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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Bulky Cation-Modified Interfaces for Thermally Stable Lead Halide Perovskite Solar Cells

Charged conjugated organic molecules offer promising prospects for reducing nonradiative recombination at interfaces in perovskite solar cells, while protecting the active layer from moisture. However, several studies have shown that the heat induced diffusion of these cations leads to irreversible solar cell degradation. Passivation molecules for perovskite can reconstruct the film surface into lower-dimensional phases when exposed to thermal stress, impeding charge extraction and affecting the photoconversion efficiency (PCE) of devices. In this work, we study how molecular interactions between passivation molecules and 3D CsFAPbI 3 perovskite impact stability and charge extraction at the perovskite/hole transport layer interfaces. Two model π- conjugated molecules are studied: 2-([2,2′-bithiophen]-5-yl)ethan-1-aminium iodide (2TI) and 2-(3‴,4′-dimethyl-[2,2′:5′,2″:5″,2‴- quaterthiophen]-5-yl)ethan-1-ammonium iodide (4TmI). We demonstrate that the speed of surface layer reconstruction under thermal stress can be controlled by the cation size and correlate these structural changes with the solar cell performance and stability. Devices treated with 2TI and 4TmI achieve PCEs over 21% and maintain their performance under thermal stress. Our findings demonstrate that thermal stability in PSCs can be achieved via the design engineering of passivation agents, offering a blueprint for developing next-generation passivation molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Assessing the role of surface carbon on the surface stability and reactivity of β-Mo 2 C catalysts

Transition-metal carbides, e.g., Mo 2 C, promote industrially important catalytic reactions with activities comparable to precious-metal catalysts. Yet, the nature of the catalytically active sites remains unclear. Herein, density functional theory calculations are applied to systematically assess the stability of low-Miller index facets of β-Mo 2 C as a function of carbon chemical potential (uC) and surface-carbon coverage (nC). When reconstruction of surface carbon is considered to characterize β-Mo 2 C under varying environments, the (111) and (101) surfaces are predicted to be most stable, dominating the Wulff particle surface area across a broad range of uC. The surface-carbon coverage is predicted to steadily increase for all low-index facets under more carburizing reaction conditions, leading to distinct effects on the adsorption energetics for atomic hydrogen and oxygen. Whereas H binding is only slightly affected by surface carbon, O is systematically destabilized. The findings reported indicate that consideration of only bulk-terminated surfaces, and the common focus of theoretical studies on the bulk-truncated, close-packed (100) surface, is likely insufficient to capture the reactivity of the working ..beta..-Mo 2 C catalyst. Similar to metal oxides, β-Mo2C catalysts are predicted to be dynamic materials with surface compositions and reactivities that evolve in response to the environment.

36 MATERIALS SCIENCE↗
DOE OSTI2022

How Water Attacks MXene

Two-dimensional (2D) transition metal carbides and nitrides (MXenes) have shown outstanding performances in electrochemical energy storage and many other applications. However, the stability of MXene remains a concern, especially its quick degradation in aqueous solutions under ambient conditions. Here, we report on the water/Ti 3 C 2 O 2 -MXene interfacial chemistry from first-principles molecular dynamics simulations at room temperature. Surprisingly, we find that the water molecules can attack the basal plane of Ti 3 C 2 O 2 and pull the surface Ti atoms out, thereby reconstructing the surface. Further, by tracking close encounters of water molecules and surface Ti atoms on the basal plane of Ti 3 C 2 O 2 , we show that the attack is initiated by the chemisorption of a water molecule on a surface Ti atom, followed by the breaking of Ti–C bonds and deprotonation of the water molecule, leading to the formation of Ti–OH on the Ti 3 C 2 O 2 surface and a hydronium ion in the aqueous phase. Our finding highlights the susceptibility of Ti 3 C 2 O 2 MXene to water attack, supporting recent experimental observations. Furthermore, we demonstrate that preventing close encounters of water molecules and the surface Ti atoms is key to the stability of the basal plane and can be realized by negatively charging the surface (thereby reorienting the O atoms of water away from the surface) or converting the surface O to -OH groups (thereby shifting the water layer further away from the surface). Our insights and approach highlight the importance of the reactivity of water when interfacing with 2D materials such as MXenes.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Interplay of structure and charge order revealed by quantum oscillations in thin films of Pr 2 CuO 4 ± δ

The discovery of quantum oscillations in hole- A nd electron-doped cuprate families has underscored the importance of the Fermi surface in cuprate superconductivity. While the observed quantum oscillations in both families have revealed the presence of reconstructed Fermi surfaces, there remains an important distinction between the two. In hole-doped cuprates the oscillations are thought to arise from the effects of a charge density wave, while in the electron-doped cuprates it is thought that these oscillations occur from an antiferromagnetically reconstructed Fermi surface, despite the fact that the oscillations are observed in overdoped compounds, far from the putative antiferromagnetic critical point. In this work we study thin films of Pr 2 CuO 4±δ , whose apparent doping can be finely tuned by annealing, allowing studies of quantum oscillations in samples straddling the critical point. Here, we show that even though there is a mass enhancement of the quasiparticles, there are only small changes to the Fermi surface itself, suggesting that charge order is a more likely origin, with electronic correlations that are strongly dependent on the structural parameters.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Valence transition and termination-dependent surface states in the topological Kondo semimetal YbPtBi

Here, the Yb-terminated and Bi-terminated (111) surface electronic structure of topological Kondo semimetal YbPtBi is investigated using both density-functional-theory (DFT) -based calculations and angle-resolved photoemission spectroscopy (ARPES). The cleavage plane is found to be between Yb-layers and Bi-layers in both experiment and theory, and the broken inversion symmetry ensures the Yb-terminated surface does not mix with the Bi-terminated surface. The ARPES results at the Bi-terminated surface are similar to those reported for YPtBi or LuPtBi, and they can be well explained using DFT calculations assuming trivalent Yb atoms. In contrast, at the Yb-terminated surface, a trivalent to divalent transition and reduced hybridization with conduction electrons for the topmost Yb atoms are observed, as a result of reduced bonding with Bi-atoms. In addition, the Fermi arc features induced by the triply degenerate-points, which are missing at the Bi-terminated surface, can be identified at the Yb-terminated surface. Our study demonstrates unambiguously the reconstruction of surface electronic structure due to the valence transition of the lanthanide element in a Kondo lattice system.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Impacts of Solvent Washing on the Electrochemical Remediation of Commercial End-of-Life Cathodes

Changes to surface structure and chemistry occurring throughout the functional lifetime of lithium-ion batteries (LIBs) may impact the effectiveness of end-of-life rejuvenation methods. Solvent washing prior to electrochemical relithiation is shown to both increase relithiation efficacy and beneficially alter the interfacial chemistry of heavily degraded industrial cathode material. Four common solvents (acetone, diethyl carbonate, isopropyl alcohol, propylene carbonate) are employed to investigate the role of varying physicochemical solvent properties on the mechanism of capacity recovery. Electrochemical (dQ/dV, EIS), structural (XRD), and chemical (SPME-GC-MS) analysis techniques are employed to comprehensively analyze solvent-cathode interactions. Highly nucleophilic solvents (acetone, DEC) are found to reduce cathode charge-transfer impedance and enable stable impedance growth throughout subsequent cycling. The use of nucleophilic solvents under mechanically aggressive washing conditions may also enable the reintroduction of bulk lattice oxygen, thereby restoring anionic redox capacity. Further, the four solvents are found to selectively remove a subset of surface species from the aged cathode material, including residual electrolyte, additives, and electrolyte-additive reaction products, which are qualitatively analyzed. Surface species removal by each solvent is correlated with the electrochemical performance of the correspondingly washed cathode, highlighting the importance of an optimized washing protocol to effective remediation in the context of direct LIB recycling. For the material under study, the use of a simple acetone washing protocol prior to electrochemical relithiation enables up to 174% capacity recovery relative to unwashed/relithiated black mass.

ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2023

Divergent urbanization-induced impacts on global surface urban heat island trends since 1980s

Urbanization experiences different speeds and forms under diverse development stages across the globe. However, urbanization-induced impacts on long-term surface urban heat island intensity (I s ) trends across global cities and the regulators of such impacts remain understudied. Here we estimate interannual trends in daytime I s (i.e., urban-rural differences in surface temperatures) across 511 major cities for 1985 –2020 using annual averages calculated by using reconstructed land surface temperature data derived from more than >250,000 Landsat thermal images. Our study reveals that the global mean I s growth rate is 0.156 °C/decade. We further examine I s change associated with per 1% impervious land growth (denoted as ß) in each city throughout the research period and during different periods. The global mean ß is 0.018 ± 0.025 °C/% (mean ± 1 standard deviation) for the whole period, with greater values in humid than in arid climates; and the ß may change during different periods, e.g., it has more than tripled when urban impervious land exceeds 30%, indicating the spatiotemporally divergent impacts of urbanization on Is trends across global cities. The spatial variations in ß across global cities are well correlated with rural vegetation abundance and precipitation but not with urban population. Among these three factors, rural vegetation abundance possesses the greatest standardized regression coefficient of partial least-squares model, signifying the critical role of biome background in regulating ß. Furthermore, the finding implies that future urbanization over densely vegetated regions should be more carefully and strategically planned due to the greater urbanization-induced surface warming effect.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Bulk‐Boundary Correspondence of Semimetal Ru 3 Sn 7 and Topological Surface States on Chemically Realistic Terminations

Ru 3 Sn 7 is experimentally demonstrated as an efficient catalyst, with potential utilization of topological surface states for hydrogen evolution reaction. Despite its promising catalytic performance, the topological nature of Ru 3 Sn 7 remains uncertain. Particularly, the bulk-boundary correspondence has not yet been established, hence hindering a rigorous justification of its topologically-protected surface states. In this work, the bulk topology of Ru 3 Sn 7 is detailed using first-principles calculations and the topological quantum chemistry formalism. Ru3Sn7 turns out to be an enforced semimetal possessing symmetry-protected crossings within a set of bands near the Fermi level, which are enforced and prescribed by the violations of symmetry-prescribed compatibility relations. Moreover, the surface states and the associated origin from the same set of entangled bands are identified, thereby establishing the bulk-boundary correspondence. To evaluate the effects of chemical modifications, the response of topological surface states to various surface terminations, stoichiometry, and oxidation is examined. The surface structures are globally optimized, and the phase diagrams for various experimental conditions are built. It is shown that, due to changes in the local chemical environment, the original surface states are significantly altered. Modified surface bands can be observed near the Fermi level on surface terminations that preserve the C 4v symmetry.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The Role of Secondary Particle Structures in Surface Phase Transitions of Ni-Rich Cathodes

Nanometer-thick reconstruction layers on layered cathode surfaces have been widely observed on both pristine and cycled materials. However, the mechanisms of reconstruction and the role that these structures play in electrochemical performance are not fully understood. From a crystallographic perspective, such surface reconstruction layers result from cation site-mixing between Li and transition-metal ions, but it remains far from clear as to what the critical factors are that control such cation mixing for various cathode chemistries. In this paper, we report observations on surface transformations during cycling of a Ni-rich cathode-oxide that are governed by direct contact with the liquid electrolyte. Specifically, within a secondary particle, the three-dimensional hierarchical aggregate of primary particles leads to the formation of grain boundaries of different characteristics, including open grain boundaries that allow the permeation of liquid electrolyte, and closed grain boundaries that exclude liquid electrolyte penetration. Upon battery cycling, surfaces in direct contact with the liquid electrolyte showed a surface reconstruction layer while the surfaces that did not have contact with the electrolyte showed no such reconstructions. In addition, the critical role of oxygen in reconstruction of grain boundaries is demonstrated, and the unexpected oxygen depletion at twin boundaries result in severe phase transitions. The present work provides further insights into phase transitions at solid-solid and solid-liquid interfaces within secondary cathode particles and suggests strategies for mitigating surface/interfacial degradation.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Performance of plane wavefront Fizeau interferometers in power spectral density measurements with tilted plane optics

Binary pseudo-random array (BPRA) test samples are useful devices for calibrating the instrument transfer function (ITF) of Fizeau interferometers, interferometric microscopes, and other optical and non-optical surface and wavefront metrology instruments. The intrinsic white noise character of the power spectral density (PSD) function of the BPRA pattern simplifies the extraction of the ITF from the measured PSD. The ITF determined in a dedicated calibration experiment can be used to reconstruct the surface height profile from the measured data, effectively enhancing the instrument’s spatial resolution. For a high confidence reconstruction procedure, a reliable analytical model of the IFT is desirable. Usually, the model accounts for the contributions to the ITF related the imperfections of the instrument’s optical and detector systems. Here, we experimentally demonstrate that in the case of surface height metrology with Fizeau interferometers, the PSD measurements and, therefore, the efficacy of the ITF calibration of the tool, are strongly affected by the instrument data acquisition and processing procedures, as well as by the shape of the optic under test and its alignment with respect to the interferometer.

Yashchuk, V V↗
DOE OSTI2020

Reconstruction of events recorded with the surface detector of the Pierre Auger Observatory

Cosmic rays arriving at Earth collide with the upper parts of the atmosphere, thereby inducing extensive air showers. When secondary particles from the cascade arrive at the ground, they are measured by surface detector arrays. We describe the methods applied to the measurements of the surface detector of the Pierre Auger Observatory to reconstruct events with zenith angles less than $60^\circ$ using the timing and signal information recorded using the water-Cherenkov detector stations. In addition, we assess the accuracy of these methods in reconstructing the arrival directions of the primary cosmic ray particles and the sizes of the induced showers.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Mutual modulation between surface chemistry and bulk microstructure within secondary particles of nickel-rich layered oxides

Abstract Surface lattice reconstruction is commonly observed in nickel-rich layered oxide battery cathode materials, causing unsatisfactory high-voltage cycling performance. However, the interplay of the surface chemistry and the bulk microstructure remains largely unexplored due to the intrinsic structural complexity and the lack of integrated diagnostic tools for a thorough investigation at complementary length scales. Herein, by combining nano-resolution X-ray probes in both soft and hard X-ray regimes, we demonstrate correlative surface chemical mapping and bulk microstructure imaging over a single charged LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) secondary particle. We reveal that the sub-particle regions with more micro cracks are associated with more severe surface degradation. A mechanism of mutual modulation between the surface chemistry and the bulk microstructure is formulated based on our experimental observations and finite element modeling. Such a surface-to-bulk reaction coupling effect is fundamentally important for the design of the next generation battery cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2022

Geometric prior of multi-resolution yielding manifolds and the local closest point projection for nearly non-smooth plasticity

Elastoplasticity models often introduce a scalar-valued yield function to implicitly represent the boundary between elastic and plastic material states. Here this paper introduces a new alternative where the yield envelope is represented by a manifold of which the topology and the geometry are learned from a set of data points in a parametric space (e.g. principal stress space, π-plane). Here, deep geometric learning enables us to reconstruct a highly complex yield envelope by breaking it down into multiple coordinate charts. The global atlas that consists of these coordinate charts in return allows us to represent the yield surface via multiple overlapping patches, each with a specific local parametrization. This setup provides several advantages over the classical implicit function representation approach. For instance, the availability of coordinate charts enables us to introduce an alternative stress integration algorithm where the trial stress may project directly on a local patch and hence circumvent the issues related to non-smoothness and the lack of convexity of yield surfaces. Meanwhile, the local parametric approach also enables us to predict hardening/softening locally in the parametric space, even without complete knowledge of the yield surface. Comparisons between the classical yield function approach on the non-smooth plasticity and anisotropic cam-clay plasticity model are provided to demonstrate the capacity of the models for highly precise yield surface and the feasibility of the implementation of the learned model in the local stress integration algorithm.

42 ENGINEERING↗
DOE OSTI2022

Competing electronic states emerging on polar surfaces

Excess charge on polar surfaces of ionic compounds is commonly described by the two-dimensional electron gas (2DEG) model, a homogeneous distribution of charge, spatially-confined in a few atomic layers. Here, by combining scanning probe microscopy with density functional theory calculations, we show that excess charge on the polar TaO 2 termination of KTaO 3 (001) forms more complex electronic states with different degrees of spatial and electronic localization: charge density waves (CDW) coexist with strongly-localized electron polarons and bipolarons. These surface electronic reconstructions, originating from the combined action of electron-lattice interaction and electronic correlation, are energetically more favorable than the 2DEG solution. They exhibit distinct spectroscopy signals and impact on the surface properties, as manifested by a local suppression of ferroelectric distortions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A Satellite-Derived Upper-Ocean Stratification Data Set for the Tropical North Atlantic With Potential Applications for Hurricane Intensity Prediction

Upper-ocean stratification strongly impacts vertical mixing and the heat flux between the ocean and atmosphere, especially under extreme conditions of tropical cyclones (TCs). Knowledge of prestorm stratification is important for accurate TC intensity prediction. In situ observations of the tropical ocean have significantly increased in the past decade. However, they are still too sparse to resolve ocean stratification variability in near-real time and on small spatial scales. Here, in this study, based on long-term observations and an ocean reanalysis data set from 2004–2017, we investigate the possibility of retrieving upper-ocean stratification from sea surface temperature (SST), sea surface salinity (SSS), and sea surface height (SSH) using a simple regression method. It is found that more than 90% of the mean seasonal cycle and about 30% to 80% of temperature and salinity stratification anomalies can be reconstructed using surface data from either observations or an ocean reanalysis. Simple regression can be used with satellite observations to create a high-resolution, near-real-time-gridded ocean stratification data set that successfully reproduces both the large and mesoscale variability of ocean stratification. When used in a simple expression for TC-induced SST cooling, the satellite-derived stratification shows improvements over an ocean analysis in terms of variance explained of SST cooling, offering promise as a near-real-time indicator of the ocean's impact on TC intensification.

54 ENVIRONMENTAL SCIENCES↗