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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

ON THE VERY HIGH ENERGY SPECTRUM OF THE CRAB PULSAR

In the present paper, we construct a self-consistent theory interpreting the observations from the MAGIC Cherenkov Telescope of the very high energy (VHE) pulsed emission from the Crab pulsar. In particular, on the basis of Vlasov's kinetic equation, we study the process of quasi-linear diffusion (QLD) developed by means of the cyclotron instability. This mechanism provides simultaneous generation of low (radio) and VHE (0.01-25 GeV) emission on light cylinder scales in one location of the pulsar magnetosphere. A different approach to the synchrotron emission is considered, giving the spectral index of the VHE emission ({beta} = 2) and the exponential cutoff energy (23 GeV) in good agreement with the observational data.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2011

Real-Valued Semigroups and (Causal) Diffusion

It can be shown that a process modeled by a strongly continuous real-valued semigroup (that has a space convolution operator as infinitesimal generator) cannot satisfy causality. By causality we mean that a characteristic feature of a process like an interface or a front must propagate with a finite speed. We present and discuss a causal model of diffusion that satisfies the semigroup property at a discrete set of time instants M:={l_brace}m{tau}|m is an element of N{sub 0}{r_brace} and that in contrast to the classical diffusion model is not smooth. More precisely, if v denotes the concentration of a substance diffusing with constant speed, then v is continuous but its time derivative is discontinuous at the discrete set M of time instants. It is this property of (causal) diffusion that forbids the classical limit procedure {tau}{yields}0 that leads to the noncausal diffusion model in Stochastics. Finally, we give two explanations why in some cases the discretization of the noncausal diffusion model can be considered as an approximation of the causal diffusion model. In particular, we present an inhomogeneous wave equation with a time dependent coefficient that is satisfied by causal diffusion.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Improved Water Management of Electrospun Nanofiber Membrane Electrode Assemblies at High Current Densities Measured in Operando Using Neutron Radiography

Neutron radiography was used to measure water concentrations through the cross-sections of sprayed gas diffusion electrodes (GDE) and electrospun perfluorosulfonic acid-platinum nanofiber (NF) electrodes during fuel cell operation. The performance of Generation 1 poly(acrylic acid)-based NF electrodes is improved at high current densities compared to the baseline given by a GDE cell. Through-thickness water profiles reveal that at high current densities, the water concentrations within the membrane electrode assembly (MEA) and gas diffusion layers are around 2x lower in the nanofiber-containing MEA compared to the baseline GDE, commensurate with the observed polarization performance. In Generation 2 electrospun nanofiber electrodes, poly(ethylene oxide)-based electrodes show higher performance than poly(acrylic acid) electrodes, while retaining less water in the MEA. Furthermore, these results imply that the electrospun nanofiber electrodes have an improved ability to maintain hydration without flooding, which leads to improved performance over a range of relative humidities.

42 ENGINEERING↗
DOE OSTI2022

On the effect of scalar flux weighing of linearly anisotropic scattering matrices in few-group transport calculations

The majority of the codes available for homogenized group constant generation for deterministic transport calculations apply the approximation of scalar flux weighting during energy group condensation of higher-order anisotropic scattering matrices. In this paper, we discuss the effect of scalar flux weighting of the linearly anisotropic scattering matrices in the frame of S P{sub 3} and S{sub 12} calculations performed for a two-dimensional VVER-440 reactor benchmark. To compare group constants generated for two neutron energy groups, an infinite pin cell was homogenized with Serpent 2 and ERANOS ECCO. Serpent 2 applies scalar flux, while ERANOS ECCO performs current weighting of the linearly anisotropic scattering matrices during energy group condensation. For analyzing the effect of the various weighting options, three simple reactor models were built assuming different core sizes using standard rectangular assemblies with 15*15 fuel pins. Diffusion, SP{sub 3} and S{sub 12} calculations were performed for the 3 models using group constants generated with Serpent 2 and ERANOS ECCO. The effect of scalar flux weighting of linearly anisotropic scattering matrices is shown by comparing the decrease in reactivity due to the decreased reactor size, as well as the assembly power distribution to reference results obtained with Serpent 2 Monte Carlo calculations. Neglecting higher than linearly anisotropic scattering and indirect application of diffusion coefficients in higher-order transport calculations is advised if angular flux-moment spectra weighted higher-order scattering matrices cannot be generated. (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
NASA NTRS1989

Modularity in robotic systems

Most robotic systems today are designed one at a time, at a high cost of time and money. This wasteful approach has been necessary because the industry has not established a foundation for the continued evolution of intelligent machines. The next generation of robots will have to be generic, versatile machines capable of absorbing new technology rapidly and economically. This approach is demonstrated in the success of the personal computer, which can be upgraded or expanded with new software and hardware at virtually every level. Modularity is perceived as a major opportunity to reduce the 6 to 7 year design cycle time now required for new robotic manipulators, greatly increasing the breadth and speed of diffusion of robotic systems in manufacturing. Modularity and its crucial role in the next generation of intelligent machines are the focus of interest. The main advantages that modularity provides are examined; types of modules needed to create a generic robot are discussed. Structural modules designed by the robotics group at the University of Texas at Austin are examined to demonstrate the advantages of modular design.

Tesar, Delbert↗
DOE OSTI2014

Study of Interfacial Interactions Using Thing Film Surface Modification: Radiation and Oxidation Effects in Materials

Interfaces play a key role in dictating the long-term stability of materials under the influence of radiation and high temperatures. For example, grain boundaries affect corrosion by way of providing kinetically favorable paths for elemental diffusion, but they can also act as sinks for defects and helium generated during irradiation. Likewise, the retention of high-temperature strength in nanostructured, oxide-dispersion strengthened steels depends strongly on the stoichiometric and physical stability of the (Y, Ti)-oxide particles/matrix interface under radiation and high temperatures. An understanding of these interfacial effects at a fundamental level is important for the development of materials for extreme environments of nuclear reactors. The goal of this project is to develop an understanding stability of interfaces by depositing thin films of materials on substrates followed by ion irradiation of the film-substrate system at elevated temperatures followed by post-irradiation oxidation treatments. Specifically, the research will be performed by depositing thin films of yttrium and titanium (~500 nm) on Fe-12%Cr binary alloy substrate. Y and Ti have been selected as thin-film materials because they form highly stable protective oxides layers. The Fe-12%Cr binary alloy has been selected because it is representative of ferritic steels that are widely used in nuclear systems. The absence of other alloying elements in this binary alloy would allow for a clearer examination of structures and compositions that evolve during high-temperature irradiations and oxidation treatments. The research is divided into four specific tasks: (1) sputter deposition of 500 nm thick films of Y and Ti on Fe-12%Cr alloy substrates, (2) ion irradiation of the film-substrate system with 2MeV protons to a dose of 2 dpa at temperatures of 300°C, 500°C, and 700°C, (3) oxidation of as-deposited and ion-irradiated samples in a controlled oxygen environment at 500°C and 700°C, (4) multi-scale computational modeling involving first- principle molecular dynamics (FPMD) and coarse-grained dissipative particle dynamics (DPD) approaches to develop theories underlying the evolution and stability of structures and phases. Samples from Tasks 1 to 3 (above) will be rigorously characterized and analyzed using scanning electron microscopy, Auger electron microscopy, x-ray diffraction, Rutherford back scatter spectroscopy, and transmission electron microscopy. Expected outcomes of the experimental work include a quantitative understanding film-substrate interface mixing, evolution of defects and other phases at the interface, interaction of interfaces with defects, and the ability of the Y and Ti films to mitigate irradiation-assisted oxidation.The aforementioned experimental work will be closely coupled with multi-scale molecular dynamics (MD) modeling to understand the reactions at the surface, the transport of oxidant through the thin film, and the stabilities of the deposited thin films under radiation and oxidation. Simulations of materials property changes under conditions of radiation and oxidation require multiple size domains and a different simulation scheme for each of these domains. This will be achieved by coupling the FPMD and coarse-grained kinetic Monte Carlo (KMC). This will enable the comparison of the results of each simulation approach with the experimental results.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Phase-space entropy cascade and irreversibility of stochastic heating in nearly collisionless plasma turbulence

We consider a nearly collisionless plasma consisting of a species of “test particles” in one spatial and one velocity dimension, stirred by an externally imposed stochastic electric field—a kinetic analog of the Kraichnan model of passive advection. The mean effect on the particle distribution function is turbulent diffusion in velocity space—known as stochastic heating. Accompanying this heating is the generation of fine-scale structure in the distribution function, which we characterize with the collisionless (Casimir) invariant C 2 ∝ ∫ ∫ d x d v 〈 f 2 〉 —a quantity that here plays the role of (negative) entropy of the distribution function. We find that C 2 is transferred from large scales to small scales in both position and velocity space via a phase-space cascade enabled by both particle streaming and nonlinear interactions between particles and the stochastic electric field. We compute the steady-state fluxes and spectrum of C 2 in Fourier space, with k and s denoting spatial and velocity wave numbers, respectively. In our model, the nonlinearity in the evolution equation for the spectrum turns into a fractional Laplacian operator in k space, leading to anomalous diffusion. Whereas even the linear phase mixing alone would lead to a constant flux of C 2 to high s (towards the collisional dissipation range) at every k , the nonlinearity accelerates this cascade by intertwining velocity and position space so that the flux of C 2 is to both high k and high s simultaneously. Integrating over velocity (spatial) wave numbers, the k -space ( s -space) flux of C 2 is constant down to a dissipation length (velocity) scale that tends to zero as the collision frequency does, even though the rate of collisional dissipation remains finite. The resulting spectrum in the inertial range is a self-similar function in the ( k , s ) plane, with power-law asymptotics at large k and s . Our model is fully analytically solvable, but the asymptotic scalings of the spectrum can also be found via a simple phenomenological theory whose key assumption is that the cascade is governed by a “critical balance” in phase space between the linear and nonlinear timescales. We argue that stochastic heating is made irreversible by this entropy cascade and that, while collisional dissipation accessed via phase mixing occurs only at small spatial scales rather than at every scale as it would in a linear system, the cascade makes phase mixing even more effective overall in the nonlinear regime than in the linear one. Published by the American Physical Society 2024

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Pressure solution creep of random packs of spheres

Abstract We performed numerical calculations of compaction in aggregates of spherical grains, using Lehner and Leroy's (2004, hereinafter LL) constitutive model of pressure solution at grain contacts. That model is founded on a local definition of the thermodynamic driving force and leads to a fully coupled formulation of elastic deformation, dissolution, and diffusive transport along the grain boundaries. The initial geometry of the aggregate was generated by random packing of spheres with a small standard deviation of the diameters. During the simulations, isostatic loading was applied. The elastic displacements at the contacts were calculated according to Digby's (1981) nonlinear contact force model, and deformation by dissolution was evaluated using the LL formulation. The aggregate strain and porosity were tracked as a function of time for fixed temperature, applied effective pressure, and grain size. We also monitored values of the average and standard deviation of total load at each contact, the coordination number for packing, and the statistics of the contact dimensions. Because the simulations explicitly exclude processes such as fracturing, plastic flow, and transport owing to surface curvature, they can be used to test the influence of relative changes in the kinetics of dissolution and diffusion processes caused by contact growth and packing rearrangements. We found that the simulated strain data could be empirically fitted by two successive power laws of the form, ε x ∝ t ξ , where ξ was equal to 1 at very early times, but dropped to as low as 0.3 at longer times. The apparent sensitivity of strain rate to stress found in the simulations was much lower than predicted from constitutive laws that assume a single dominant process driven by average macroscopic loads. Likewise, the apparent activation enthalpy obtained from the simulated data was intermediate between that assumed for dissolution and diffusion, and, further, tended to decrease with time. These results are similar to the experimental observations of Visser et al.'s (2012), who used an aggregate geometry and physical conditions closely resembling the present numerical simulations.

Bernabé, Y.↗
DOE OSTI2017

Innovative coating of nanostructured vanadium carbide on the F/M cladding tube inner surface for mitigating the fuel cladding chemical interactions

Fuel cladding chemical interactions (FCCI) have been acknowledged as a critical issue in a metallic fuel/steel cladding system due to the formation of low melting intermetallic eutectic compounds between the fuel and cladding steel, resulting in reduction in cladding wall thickness as well as a formation of eutectic compounds that can initiate melting in the fuel at lower temperature. In order to mitigate FCCI, diffusion barrier coatings on the cladding inner surface have been considered. In order to generate the required coating techniques, pack cementation, electroplating, and electrophoretic deposition have been investigated. However, these methods require a high processing temperature of above 700 oC, resulting in decarburization and decomposition of the martensites in a ferritic/martensitic (F/M) cladding steel. Alternatively, organometallic chemical vapor deposition (OMCVD) can be a promising process due to its low processing temperature of below 600 oC. The aim of the project is to conduct applied and fundamental research towards the development of diffusion barrier coatings on the inner surface of F/M fuel cladding tubes. Advanced cladding steels such as T91, HT9 and NF616 have been developed and extensively studied as advanced cladding materials due to their excellent irradiation and corrosion resistance. However, the FCCI accelerated by the elevated temperature and high neutron exposure anticipated in fast reactors, can have severe detrimental effects on the cladding steels through the diffusion of Fe into fuel and lanthanides towards into the claddings. To test the functionality of developed coating layer, the diffusion couple experiments were focused on using T91 as cladding and Ce as a surrogate lanthanum fission product. By using the customized OMCVD coating equipment, thin and compact layers with a few micron between 1.5 µm and 8 µm thick and average grain size of 200 nm and 5 µm were successfully obtained at the specimen coated between 300oC and 500 oC, respectively. The coating layer contains both carbon and vanadium elements as quantified by WED, and the phases mainly consist of a mixture of V2C and VC, which was confirmed using X-ray diffraction patterns. In addition, the ratio between V and C varies with processing temperature, and it was observed that a higher temperature promotes the carbon adsorption and increases thickness of the coating. With optimized deposition conditions, we can apply the coating technique toward the actual T91 cladding materials, and provide the possibilities for the real application in sodium-cooled fast reactors (SFRs). Diffusion couple experiments were performed at both 550 oC and 690 oC, which corresponds to normal and aggressive operating temperatures, respectively. The results show that vanadium carbide coating with wider thickness (8 µm) and lower carbon concentration (27 at.%) reduced the width of the inter diffusion region, indicating that vanadium carbide coating can mitigate FCCI effectively. In specific, inter-diffusion between Fe and Ce was prohibited over most area, but Ce diffusion occurred toward the coating and the Fe substrate through thinner coating layer, which needs further optimization in terms of uniform coating thickness. Overall, it is concluded that this coating process can be successfully applied onto the inner surface of HT9 cladding tubes and the FCCI can be effectively mitigated if not totally eliminated.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Mechanical and electrochemical response of a LiCoO 2 cathode using reconstructed microstructures

As LiCoO 2 cathodes are charged, delithiation of the LiCoO 2 active material leads to an increase in the lattice spacing, causing swelling of the particles. When these particles are packed into a bicontinuous, percolated network, as is the case in a battery electrode, this swelling leads to the generation of significant mechanical stress. In this study we performed coupled electrochemical-mechanical simulations of the charging of a LiCoO 2 cathode in order to elucidate the mechanisms of stress generation and the effect of charge rate and microstructure on these stresses. Energy dispersive spectroscopy combined with scanning electron microscopy imaging was used to create 3D reconstructions of a LiCoO 2 cathode, and the Conformal Decomposition Finite Element Method is used to automatically generate computational meshes on this reconstructed microstructure. Replacement of the ideal solution Fickian diffusion model, typically used in battery simulations, with a more general non-ideal solution model shows substantially smaller gradients of lithium within particles than is typically observed in the literature. Using this more general model, lithium gradients only appear at states of charge where the open-circuit voltage is relatively constant. While lithium gradients do affect the mechanical stress state in the particles, the maximum stresses are always found in the fully-charged state and are strongly affected by the local details of the microstructure and particle-to-particle contacts. These coupled electrochemical-mechanical simulations begin to yield insight into the partitioning of volume change between reducing pore space and macroscopically swelling the electrode. Lastly, preliminary studies that include the presence of the polymeric binder suggest that it can greatly impact stress generation and that it is an important area for future research.

25 ENERGY STORAGE↗
DOE OSTI2011

Constraint on dark matter annihilation with dark star formation using Fermi extragalactic diffuse gamma-ray background data

It has been proposed that during the formation of the first generation stars there might be a ''dark star'' phase in which the power of the star comes from dark matter annihilation. The adiabatic contraction process to form the dark star would result in a highly concentrated density profile of the host halo at the same time, which may give enhanced indirect detection signals of dark matter. In this work we investigate the extragalactic γ-ray background from dark matter annihilation with such a dark star formation scenario, and employ the isotropic γ-ray data from Fermi-LAT to constrain the model parameters of dark matter. The results suffer from large uncertainties of both the formation rate of the first generation stars and the subsequent evolution effects of the host halos of the dark stars. We find, in the most optimistic case for γ-ray production via dark matter annihilation, the expected extragalactic γ-ray flux will be enhanced by 1-2 orders of magnitude. In such a case, the annihilation cross section of the supersymmetric dark matter can be constrained to the thermal production level, and the leptonic dark matter model which is proposed to explain the positron/electron excesses can be well excluded. Conversely, if the positron/electron excesses are of a dark matter annihilation origin, then the early Universe environment is such that no dark star can form.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1990

A model for the distribution of material generating the soft X-ray background

The observational evidence relating to the soft X-ray diffuse background is discussed, and a simple model for its source and spatial structure is presented. In this simple model with one free parameter, the observed 1/4 keV X-ray intensity originates as thermal emission from a uniform hot plasma filling a cavity in the neutral material of the Galactic disk which contains the sun. Variations in the observed X-ray intensity are due to variations in the extent of the emission volume and therefore the emission measure of the plasma. The model reproduces the observed negative correlation between X-ray intensity and H I column density and predicts reasonable values for interstellar medium parameters.

Snowden, S. L.↗
DOE OSTI2017

Simulated impedance of diffusion in porous media

This paper describes the use of a frequency domain, finite-difference scheme to simulate the impedance spectra of diffusion in porous microstructures. We investigate both open and closed systems for a range of ideal geometries, as well as some randomly generated synthetic volumes and tomographically derived microstructural data. In many cases, the spectra deviate significantly from the conventional Warburg-type elements typically used to represent diffusion in equivalent circuit analysis. Furthermore, a key finding is that certain microstructures show multiple peaks in the complex plane, which may be misinterpreted as separate electrochemical processes in real impedance data. This is relevant to battery electrode design as the techniques for nano-scale fabrication become more widespread. This simulation tool is provided as an open-source MatLab application and is freely available online as part of the TauFactor platform.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Deep Learning Approaches to Surrogates for Solving the Diffusion Equation for Mechanistic Real-World Simulations

In many mechanistic medical, biological, physical, and engineered spatiotemporal dynamic models the numerical solution of partial differential equations (PDEs), especially for diffusion, fluid flow and mechanical relaxation, can make simulations impractically slow. Biological models of tissues and organs often require the simultaneous calculation of the spatial variation of concentration of dozens of diffusing chemical species. One clinical example where rapid calculation of a diffusing field is of use is the estimation of oxygen gradients in the retina, based on imaging of the retinal vasculature, to guide surgical interventions in diabetic retinopathy. Furthermore, the ability to predict blood perfusion and oxygenation may one day guide clinical interventions in diverse settings, i.e., from stent placement in treating heart disease to BOLD fMRI interpretation in evaluating cognitive function (Xie et al., 2019; Lee et al., 2020). Since the quasi-steady-state solutions required for fast-diffusing chemical species like oxygen are particularly computationally costly, we consider the use of a neural network to provide an approximate solution to the steady-state diffusion equation. Machine learning surrogates, neural networks trained to provide approximate solutions to such complicated numerical problems, can often provide speed-ups of several orders of magnitude compared to direct calculation. Surrogates of PDEs could enable use of larger and more detailed models than are possible with direct calculation and can make including such simulations in real-time or near-real time workflows practical. Creating a surrogate requires running the direct calculation tens of thousands of times to generate training data and then training the neural network, both of which are computationally expensive. Often the practical applications of such models require thousands to millions of replica simulations, for example for parameter identification and uncertainty quantification, each of which gains speed from surrogate use and rapidly recovers the up-front costs of surrogate generation. We use a Convolutional Neural Network to approximate the stationary solution to the diffusion equation in the case of two equal-diameter, circular, constant-value sources located at random positions in a two-dimensional square domain with absorbing boundary conditions. Such a configuration caricatures the chemical concentration field of a fast-diffusing species like oxygen in a tissue with two parallel blood vessels in a cross section perpendicular to the two blood vessels. To improve convergence during training, we apply a training approach that uses roll-back to reject stochastic changes to the network that increase the loss function. The trained neural network approximation is about 1000 times faster than the direct calculation for individual replicas. Because different applications will have different criteria for acceptable approximation accuracy, we discuss a variety of loss functions and accuracy estimators that can help select the best network for a particular application. We briefly discuss some of the issues we encountered with overfitting, mismapping of the field values and the geometrical conditions that lead to large absolute and relative errors in the approximate solution.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

Interfacial microstructure evolution and weld formation during ultrasonic welding of Al alloy to Cu

Highlights: • Surface oxide layer was fractured and dispersed around the weld interface during ultrasonic welding of Al alloy to Cu. • Mechanical mixing around the weld interface was caused by compressive deformation with ultrasonic vibration. • Once micro-bonds were generated between Al and Cu, shear deformation occurred around the weld interface. • Enhanced Cu diffusion into Al in the severely deformed region significantly contributed to the weld formation. - Abstract: Dissimilar welds of Al alloy 1050 to Cu were prepared via ultrasonic spot welding in order to understand the formation of welds and interfacial microstructures. To observe oxide layer behavior at the weld interface, the anodized Al alloy 1050 was also welded to Cu. Mechanical mixing and material flow during ultrasonic welding broke and dispersed the oxide layers into the Al matrix. This material flow is attributed to compressive deformation that occurred due to ultrasonic vibrations. Direct bonding in the Al/Cu region increased with welding time. Once micro-bonds were generated between Al and Cu, the Al matrix in the vicinity of the weld interface was severely deformed in the direction of the ultrasonic vibrations. Consequently, a recrystallized microstructure with shear texture was formed in the Al matrix. Deformation heating and severe shear deformation formed Al{sub 2}Cu intermetallic compound layers at the weld interface. The growth rate of the Al{sub 2}Cu layer was much faster than had previously been estimated based upon the peak temperature and ultrasonic welding heating time. This is likely due to the increased rate of Cu diffusion into Al in the severely deformed region.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Localized and Intense Energy Conversion in the Diffusion Region of Asymmetric Magnetic Reconnection

We assess a high-resolution simulation of magnetopause reconnection observed by the Magnetospheric Multiscale mission and explain the occurrence of strongly localized dissipation with an amplitude more than an order of magnitude larger than expected. Unlike symmetric reconnection, wherein reconnection of the ambient reversed magnetic field drives the dissipation, we discover that the annihilation of the self-generated, out-of-plane (Hall) magnetic field plays the dominant role. Electrons flow along the magnetosheath separatrices, converge in the diffusion region, and jet past the X-point into the magnetosphere. The resulting accumulation of negative charge generates intense parallel electric fields that eject electrons along the magnetospheric separatrices and produce field-aligned beams. Many of these features match Magnetospheric Multiscale observations.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Surface Atomic Rearrangement with High Cation Ordering for Ultra-Stable Single-Crystal Ni-Rich Co-Less Cathode Materials

It is crucial to minimize cobalt content in Ni-rich layered single-crystal cathodes due to their high price and limited availability, yet it will inevitably lead to cation disordering, capacity degradation, and thermal issues. Herein, to overcome the intrinsic trade-off between performance and composition of Ni-rich Co-less single-crystal cathodes, a precursor engineering strategy with an epitaxially grown cobalt enrichment on the surface is innovatively proposed. In contrast to traditional coating modifications with random orientation and rigid surface-bulk boundary, the epitaxially enriched surface cobalt layer on the precursor undergoes rapid interdiffusion with the internal Ni 3+ during the optimized sintering process. This interdiffusion eliminates the surface-bulk boundary, promoting the uniform distribution of cobalt and synergistically addressing the Li/Ni intermixing. Moreover, an enhanced surface Li + diffusion is obtained, thereby suppressing the Li + concentration gradient and intragranular cracks generation. Consequently, the modified LiNi 0.7 Co 0.07 Mn 0.23 O 2 exhibits impressive cycling stability with increased capacity retention in both coin-type half-cells and pouch-type full-cells (91% after 1000 cycles), even under the harsh condition of high-temperature, surpassing the majority of previously reported Ni-rich cathodes. Finally, this work opens new avenues toward the low cost, high energy density, thermal stability, and long cyclic life for Ni-rich Co-less cathodes and sheds light on large-scale commercial production.

25 ENERGY STORAGE↗
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↗