸 lab ≤600MeV) are analyzed within the framework of the optical model (OPM) using nonmonotonic (NM) nucleus–nucleus potentials. The real part of the NM potentials is derived from the Pauli-embodied energy density-functional (EDF) formalism with the sudden approximation. The real part of the noncentral spin-orbit and tensor terms, as well as the imaginary parts, are treated phenomenologically. The effect of the radius of sensitivity on the CS and AP data is found to be more important at lower energies. The diffractive and refractive scattering with Airy structures in the whole angular region of the elastic scattering across the studied energy range is successfully described within the OPM using the NM 6 Li + 12 C potential. The near- and far-side (N and F) decomposition of the total elastic-scattering amplitudes has also been studied using our NM potentials. The evolution of the Airy minima in the angular distributions, coupled with the fitting of the AP data, provides an accurate description of Airy minima of different orders. The OPM calculations with the NM potentials describe exceptionally well the CS, vector analyzing power (VAP), and tensor analyzing power data at 𝐸 lab =9.0,19.24,20,30, and 50MeV. In agreement with our past successful descriptions of CS and the opposite signs of the VAP data for the 6 Li and 7 Li elastic scattering using NM potentials in OPM, the present results appear to provide a better fit, so far, than those obtained from the coupled-channels method. The fusion cross sections of 6 Li + 12 C have been predicted in the energy range (4.5MeV≤𝐸 lab ≤20MeV), fitting the experimental data well in the range 𝐸 lab =2.97–11.77MeV. The EDF potential without any energy dependence and renormalization is also found to describe satisfactorily the experimental CS and AP data at energies up to several hundreds of MeV.

6 ≤ A ≤ 19↗
DOE OSTI2020

Phase Transformation of Thermally Aged and Neutron Irradiated Duplex Stainless Steel Used in LWRs. Final report

The lifetime of reactor components made of duplex stainless steels can be limited by the embrittlement from thermal aging, neutron irradiation or a synergistic effect between thermal aging and neutron irradiation. There is still a large scientific knowledge gap in understanding the phase evolution in duplex stainless steels upon thermal aging with or without neutron irradiation, the synergistic effect between thermal aging and neutron irradiation, and the impacts of structural evolution on material mechanical responses. In this project, totally, five major tasks were completed through this project: a) the in-situ WAXS tensile tests of thermally aged cast duplex stainless steels, b) the EXAFS investigation of thermally aged cast austenitic stainless steel and welds of austenite sainless steel, c) the characterization of irradiation effect on neutron irradiated CASS using APT, d) characterize the ferrite hardening of neutron irradiated CASS using nanoindentation, and e) the FEM modelling to validate the in-situ WAXS tensile tests and to simulate the stress/strain distribution during deformation for thermally aged duplex stainless steel. In summary, the thermal aging without neutron irradiation can significantly increase the strength of ferrite phase through the spinodal decomposition and G-phase precipitations. The in-situ X-ray experiments show that the hardening effect in ferrite phase can significantly alter the load partition between the ferrite and austenite phases. Atom probe tomography characterizations on samples irradiated to 0.08, 3, 5, 10, 20, and 40 dpa shows that neutron irradiation has dominated the microstructural evolution after 3 dpa, and the spinodal decomposition has saturated yet even at 40 dpa based on the quantified wavelength and amplitude.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2019

Enabling immersive engagement in energy system models with deep learning

Complex ensembles of energy simulation models have become crucial components of renewable energy research in recent years. Often the increasing computational cost, high-dimensional structure, and other complexities hinder researchers from fully utilizing these data sources for knowledge building. Researchers at National Renewable Energy Laboratory have determined an immersive visualization workflow to dramatically improve user engagement and analysis capability through a combination of low-dimensional structure analysis, deep learning, and custom visualization methods. We present case studies for two energy simulation platforms.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2015

Focus: Two-dimensional electron-electron double resonance and molecular motions: The challenge of higher frequencies

The development, applications, and current challenges of the pulsed ESR technique of two-dimensional Electron-Electron Double Resonance (2D ELDOR) are described. This is a three-pulse technique akin to 2D Exchange Nuclear Magnetic Resonance, but involving electron spins, usually in the form of spin-probes or spin-labels. As a result, it required the extension to much higher frequencies, i.e., microwaves, and much faster time scales, with π/2 pulses in the 2-3 ns range. It has proven very useful for studying molecular dynamics in complex fluids, and spectral results can be explained by fitting theoretical models (also described) that provide a detailed analysis of the molecular dynamics and structure. We discuss concepts that also appear in other forms of 2D spectroscopy but emphasize the unique advantages and difficulties that are intrinsic to ESR. Advantages include the ability to tune the resonance frequency, in order to probe different motional ranges, while challenges include the high ratio of the detection dead time vs. the relaxation times. We review several important 2D ELDOR studies of molecular dynamics. (1) The results from a spin probe dissolved in a liquid crystal are followed throughout the isotropic → nematic → liquid-like smectic → solid-like smectic → crystalline phases as the temperature is reduced and are interpreted in terms of the slowly relaxing local structure model. Here, the labeled molecule is undergoing overall motion in the macroscopically aligned sample, as well as responding to local site fluctuations. (2) Several examples involving model phospholipid membranes are provided, including the dynamic structural characterization of the boundary lipid that coats a transmembrane peptide dimer. Additionally, subtle differences can be elicited for the phospholipid membrane phases: liquid disordered, liquid ordered, and gel, and the subtle effects upon the membrane, of antigen cross-linking of receptors on the surface of plasma membrane, vesicles can be observed. These 2D ELDOR experiments are performed as a function of mixing time, T{sub m}, i.e., the time between the second and third π/2 pulses, which provides a third dimension. In fact, a fourth dimension may be added by varying the ESR frequency/magnetic field combination. Therefore, (3) it is shown how continuous-wave multifrequency ESR studies enable the decomposition of complex dynamics of, e.g., proteins by virtue of their respective time scales. These studies motivate our current efforts that are directed to extend 2D ELDOR to higher frequencies, 95 GHz in particular (from 9 and 17 GHz), in order to enable multi-frequency 2D ELDOR. This required the development of quasi-optical methods for performing the mm-wave experiments, which are summarized. We demonstrate state-of-the-art 95 GHz 2D ELDOR spectroscopy through its ability to resolve the two signals from a spin probe dissolved in both the lipid phase and the coexisting aqueous phase. As current 95 GHz experiments are restricted by limited spectral coverage of the π/2 pulse, as well as the very short T{sub 2} relaxation times of the electron spins, we discuss how these limitations are being addressed.

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

Extended dynamic mode decomposition for model reduction in fluid dynamics simulations

High computational cost and storage/memory requirements of fluid dynamics simulations constrain their usefulness as a predictive tool. Reduced-order models (ROMs) provide a viable solution to this challenge by extracting the key underlying dynamics of a complex system directly from data. We investigate the efficacy and robustness of an extended dynamic mode decomposition (xDMD) algorithm in constructing ROMs of three-dimensional cardiovascular computations. Focusing on the ROMs' accuracy in representation and interpolation, we relate these metrics to the truncation rank of singular value decomposition, which underpins xDMD and other approaches to ROM construction. Our key innovation is to relate the truncation rank to the singular values of the original flow problem. This result establishes a priori guidelines for the xDMD deployment and its likely success as a means of data compression and reconstruction of the system's dynamics from dominant spatiotemporal structures present in the data.

Mechanics↗
DOE OSTI2021

Foundations of variational discrete action theory

Variational wave functions and Green's functions are two important paradigms for solving quantum Hamiltonians, each having their own advantages. Here we detail the variational discrete action theory (VDAT), which exploits the advantages of both paradigms in order to approximately solve the ground state of quantum Hamiltonians. VDAT consists of two central components: the sequential product density matrix (SPD) ansatz and a discrete action associated with the SPD. The SPD is a variational ansatz inspired by the Trotter decomposition and characterized by an integer $\mathscr{N}$, recovering many well-known variational wave functions, in addition to the exact solution for $\mathscr{N}$ = ∞. The discrete action describes all dynamical information of an effective integer time evolution with respect to the SPD. We generalize the path integral to our integer time formalism, which converts a dynamic correlation function in integer time to a static correlation function in a compound space. We also generalize the usual many-body Green's function formalism to integer time, which results in analogous but distinct mathematical structures, yielding integer time versions of the generating functional, Dyson equation, and Bethe-Salpeter equation. We prove that the SPD can be exactly evaluated in the multiband Anderson impurity model (AIM) by summing a finite number of diagrams. For the multiband Hubbard model, we prove that the self-consistent canonical discrete action approximation (SCDA), which is the integer time analog of the dynamical mean-field theory, exactly evaluates the SPD for d = ∞. VDAT within the SCDA provides an efficient yet reliable method for capturing the local physics of quantum lattice models, which will have broad applications for strongly correlated electron materials. More generally, VDAT should find applications in various many-body problems in physics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Structural and chemical changes in hardwood cell walls during early stages of flash pyrolysis

Volatile products from thermal decomposition of lignocellulosic biomass have been well characterized, but the solid- and liquid-phase reactions during the early stages of decomposition are largely unknown. Here the initial solid-phase biomass thermal deconstruction reactions were analyzed in situ and with high particle heating rates, delineating how these processes occur. A variety of instrumentation was used to quantify the extent and relative rates of deconstruction, demonstrating that biopolymers resist the thermally energetic conditions to differing degrees, even when ensconced in biomass cell walls. Hemicellulose and the more frangible lignin components decompose and volatilize more readily than cellulose, which temporarily enriches biomass with cellulose. These chemical changes manifest in larger cell wall structural and mechanical property transformations. In all, this investigation concludes that these solid-phase reactions strongly influence the production rates of volatile species and will require additional study before these processes can be modeled precisely to improve yields of desired product.

09 BIOMASS FUELS↗
DOE OSTI2019

Simulation of unsteady blood flows in a patient-specific compliant pulmonary artery with a highly parallel monolithically coupled fluid-structure interaction algorithm

Computational fluid dynamics (CFD) is increasingly used to study blood flows in patient-specific arteries for understanding certain cardiovascular diseases. The techniques work quite well for relatively simple problems, but need improvements when the problems become harder in the case when (1) the geometry becomes complex (from a few branches to a full pulmonary artery), (2) the model becomes more complex (from fluid-only calculation to coupled fluid-structure interaction calculation), (3) both the fluid and wall models become highly nonlinear, and (4) the computer on which we run the simulation is a supercomputer with tens of thousands of processor cores. To push the limit of CFD in all four fronts, in this paper, we develop and study a highly parallel algorithm for solving a monolithically coupled fluid-structure system for the modeling of the interaction of the blood flow and the arterial wall. As a case study, we consider a patient-specific, full size pulmonary artery obtained from CT (Computed Tomography) images, with an artificially added layer of wall with a fixed thickness. The fluid is modeled with a system of incompressible Navier-Stokes equations and the wall is modeled by a geometrically nonlinear elasticity equation. As far as we know this is the first time the unsteady blood flow in a full pulmonary artery is simulated without assuming a rigid wall. We report the proposed numerical algorithm and software scale well beyond 10,000 processor cores on a supercomputer for solving the fluid-structure interaction problem discretized with a stabilized finite element method in space and an implicit scheme in time involving hundreds of millions of unknowns.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2023

Effect of Salt Concentration on the Interfacial Solvation Structure and Early Stage of Solid–Electrolyte Interphase Formation in Ca(BH 4 ) 2 /THF for Ca Batteries

The Ca 2+ solvation structure at the electrolyte/electrode interface is of central importance to understand electroreduction stability and solid–electrolyte interphase (SEI) formation for the novel multivalent Ca battery systems. Here, using an exemplar electrolyte, the concentration-dependent solvation structure of Ca(BH 4 ) 2 -tetrahydrofuran on a gold model electrode has been investigated with various electrolyte concentrations via electrochemical quartz crystal microbalance with dissipation (EQCM-D) and X-ray photoelectron spectroscopy (XPS). For the first time, in situ EQCM-D results prove that the prevalent species adsorbed at the interface is CaBH 4 + across all concentrations. As the salt concentration increases, the number of BH 4 – anions associated with Ca 2+ increases, and much larger solvated complexes such as CaBH 4 + ·4THF or Ca(BH 4 ) 3 – ·4THF form at the interface at high concentrations prior to Ca plating. Different interfacial chemistries lead to the formation of SEIs with different components demonstrated by XPS. High electrolyte concentrations reduce the solvent decomposition and promote the formation of thick, uniform, and inorganic-rich (i.e., CaO) SEI layers, which contribute to improved Ca plating efficiency and current density in electrochemical measurements.

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

Large eddy simulation of flow through an axisymmetric sudden expansion

Here, this study aims at investigating the inlet flow conditions of flow through an axisymmetric sudden expansion with an expansion ratio of 2.0. A series of large eddy simulations with the WALE model were conducted for different inlet Reynolds numbers ( Re) and turbulence intensities ($u_{rms}/\bar{U}_m$). The reattachment length, defined as the length measured downstream of the expansion where the flow direction is reversed adjacent to the wall ( Lr), was measured for each case. For widely studied inlet turbulence intensity values (TI), the simulation results are in good agreement with the experimental and numerical results reported in the literature. Parametric studies revealed that turbulence intensity affects the critical Reynolds number, marking the transition between the laminar and transition regions and the reattachment length. The critical Reynolds number was found to decrease with increasing turbulence intensity. A correlation expression is proposed. Additional analysis with proper orthogonal decomposition was performed to enhance the understanding of complex flow structures downstream of the expansion. Finally, an overall correlation expression for the reattachment length was obtained for 500 ≤ Re ≤15 000 and 0.2 ≤ TI (%) ≤ 20. For a given turbulence intensity, the reattachment length can be expressed for laminar and turbulent regions as a function of the Reynolds number. The reattachment length in the transition region can be expressed as a fractional average of reattachment lengths for laminar and turbulent flows.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2016

Forward-backward multiplicity fluctuation and longitudinal harmonics in high-energy nuclear collisions

In this paper, an analysis method is proposed to study the forward-backward (FB) multiplicity fluctuation in high-energy nuclear collisions, built on the earlier work of Bzdak and Teaney [Phys. Rev. C 87, 024906 (2013)]. The method allows the decomposition of the centrality dependence of average multiplicity from the dynamical event-by-event (EbyE) fluctuation of multiplicity in pseudorapidity. Application of the method to AMPT (A Multi-Phase Transport model) and HIJING (Heavy Ion Jet INteraction Generator) models shows that the long-range component of the FB correlation is captured by a few longitudinal harmonics, with the first component driven by the asymmetry in the number of participating nucleons in the two colliding nuclei. The higher-order longitudinal harmonics are found to be strongly damped in AMPT compared to HIJING, due to weaker short-range correlations as well as the final-state effects present in the AMPT model. Two-particle pseudorapidity correlation reveals interesting charge-dependent short-range structures that are absent in HIJING model. Lastly, the proposed method opens an avenue to elucidate the particle production mechanism and early time dynamics in heavy-ion collisions. Future analysis directions and prospects of using the pseudorapidity correlation function to understand the centrality bias in p + p, p + A, and A + A collisions are discussed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2017

Response of Water Use Efficiency to Global Environmental Change Based on Output From Terrestrial Biosphere Models

Here, water use efficiency (WUE), defined as the ratio of gross primary productivity and evapotranspiration at the ecosystem scale, is a critical variable linking the carbon and water cycles. Incorporating a dependency on vapor pressure deficit, apparent underlying WUE (uWUE) provides a better indicator of how terrestrial ecosystems respond to environmental changes than other WUE formulations. Here we used 20th century simulations from four terrestrial biosphere models to develop a novel variance decomposition method. With this method, we attributed variations in apparent uWUE to both the trend and interannual variation of environmental drivers. The secular increase in atmospheric CO 2 explained a clear majority of total variation (66 ± 32%: mean ± one standard deviation), followed by positive trends in nitrogen deposition and climate, as well as a negative trend in land use change. In contrast, interannual variation was mostly driven by interannual climate variability. To analyze the mechanism of the CO 2 effect, we partitioned the apparent uWUE into the transpiration ratio (transpiration over evapotranspiration) and potential uWUE. The relative increase in potential uWUE parallels that of CO 2 , but this direct CO 2 effect was offset by 20 ± 4% by changes in ecosystem structure, that is, leaf area index for different vegetation types. However, the decrease in transpiration due to stomatal closure with rising CO 2 was reduced by 84% by an increase in leaf area index, resulting in small changes in the transpiration ratio. CO 2 concentration thus plays a dominant role in driving apparent uWUE variations over time, but its role differs for the two constituent components: potential uWUE and transpiration.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Nanoscale imaging of He-ion irradiation effects on amorphous TaO x toward electroforming-free neuromorphic functions

Resistive switching in thin films has been widely studied in a broad range of materials. Yet, the mechanisms behind electroresistive switching have been persistently difficult to decipher and control, in part due to their non-equilibrium nature. Here, we demonstrate new experimental approaches that can probe resistive switching phenomena, utilizing amorphous TaO x as a model material system. Specifically, we applied scanning microwave impedance microscopy and cathodoluminescence (CL) microscopy as direct probes of conductance and electronic structure, respectively. These methods provide direct evidence of the electronic state of TaO x despite its amorphous nature. For example, CL identifies characteristic impurity levels in TaO x , in agreement with first principles calculations. We applied these methods to investigate He-ion-beam irradiation as a path to activate conductivity of materials and enable electroforming-free control over resistive switching. However, we find that even though He-ions begin to modify the nature of bonds even at the lowest doses, the films' conductive properties exhibit remarkable stability with large displacement damage and they are driven to metallic states only at the limit of structural decomposition. Finally, we show that electroforming in a nanoscale junction can be carried out with a dissipated power of <20 nW, a much smaller value compared to earlier studies and one that minimizes irreversible structural modifications of the films. Importantly, the multimodal approach described here provides a new framework toward the theory/experiment guided design and optimization of electroresistive materials.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Spectral functions with the density matrix renormalization group: Krylov-space approach for correction vectors

Frequency-dependent correlations, such as the spectral function and the dynamical structure factor, help illustrate condensed matter experiments. Within the density matrix renormalization group (DMRG) framework, an accurate method for calculating spectral functions directly in frequency is the correction-vector method. The correction vector can be computed by solving a linear equation or by minimizing a functional. Our paper proposes an alternative to calculate the correction vector: to use the Krylov-space approach. Further, this paper also studies the accuracy and performance of the Krylov-space approach, when applied to the Heisenberg, the t-J, and the Hubbard models. The cases we studied indicate that the Krylov-space approach can be more accurate and efficient than the conjugate gradient, and that the error of the former integrates best when a Krylov-space decomposition is also used for ground state DMRG.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Computational evaluation of new lithium-3 garnets for lithium-ion battery applications as anodes, cathodes, and solid-state electrolytes

In this work, we explore a set of new garnet oxide structures that can be used as an anode, cathode or solid-electrolyte in lithium-ion batteries (LIBs) using high-throughput density functional theory. Specifically, we tested around 180 combinations of elemental substitutions for the dodecahedral X sites and octahedral Y sites in the Li 3 X 3 Y 2 O 12 type garnet structure and identified 19 stable (i.e., on the convex hull) and 11 nearly stable (i.e., within 50 meV/atom of the convex hull) Li 3 garnets with respect to decomposition to other stable phases in the Open Quantum Materials Database in the respective four-dimensional Li-X-Y -O chemical spaces. Our high-throughput screening strategy allows us to elucidate rules for garnet stability in terms of the ionic radii of the constituent elements. We evaluated the electrochemical window of these new, stable/nearly stable Li3-garnet compounds and classify each for potential applications as an anode, cathode, or solid-state electrolyte to be used in LIBs. Finally, Li + ion diffusivity is calculated for the representative Li 3 Nd 3 W 2 O 12 model system. The results we present here are expected to serve as a guideline for designing new garnet oxides for Li-ion battery applications.

25 ENERGY STORAGE↗
DOE OSTI2022

Prediction of Multiple Hydrogen Ligation at a Vanadium(II) Site in a Metal–Organic Framework

Densifying hydrogen in a metal-organic framework (MOF) at moderate pressures can circumvent challenges associated with high-pressure compression. The highly tunable structural and chemical composition in MOFs affords vast possibilities to optimize binding interactions. At the heart of this search are the nanoscale characteristics of molecular adsorption at the binding site(s). Using density functional theory (DFT) to model binding interactions of hydrogen to the exposed metal site of cation-exchanged MFU-4 l , we predict multiple hydrogen ligation of H 2 at the first coordination sphere of V(II) in V(II)-exchanged MFU-4 l . We find that the strength of this binding between the metal site and H 2 molecules can be tuned by altering the halide counterion adjacent to the metal site and that the fluoride containing node affords the most favorable interactions for high-density H 2 storage. In conclusion, using energy decomposition analysis, we delineate electronic contributions that enable multiple hydrogen ligation and demonstrate its benefits for hydrogen adsorption and release at modest pressures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗