Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “structural evolution”

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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Detonation-induced transformation of graphite to hexagonal diamond

In this work, we explore the structural evolution of highly oriented pyrolytic graphite (HOPG) under detonation-induced shock conditions using in situ synchrotron x-ray diffraction in the ns timescale. We observe the formation of hexagonal diamond (lonsdaleite) at pressures above 50 GPa, in qualitative agreement with recent gas gun experiments. First-principles density functional calculations reveal that under uniaxial compression, the energy barrier for the transition toward hexagonal diamond is lower than that for cubic diamond. Finally, no indication of cubic diamond formation was observed up to >70 GPa.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Effects of dose rate on the microstructure and deuterium retention in γ-LiAlO 2 pellets

This report presents experimental findings obtained from November 2024 to September 2025. Defect accumulation and microstructural evolution during ion irradiation at elevated temperatures are governed by two competing processes: defect production, driven by dose rate, and defect recovery, controlled by defect diffusion, interaction, and annihilation. At a given dose, the resulting microstructural evolution depends on both the dose rate and irradiation temperature. As a continuation of our FY24 tritium science project, which investigated temperature effects at a fixed dose rate, this study focuses on dose-rate effects at a fixed temperature to provide deeper insights into the irradiated microstructure and compositional changes in γ-LiAlO 2 pellets. The study aims to elucidate the impact of dose rate on microstructure, precipitate morphology, deuterium retention, and lithium volatility in γ-LiAlO 2 pellets under sequential 120 keV He + and 80 keV D 2 + ion irradiation. Three dose rates of 7.3×10 4 , 2.9×10 4 and 6.8×10 5 dpa/s were applied to achieve the same total ion fluence of 2×10 17 (He + +D + )/cm 2 at 500 °C, corresponding to a maximum combined dose of 7.55 dpa at ~255 nm. The irradiated pellets were subsequently characterized using scanning transmission electron microscopy (STEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The microstructural response of γ-LiAlO 2 to ion irradiation was found to be strongly dose-rate dependent. At medium and high dose rates, irradiation produced a surface amorphized layer and an underlying crystalline layer containing LiAl 5 O 8 precipitates, with implanted gases accumulating and forming blisters at the crystalline-amorphous interface. It remains to be investigated whether the amorphized layer was produced by He + ion irradiation prior to D 2 + ion irradiation. In contrast, at low dose rates, the material remained crystalline, with cavities, likely gas-filled, distributed around precipitates, within the γ-LiAlO 2 matrix, and along grain boundaries. While precipitate morphology exhibited anisotropy, their size showed little sensitivity to dose rate in the applied range of this study. This result, however, does not rule out the possibility that further reductions in dose rate could influence precipitate size. High dose-rate irradiation enhanced protonium–deuterium isotopic exchange and lithium depletion in the amorphized region. Collectively, the results show that dose rate governs amorphization, gas redistribution, isotopic exchange, and lithium depletion, providing important insights into the mechanisms underlying structural evolution in γ-LiAlO 2 pellets under reactor-relevant irradiation conditions.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2023

Achieving Thermodynamic Stability of Single-Crystal Co-Free Ni-Rich Cathode Material for High Voltage Lithium-Ion Batteries

Ni-rich layered cathode materials are progressively considered as the standard configuration of high-energy electric vehicles by virtues of their high capacity and eliminated “range anxiety.” However, the poor cyclic stability and severe cobalt supply crisis would restrain their wide commercial applicability. Here, a cost-effective single-crystal Co-free Ni-rich cathode material LiNi 0.8 Mn 0.18 Fe 0.02 O 2 (NMF), which outperforms widely commercial polycrystalline LiNi 0.83 Co 0.11 Mn 0.06 O 2 (MNCM) and single-crystal LiNi 0.83 Co 0.11 Mn 0.06 O 2 (SNCM) is reported. Surprisingly, NMF can compensate for the reversible capacity loss under the designed conditions of high-temperature and elevated-voltage, achieving a competitive energy density compared with conventional MNCM or SNCM. Further, combining operando characterizations and density functional theory calculation, it is revealed that NMF cathode with improved dynamic structure evolution largely alleviates the mechanical strain issue commonly found in Ni-rich cathode, which can reduce the formation of intragranular cracks and improve the safety performance. Consequently, this new Co-free NMF cathode can achieve a perfect equilibrium between material cost and electrochemical performance, which not only reduces the production cost by >15%, but also demonstrates excellent thermal stability and cycling performance.

25 ENERGY STORAGE↗
DOE OSTI2024

In Situ Cyclized Polyacrylonitrile Coating: Key to Stabilizing Porous High-Entropy Oxide Anodes for High-Performance Lithium-Ion Batteries

High-entropy oxides (HEOs) composed of multiple metal elements have attracted great attention as anode materials for lithium-ion batteries (LIBs) due to the synergistic effects of various metal species. However, the practical applications of HEOs are still plagued by poor conductivity, unstable solid electrolyte interphase (SEI) and poor cycling stability. In this work, nanosized (FeCoNiCrMn) 3 O 4 HEO (NHEO) is prepared successfully by the NaCl-assisted mechanical ball-milling strategy. Novelly, polyacrylonitrile (PAN) is used as the binder and then in situ thermochemically cyclized to construct a cyclized PAN (cPAN) outer layer onto NHEO (NHEO-cPAN). The in situ formed cPAN coating not only improves the electrical conductivity, but also reinforces the structural and interfacial stability, and thereby, the resulted NHEO-cPAN electrode exhibits significantly enhanced rate and cyclic performance. Specifically, NHEO-PAN500 electrode delivers a high reversible capacity of 560 mAh g –1 at 5 A g –1 and a high-capacity retention of 83% over 800 cycles at 3 A g –1 . Furthermore, the structural evolution and electrochemical behavior of NHEO-PAN electrode during discharge/charge is systematically investigated by operando X-ray diffraction, in situ impedance spectroscopy and ex situ high-resolution transmission electron microscopy. Therefore, this work provides new insights into the engineering of electrode and interphase for high-performance HEO electrode materials, potentially enlightening the practical applications of HEO-based LIBs.

25 ENERGY STORAGE↗
DOE OSTI2025

Domain Nucleation and Growth in an Epitaxially Grown Wurtzite Ferroelectric

Ferroelectric domain nucleation and growth in epitaxial (Al, B, Sc)N films grown on n-GaN substrates are explored using a combination of ferroelectric property measurements and scanning transmission electron microscopy, including novel in situ switching studies. The films are electrically switched to nitrogen-polar (N-polar) and metal-polar (M-polar) configurations, attaining a remanent polarization of 120 µC cm −2 with coercive fields of ≈6 MV cm −1 . In the initial switching cycle, the ferroelectric domains nucleate near the bottom n-GaN electrode and develop domain walls with zigzag morphologies, while residual “dead layers” that do not switch from the as-deposited orientation persist at the top and bottom electrodes. The in situ microscopy experiments reveal that domain walls propagate fastest in the lateral direction, parallel to the electrode/film interface. These findings provide insights into the domain dynamics and structural evolution of wurtzite ferroelectrics, offering implications for next-generation electronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Reaching the Excitonic Limit in 2D Janus Monolayers by In Situ Deterministic Growth

Abstract Named after the two‐faced Roman god of transitions, transition metal dichalcogenide (TMD) Janus monolayers have two different chalcogen surfaces, inherently breaking the out‐of‐plane mirror symmetry. The broken mirror symmetry and the resulting potential gradient lead to the emergence of quantum properties such as the Rashba effect and the formation of dipolar excitons. Experimental access to these quantum properties, however, hinges on the ability to produce high‐quality 2D Janus monolayers. Here, these results introduce a holistic 2D Janus synthesis technique that allows real‐time monitoring of the growth process. This prototype chamber integrates in situ spectroscopy, offering fundamental insights into the structural evolution and growth kinetics, that allow the evaluation and optimization of the quality of Janus monolayers. The versatility of this method is demonstrated by synthesizing and monitoring the conversion of SWSe, SNbSe, and SMoSe Janus monolayers. Deterministic conversion and real‐time data collection further aid in conversion of exfoliated TMDs to Janus monolayers and unparalleled exciton linewidth values are reached, compared to the current best standard. The results offer an insight into the process kinetics and aid in the development of new Janus monolayers with high optical quality, which is much needed to access their exotic properties.

2D materials↗
DOE OSTI2021

Elucidating and Mitigating High-Voltage Degradation Cascades in Cobalt-Free LiNiO 2 Lithium-Ion Battery Cathodes

LiNiO 2 (LNO) is a promising cathode material for next-generation Li-ion batteries due to its exceptionally high capacity and cobalt-free composition that enables more sustainable and ethical large-scale manufacturing. However, its poor cycle life at high operating voltages over 4.1 V impedes its practical use, thus motivating efforts to elucidate and mitigate LiNiO 2 degradation mechanisms at high states of charge. Here, a multiscale exploration of high-voltage degradation cascades associated with oxygen stacking chemistry in cobalt-free LiNiO 2 , is presented. In this work, lattice oxygen loss is found to play a critical role in the local O3–O1 stacking transition at high states of charge, which subsequently leads to Ni-ion migration and irreversible stacking faults during cycling. This undesirable atomic-scale structural evolution accelerates microscale electrochemical creep, cracking, and even bending of layers, ultimately resulting in macroscopic mechanical degradation of LNO particles. By employing a graphene-based hermetic surface coating, oxygen loss is attenuated in LNO at high states of charge, which suppresses the initiation of the degradation cascade and thus substantially improves the high-voltage capacity retention of LNO. Overall, this study provides mechanistic insight into the high-voltage degradation of LNO, which will inform ongoing efforts to employ cobalt-free cathodes in Li-ion battery technology.

25 ENERGY STORAGE↗
DOE OSTI2023

Stabilizing the Deep Sodiation Process in Layered Sodium Manganese Cathodes by Anchoring Boron Ions

Advanced high-energy-density sodium-ion batteries (SIBs) are inseparable from cathode materials with high specific capacities. Layered manganese-rich oxides (Na x MnO 2 , 0.6 ≤ x ≤1) are promising cathode materials owing to their ease of intercalation and extraction of a considerable amount of sodium ions. However, lattice interactions, especially electrostatic repulsive forces and anisotropic stresses, are usually caused by deep desodiatin/sodiation process, resulting in intragranular cracks and capacity degradation in SIBs. Here, boron ions are introduced into the layered structure to build up B-O-Mn bonds. Further, the regulated electronic structure in Na 0.637 B 0.038 MnO 2 (B-NMO) materials inhibits the deformation of MnO 6 octahedra, which finally achieves a gentle structural transition during the deep sodiation process. B-NMO electrode exhibits a high capacity (141 mAh g –1 ) at 1 C with a capacity retention of 81% after 100 cycles. Therefore, anchoring boron to manganese-rich materials inhibits the detrimental structural evolution of deep sodiation and can be used to obtain excellent cathode materials for SIBs.

25 ENERGY STORAGE↗
DOE OSTI2026

Phase Transformation and Water Adsorption Behavior of As‐Deposited and Annealed Ru Metal Thin Films Prepared by Atomic Layer Deposition

ABSTRACT Surfaces play a central role in catalytic processes, and understanding the transformation of ruthenium metal into ruthenium oxide during annealing is essential for tailoring functional catalytic interfaces. In this study, we systematically investigate ≈22 nm thick Ru metal films deposited by atomic layer deposition (ALD) at 300°C, focusing on their chemical composition, structural evolution, and surface hydration behavior following post‐deposition annealing in air from 400 to 600°C. Lab‐based and synchrotron X‐ray photoelectron spectroscopy (XPS) reveal a gradual conversion from metallic Ru to fully oxidized Ru 4+ with increasing annealing temperature, accompanied by a corresponding increase in lattice oxygen. X‐ray diffraction (XRD) shows amorphous Ru oxide phases at 400°C and 500°C that evolve into crystalline RuO 2 at 600°C, while atomic force microscopy (AFM) indicates enhanced grain growth and surface roughening upon annealing. Ambient‐pressure XPS (AP‐XPS) under controlled H 2 O vapor environments (1–17 Torr) demonstrates that samples annealed at 400°C and 500°C exhibit initially high hydroxyl coverage that decreases with increasing water vapor pressure, concurrent with a rise in molecular H 2 O adsorption. In contrast, the crystalline RuO 2 surface formed at 600°C maintains stable hydroxylation and supports increased water uptake. Overall, this work provides fundamental insight into Ru oxide–H 2 O interactions and establishes design principles for engineering oxide surfaces optimized for electrocatalytic applications.

APXPS↗
DOE OSTI2022

Luminescence from Self‐Trapped Excitons and Energy Transfers in Vacancy‐Ordered Hexagonal Halide Perovskite Cs 2 HfF 6 Doped with Rare Earths for Radiation Detection

Abstract Compared to halides Cs 2 HfX 6 (X = Cl, Br, I) with a vacancy‐ordered cubic double perovskite structure, the halide Cs 2 HfF 6 (CHF), with a hexagonal Bravais lattice, possesses a higher mass density and chemical stability for radiation detection. Luminescence properties and energy transfer mechanisms of rare‐earths‐doped CHF materials are studied here. The structure of CHF is identified as a new type of vacancy‐ordered hexagonal perovskite, with the same type of building blocks of the double perovskite but stacked with single layers. Density‐functional theory calculations reveal a large bandgap of CHF. A broad emission is observed from the pristine CHF host, which is suggested to be associated with self‐trapped excitons (STEs). A series of rare‐earths‐doped materials are designed utilizing the STE emissions, and efficient energy transfers from STEs and Tb 3+ to Eu 3+ are achieved for tunable emissions. The codoped material shows stable emission under X‐ray irradiation, with 10.2% reduction from its initial emission intensity, associated with possible structural evolution by radiation‐induced deformation of the soft host. The radiation responses of singly and codoped materials are evaluated, and the codoped material is found to be more sensitive to the radiation energy than the singly doped or pristine CHF for radiation detection.

36 MATERIALS SCIENCE↗
DOE OSTI2023

The Interplay Between Ferroelectricity and Electrochemical Reactivity on the Surface of Binary Ferroelectric Al x B 1–x N

Polarization dynamics and domain structure evolution in ferroelectric Al 0.93 B 0.07 N are studied using piezoresponse force microscopy and spectroscopies in ambient and controlled atmosphere environments. The application of negative unipolar and bipolar first-order reverse curve (FORC) waveforms leads to a protrusion-like feature on the Al 0.93 B 0.07 N surface and a reduction of electromechanical response due to electrochemical reactivity. A surface change is also observed on the application of fast alternating current bias. At the same time, the application of positive biases does not lead to surface changes. Comparatively in a controlled glove box atmosphere, stable polarization patterns can be observed, with minuscule changes in surface morphology. This surface morphology change is not isolated to applying biases to free surface, a similar topographical change is also observed at the electrode edges when cycling a capacitor in an ambient environment. The study suggests that surface electrochemical reactivity may have a significant impact on the functionality of this material in the ambient environment. However, even in the controlled atmosphere, the participation of the surface ions in polarization switching phenomena and ionic compensation is possible.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A High-Energy NASICON-Type Cathode Material for Na-Ion Batteries

Over the last decade, Na-ion batteries have been extensively studied as low-cost alternatives to Li-ion batteries for large-scale grid storage applications; however, the development of high-energy positive electrodes remains a major challenge. Materials with a polyanionic framework, such as Na superionic conductor (NASICON)-structured cathodes with formula Na x M 2 (PO 4 ) 3 , have attracted considerable attention because of their stable 3D crystal structure and high operating potential. Herein, a novel NASICON-type compound, Na 4 MnCr(PO 4 ) 3 , is reported as a promising cathode material for Na-ion batteries that deliver a high specific capacity of 130 mAh g –1 during discharge utilizing high-voltage Mn 2+/3+ (3.5 V), Mn 3+/4+ (4.0 V), and Cr 3+/4+ (4.35 V) transition metal redox. In addition, Na 4 MnCr(PO 4 ) 3 exhibits a high rate capability (97 mAh g –1 at 5 C) and excellent all-temperature performance. In situ X-ray diffraction and synchrotron X-ray diffraction analyses reveal reversible structural evolution for both charge and discharge.

25 ENERGY STORAGE↗
DOE OSTI2022

Insight into the Fast-Rechargeability of a Novel Mo 1.5 W 1.5 Nb 14 O 44 Anode Material for High-Performance Lithium-Ion Batteries

Wadsley–Roth phased niobates are promising anode materials for lithium-ion batteries, while their inherently low electrical conductivity still limits their rate-capability. Herein, a novel doped Mo 1.5 W 1.5 Nb 14 O 44 (MWNO) material is facilely prepared via an ionothermal-synthesis-assisted doping strategy. The detailed crystal structure of MWNO is characterized by neutron powder diffraction and aberration corrected scanning transmission electron microscope, unveiling the full occupation of Mo 6+ -dopant at the t1 tetrahedral site. In half-cells, MWNO exhibits enhanced fast-rechargeability. In this work, the origin of the improved performance is investigated by ultraviolet–visible diffuse reflectance spectroscopy, density functional theory (DFT) computation, and electrochemical impedance spectroscopy, revealing that bandgap narrowing improves the electrical conductivity of MWNO. Furthermore, operando X-ray diffraction elucidates that MWNO exhibits a typical solid-solution phase conversion-based lithium-ion insertion/extraction mechanism with reversible structural evolution during the electrochemical reaction. The boosted lithium-ion diffusivity of MWNO, due to the Mo 6+ /W 6+ doping effect, is confirmed by a galvanostatic intermittent titration technique and DFT. With the simultaneously enhanced electrical conductivity and lithium-ion diffusivity, MWNO successfully demonstrates its fast-rechargeability and practicality in the LiNi 0.5 Mn 1.5 O 4 -coupled full-cells. Therefore, this work illustrates the potential of ionothermal synthesis in energy storage materials and provides a mechanistic understanding of the doping effect on improving material's electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2026

Achieving 20.1% Efficiency in Organic Solar Cells Through Interconnected Fibrillar Networks via Local Molecular Stacking

ABSTRACT The performance of organic solar cells (OSCs) is governed by how molecular packing evolves into interconnected networks that facilitate exciton dissociation and charge transport. Using an all‐small‐molecule blend DR3TSBDT:Y6 as a model system, we study how local molecular stacking evolves into performance‐relevant morphology during solvent vapor annealing (SVA) and subsequent thermal annealing (TA). SVA promotes end‐to‐end stacking of amorphous acceptors to form interconnected fibrils, while TA compacts inter‐fibril spacing without disrupting favorable local order. Such molecular‐to‐morphological refinements broaden light absorption, enhance charge transport, and markedly improve device efficiency. Extending this approach to additional blend systems (D18:Y6, D18:L8‐BO, and DR3TSBDT:L8‐BO) yields similar structural evolution and performance gains, with the D18:L8‐BO system achieving up to 20.10% PCE. Our study establishes control over local stacking in amorphous acceptors into fibrillar networks as a general and effective route to realize high‐performance OSCs.

Wu, Junying↗