Search NASA⌕ Search

SEARCH · Search NASA

Results for “Li diffusion”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Direct Observation of Defect‐Aided Structural Evolution in a Nickel‐Rich Layered Cathode

Abstract Ni‐rich LiNi 1− x − y Mn x Co y O 2 (NMC) layered compounds are the dominant cathode for lithium ion batteries. The role of crystallographic defects on structure evolution and performance degradation during electrochemical cycling is not yet fully understood. Here, we investigated the structural evolution of a Ni‐rich NMC cathode in a solid‐state cell by in situ transmission electron microscopy. Antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role on phase change. Upon Li depletion, the APB extended across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases was detected to induce the rock‐salt phase formation along the coherent TB. According to DFT calculations, Li/TM mixing and phase transition were aided by the low diffusion barriers of TM ions at planar defects. This work reveals the dynamical scenario of secondary phase evolution, helping unveil the origin of performance fading in Ni‐rich NMC.

Li, Shuang↗
NASA NTRS2018

Solar Wind Implantation Into the Lunar Regolith: Monte Carlo Simulations of H Retention in a Surface With Defects and the H2 Exosphere

The solar wind implants protons into the top 20–30 nm of lunar regolith grains, and the implanted hydrogen will diffuse out of the regolith but also interact with oxygen in the regolith oxides. We apply a statistical approach to estimate the diffusion of hydrogen in the regolith hindered by forming temporary bonds with regolith oxygen atoms. A Monte Carlo simulation was used to track the temporal evolution of bound OH surface content and the H2 exosphere. The model results are consistent with the interpretation of the Chandrayaan-1 M3 observations of infrared absorption spectra by surface hydroxyls as discussed in Li and Milliken (2017). Themodel reproduced the latitudinal concentration of OH by using a Gaussian energy distribution of f(U(o) = 0.5eV, U(w) = 0.078 – 0.1 eV) to characterize the activation energy barrier to the diffusion of hydrogen in space weathered regolith. In addition, the model results of the exospheric content of H2 are consistent with observations by the Lyman Alpha Mapping Project on the Lunar Reconnaissance Orbiter. Therefore, we provide support for hydroxyl formation by chemically trapped solar wind protons.

O. J. Tucker↗
DOE OSTI2022

Direct 2,3-Butanediol Conversion to Butene-Rich C 3+ Olefins over Copper-Modified 2D Pillared MFI: Consequence of Reduced Diffusion Length

2,3-Butanediol (2,3-BDO), a critical C 4 platform chemical derived from biomass, syngas, or CO 2 , can be converted to C 3+ olefins, serving as important renewable feedstocks for producing sustainable aviation fuels to decarbonize the hard-to-electrify air transportation sector. Herein, we report a bifunctional Cu-modified diffusion-free 2D pillared MFI catalyst (Cu/PMFI) which can selectively catalyze 2,3-BDO conversion to butene-rich C 3+ olefins (95% selectivity at 97% conversion, 523 K). 2,3-BDO conversion to butenes over Cu/PMFI primarily occurs via methyl ethyl ketone intermediate while 2-methyl propanal is also observed as another minor dehydration product that leads to butene formation. In comparison with a control mesoporous Cu/ZSM-5 sample prepared by the postsynthetic approach, Cu/PMFI shows favorable C 3+ olefin selectivity (95% over Cu/PMFI vs 80% over Cu/ZSM-5 at ~5.1 h TOS). The coke formation over Cu/PMFI is dramatically suppressed by >50% in contrast to Cu/ZSM-5 in 90 h 2,3-BDO conversion due to the reduced diffusion length. Cu/PMFI also favors butene formation and minimizes nonbutene C 3+ olefins by inhibiting the downstream oligomerization and cracking reactions. This study highlights the usefulness of the diffusion-free 2D PMFI materials in catalytic conversion of biomass-derived platform molecules and the significance of diffusion impact on catalyst coke formation and product distributions.

2,3-butanediol↗
DOE OSTI2020

Non-compact oxide-island growth induced by surface phase transition of the intermetallic NiAl during vacuum annealing

Crystal structure and composition are inter-dependent and decoupling their effects on surface reactivity is challenging. Using low-energy electron microscopy to spatially and temporally resolve the oxide film growth during the oxidation of NiAl(100), we differentiate such coupled effects by monitoring oxide growth while simultaneously fine-tuning the surface structure and composition during oxidation. We demonstrate that the oxidation of chemically ordered surfaces results in compact oxide island growth whereas non-compact oxide growth during the surface phase transition. By incorporating the surface phase transition induced chemical disordering into kinetic Monte Carlo simulations, we illustrate that the non-compact oxide growth is induced by the composition effect on the surface diffusion of oxygen, which can be described by the concept of “ant in the labyrinth”.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Helium effects on the surface and subsurface evolutions in single-crystalline tungsten

Tungsten (W) has been perceived as one of the most promising plasma facing materials (PFMs) for future fusion reactors. In the past decade, its behavior under irradiation and helium (He) plasma interaction has been extensively studied. However, some key knowledge gaps still exist, such as the influence of crystallographic orientation on the surface and subsurface evolutions. In this work, we focus on the He ion-beam irradiation damage effects in mirror-polished single-crystalline W samples with three different surface planes of {100}, {110} and {111}. Irradiation was performed at room temperature using 40 keV He+ to a fluence of 1 × 10 16 /cm 2 , followed by thermal desorption spectroscopy (TDS) up to ~1920 K. The microstructures of He-irradiated W before and after TDS heat treatment were characterized by scanning and transmission electron microscopy. Subsurface He bubbles were imaged in all irradiated samples, but newly formed <111>-oriented surface grains and surface blisters were only observed in W {100} and {110} starting orientations. These results reveal that radiation damage, He thermal desorption, and surface/subsurface evolution are all strongly dependent on crystallographic orientation. Underlying physical mechanisms are discussed based on ion channeling effects, He-vacancy interactions, and surface diffusion. In conclusion, these findings provide new insights into He effects in W.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Doping in Efficient Polycrystalline CdSeTe Solar Cells via AsCl 3 Vapor Annealing

Doping in cadmium telluride (CdTe) thin-film solar cells is a critical step in producing highly efficient CdTe solar modules. To date, copper (Cu) ex-situ diffusion doping and group V in situ doping (such as arsenic, As) have been effectively used in manufacturing CdTe solar modules. However, Cu doping is prone to rapid degradation, whereas the low activation ratio of the dopants constrains group V in situ doping. Recently, ex-situ group V doping has been developed, showing an improved doping activation ratio through a solution process. Here, in this study, we developed a vapor-based AsCl 3 doping method for diffusion doping of polycrystalline CdSeTe devices. AsCl 3 vapor annealing can promote the diffusion of As into the bulk CdSeTe through a surface chemical reaction between CdTe and AsCl 3 . This approach has led to a long carrier lifetime of over 72 ns, V oc of 850 mV, and power conversion efficiency of ~18% with Au metal electrodes. The vapor-based ex situ group V doping approach offers an effective means to perform group V diffusion doping into the CdSeTe device.

14 SOLAR ENERGY↗
NASA NTRS2001

Theory and Simulation of Self- and Mutual-Diffusion of Carrier Density and Temperature in Semiconductor Lasers

Carrier diffusion and thermal conduction play a fundamental role in the operation of high-power, broad-area semiconductor lasers. Restricted geometry, high pumping level and dynamic instability lead to inhomogeneous spatial distribution of plasma density, temperature, as well as light field, due to strong light-matter interaction. Thus, modeling and simulation of such optoelectronic devices rely on detailed descriptions of carrier dynamics and energy transport in the system. A self-consistent description of lasing and heating in large-aperture, inhomogeneous edge- or surface-emitting lasers (VCSELs) require coupled diffusion equations for carrier density and temperature. In this paper, we derive such equations from the Boltzmann transport equation for the carrier distributions. The derived self- and mutual-diffusion coefficients are in general nonlinear functions of carrier density and temperature including many-body interactions. We study the effects of many-body interactions on these coefficients, as well as the nonlinearity of these coefficients for large-area VCSELs. The effects of mutual diffusions on carrier and temperature distributions in gain-guided VCSELs will be also presented.

Li, Jian-Zhong↗
NASA NTRS2021

MODIS Reflective Solar Bands Calibration Improvements for Collection 7

Calibration of Terra and Aqua MODIS reflective solar bands (RSB) has evolved significantly since the launch of the first MODIS instrument on the Terra satellite more than 21 years ago. In NASA’s current Collection 6 and 6.1 Level 1B products (C6/C6.1 L1B), the RSB calibration algorithm continues to rely primarily on the onboard solar diffuser to calibrate the instrument gain. Lunar observations are used to track on-orbit changes in the response versus scan angle (RVS), and data from pseudo-invariant desert sites are used to apply adjustments to the gain and RVS calibration for select bands. The resulting reflectance products have in general shown a very stable performance. In recent years, some performance degradation has been noted for a few bands and algorithm changes have been tested to further improve the calibration accuracy for the upcoming Collection 7 (C7) L1B reprocess. In this paper, we present the MODIS RSB calibration improvements that will be included in C7. Major improvements include: applying polarization correction to the desert data before using it to generateRVS for Terra bands 8, 9, 3, and 10; using ocean scene data and an interband calibration approach to correct for long-term drift of Terra bands 11 and 12; applying an updated crosstalk correction to Terra SWIR bands over the entire mission; and using data from deep convective clouds in Terra SWIR band calibration, including the addition of time-dependent RVS for bands 5 and 26. All other minor calibration changes are also covered. Overall, the reflectance differences at nadir between C6.1 and C7 are within a few percent, though the differences increase in some cases at large scan angles. The Terra visible (3, 8-12) and SWIR bands (5-7, 26) have the most significant improvements. For all other Terra bands and all Aqua bands, the C7-C6.1 differences are mostly within 1%

MODIS↗
DOE OSTI2020

Imaging the Phase Evolution of the Li-N-H Hydrogen Storage System

Complex metal hydrides provide high-density hydrogen storage, which is essential for vehicular applications. However, the utility of these materials has been limited by thermodynamic and kinetic barriers present during the dehydrogenation and rehydrogenation processes as new phases form inside parent phases. Better understanding of the mixed-phase mesostructures and their interfaces may assist in improving cyclability. In this work, the evolution of the phases during hydrogenation of lithium nitride and dehydrogenation of lithium amide with lithium hydride are probed with scanning-transmission X-ray microscopy at the nitrogen K edge. With this technique, intriguing core-shell structures were observed in particles of both partially hydrogenated Li 3 N and partially dehydrogenated LiNH 2 + 2 LiH. The potential contributions of both internal hydrogen mobility and interfacial energies on the generation of these structures are discussed.

08 HYDROGEN↗
DOE OSTI2022

On the thermal coarsening and transformation of nanoscale oxide inclusions in 316L stainless steel manufactured by laser powder bed fusion and its influence on impact toughness

The thermal evolution of nanoscale oxide inclusions in 316L stainless steel (SS) manufactured by laser powder bed fusion additive manufacturing (AM) was explored. The size, chemical composition, morphology, and distribution of the oxides were characterized as the function of heat treatment conditions. The study revealed the mechanistic driving force of the rapid oxide coarsening during recrystallization. Ostwald ripening governs oxide coarsening. The active grain boundary-oxide interaction at the early stage of recrystallization accelerated oxide coarsening via enhanced solute diffusion along grain boundaries. Pipe diffusion along dislocation cellular boundaries has a negligible contribution to oxide coarsening. At high temperatures (T> 1065 °C), although lattice diffusion primarily controlled the oxide growth, the contribution from the grain-boundary diffusion was necessary. The transformation from MnSiO 3 to CrMn 2 O 4 took place in the un-recrystallized grains but was not observed when recrystallization started. The interaction of grain boundary and oxides during recrystallization resulted in a high fraction of oxides accumulated at grain boundaries. While oxide coarsening does not significantly alter the toughness value, grain-boundary oxides promote microvoid formation and intergranular fracture under Charpy impact in the recrystallized AM 316L SS.

36 MATERIALS SCIENCE↗
NASA NTRS2018

Solar Wind Implantation Into the Lunar Regolith: Monte Carlo Simulations of H Retention in a Surface With Defects and the H2 Exosphere

The solar wind implants protons into the top 20–30 nm of lunar regolith grains, and the implanted hydrogen will diffuse out of the regolith but also interact with oxygen in the regolith oxides. We apply a statistical approach to estimate the diffusion of hydrogen in the regolith hindered by forming temporary bonds with regolith oxygen atoms. A Monte Carlo simulation was used to track the temporal evolution of bound OH surface content and the H2 exosphere. The model results are consistent with the interpretation of the Chandrayaan‐1 M3 observations of infrared absorption spectra by surface hydroxyls as discussed in Li and Milliken (2017, https://doi.org/10.1126/sciadv.1701471). The model reproduced the latitudinal concentration of OH by using a Gaussian energy distribution of f(U0 = 0.5 eV, UW = 0.078–0.1 eV) to characterize the activation energy barrier to the diffusion of hydrogen in space weathered regolith. In addition, the model results of the exospheric content of H2 are consistent with observations by the Lyman Alpha Mapping Project on the Lunar Reconnaissance Orbiter. Therefore, we provide support for hydroxyl formation by chemically trapped solar wind protons.

O J Tucker↗
DOE OSTI2022

Numerical Analysis of Liquid Metal MHD Flow and Heat Transfer for Open-Surface Li Divertor in FNSF

Within the ongoing U.S.-based program on the development of liquid metal plasma-facing components, numerical simulations and analyses are performed to address the feasibility of the open-surface Li divertor. In the previous scoping studies (Smolentsev, 2021), heat-removal capabilities of the divertor were assessed using a simplified flow model for a slug-type velocity profile and constant flow thickness. Here, new analyses take into account forces acting on the flowing Li layer. Three reduced-order mathematical models are applied under the conditions of the U.S. Fusion Nuclear Science Facility (FNSF) to access magnetohydrodynamic (MHD) flow development effects, velocity distribution, and surface waves: 1) fully developed MHD flow; 2) quasi-2-D developing MHD flow; and 3) multiphase MHD flow. The obtained results for MHD flows and the surface heat flux computed with the plasma code scrape-off layer plasma simulation for ITER (SOLPS-ITER) are then used as input data to compute the temperature distribution in the divertor by solving the convection–diffusion energy equation.

Smolentsev, Sergey↗
DOE OSTI2020

ReaxFF molecular dynamics simulations of electrolyte–water systems at supercritical temperature

We have performed ReaxFF molecular dynamics simulations of alkali metal–chlorine pairs in different water densities at supercritical temperature (700 K) to elucidate the structural and dynamical properties of the system. The radial distribution function and the angular distribution function explain the inter-ionic structural and orientational arrangements of atoms during the simulation. The coordination number of water molecules in the solvation shell of ions increases with an increase in the radius of ions. We find that the self-diffusion coefficient of metal ions increases with a decrease in density under supercritical conditions due to the formation of voids within the system. The hydrogen bond dynamics has been interpreted by the residence time distribution of various ions, which shows Li+ having the highest water retaining capability. The void distribution within the system has been analyzed by using the Voronoi polyhedra algorithm providing an estimation of void formation within the system at high temperatures. We observe the formation of salt clusters of Na+ and K+ at low densities due to the loss of dielectric constants of ions. The diffusion of ions gets altered dramatically due to the formation of voids and nucleation of ions in the system.

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

Understanding Viscoelasticity of an Entangled Silicone Copolymer via Coarse-Grained Molecular Dynamics Simulations

Entangled dynamics is important for understanding rheological properties of long-chain polymers. For entangled homopolymers, the classic tube-reptation model and its refinements have been successfully applied to quantify properties like diffusion coefficient and zero-rate viscosity. However, the application of such models to copolymers has been limited despite scientific and industrial importance. Here, we study the entangled melt dynamics of poly(dimethyl-co-diphenyl)siloxane random copolymer for a range of mean-composition-ratio ϕ of the diphenyl component via long-term molecular dynamics simulation with a recently developed coarse-grained model. We found that the segmental relaxation is heterogeneous at the monomeric level because of compositional fluctuations. However, at the chain-entanglement level and higher length scales, the viscoelastic response is homogeneous with compositional dependence only through the overall diphenyl fraction ϕ. The relaxation modulus of the entangled copolymer melt conforms to the Likhtman–McLeish model, and the viscosity predicted using our current coarse-grained parameters is in good quantitative agreement with experimental data.

Copolymers↗
DOE OSTI2021

A Review of Local-to-Nonlocal Coupling Methods in Nonlocal Diffusion and Nonlocal Mechanics

Local-to-nonlocal (LtN) coupling refers to a class of methods aimed at combining nonlocal and local modeling descriptions of a given system into a unified coupled representation. This allows to consolidate the accuracy of nonlocal models with the computational expediency of their local counterparts, while often simultaneously removing nonlocal modeling issues such as surface effects. The number and variety of proposed LtN coupling approaches have significantly grown in recent years, yet the field of LtN coupling continues to grow and still has open challenges. This review provides an overview of the state of the art of LtN coupling in the context of nonlocal diffusion and nonlocal mechanics, specifically peridynamics. Furthermore, we present a classification of LtN coupling methods and discuss common features and challenges. The goal of this review is not to provide a preferred way to address LtN coupling but to present a broad perspective of the field, which would serve as guidance for practitioners in the selection of appropriate LtN coupling methods based on the characteristics and needs of the problem under consideration.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Achieving High Stability and Performance in P2-Type Mn-Based Layered Oxides with Tetravalent Cations for Sodium-Ion Batteries

We report P2-type sodium-manganese-based layered cathodes, owing to their high capacity from both cationic and anionic redox, are a potential candidate for Na-ion batteries to replace Li-ion technology in certain applications. Still, the structure instability originates from irreversible oxygen redox at high voltage remains a challenge. Here, a high sustainability cobalt-free P2- Na 0.72 Mn 0.75 Li 0.24 X 0.01 O 2 (X= Ti/Si) cathode is developed. The outstanding capacity retention and voltage retention after 150 cycles are obtained in Na half-cells. Our finding shows Ti locates on the surface while Si diffuses to the bulk of the particles. Thus, Ti can act as protective layer that alleviate side reactions in carbonate-based electrolyte. Meanwhile, Si can regulate the local electronic structure and suppress oxygen redox activities. Notably, full-cells with hard carbon (≈300-335 Whkg -1 based on the cathode mass) deliver the capacity retention of 83% for P2- Na 0.72 Mn 0.75 Li 0.24 Si 0.01 O 2 and 66% for P2-Na 0.72 Mn 0.75 Li 0.24 Ti 0.01 O 2 after 500 cycles; this electrochemical stability is the best compared to other reported cathodes based on oxygen redox at present. The superior cycle performance also stems from the ability to inhibit microcracking and planar gliding within the particles. Altogether, this finding offers new composition towards developing high performance low-cost cathodes for Na-ion batteries and highlights the unique role of Ti/Si ions.

25 ENERGY STORAGE↗
DOE OSTI2021

Stability and mobility of tungsten clusters on tungsten (110) surface: Ab initio and atomistic simulations

Quantifying the surface transport properties of tungsten (W) is of prime importance to understand the formation of nano-fuzz in fusion plasma-facing conditions. The stability and mobility of W adatom clusters (W n , n = 2-9) on the W(110) surface has been investigated by computer simulations, including ab initio calculations using density functional theory (DFT) and molecular statics (MS) simulations with multiple W interatomic potentials. The DFT results demonstrate that the sequential binding energy generally increases with number of W adatoms, except for the 5 th and 7 th W adatoms. The most common elemental migration steps of W n (n>2) clusters are observed to consist of monomer and dimer hops, while larger W n clusters can also diffuse by dissociation and recombination of smaller clusters. The threshold migration energy of W 9 is the highest, then followed by W 8 , W 4 , and W 6 , while W 3 , W 5 , and W 7 have similar migration energies. Compared to DFT, each interatomic potential evaluated overestimates the binding energies of W n clusters. Additionally, the embedded-atom potential developed by Juslin and Wirth adequately predicts the threshold migration energy of W n (n>2) clusters, although it predicts different underlying migration mechanisms. The results show that interaction mechanism between W adatoms controls the stability and mobility of W n clusters on the W(110) surface.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Gated Molecular Diffusion at Liquid–Liquid Interfaces

Abstract The jamming of nanoparticle surfactants (NPSs) at liquid–liquid interface imparts attractive properties to the interfacial assemblies and enables the structuring of liquids. Herein, we report photoresponsive supramolecular microcapsules with jammed NPS assemblies at the oil‐water interface, taking advantage of host–guest molecular recognition. The permeability of the colloidal membrane can be effectively manipulated by switching the NPSs from a jammed state to an unjammed state with a photo trigger, leading to a controlled molecular diffusion and release, affording a versatile platform for the construction of next generation smart microcapsule systems.

Li, Lianshun↗