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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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258 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Structure of the high voltage phase of layered P2-Na 2/3-z [Mn 1/2 Fe 1/2 ]O 2 and the positive effect of Ni substitution on its stability

A combination of operando X-ray diffraction, pair distribution function (PDF) analysis coupled with electrochemical measurements and Mössbauer spectroscopy elucidates the nature of the phase transitions induced by insertion and extraction of sodium ions in P2-Na 0.67 [Ni y Mn 0.5 + y Fe 0.5 -2 y ]O 2 (y = 0, 0.10, 0.15). When phase transitions are avoided, the optimal cathode material – P2-Na 0.67 Fe 0.2 Mn 0.65 Ni 0.15 O 2 - delivers 25% more energy than the unsubstituted material, sustaining high specific energy (350 Wh kg -1 ) at moderate rates and maintains 80% of the original energy density after 150 cycles - a significant improvement in performance vs. the unsubstituted analogue. The crystal structure of the high voltage phase is solved for the first time by X-ray PDF analysis of P2-Na 0.67 -z Fe0.5Mn 0.5 O 2 (where z~0.5), revealing that migration of the transition metals – particularly Fe 3+ - into tetrahedral sites in the interlayer space occurs at high potential. This results in new short range order between two adjacent layers. Although the transition metal migration is reversible as proven by electrochemical performance, it induces a large disfavourable cell polarization. The deleterious high voltage transition is mitigated by substitution of Fe 3+ by Mn 4+ /Ni 2+ , giving rise to better cycling performance. Moreover, as demonstrated by 57 Fe Mössbauer spectroscopy, the much lower ratio of Fe 4+ O6 to Fe 3+ O 6 observed systematically across the range of Ni content – compared to the values expected from a purely ionic model – suggests redox activity involves the O-2p orbitals owing to their overlap with the transition metal-3d orbitals.

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

In‐Operando Spatiotemporal Imaging of Coupled Film‐Substrate Elastodynamics During an Insulator‐to‐Metal Transition

Abstract The drive toward non‐von Neumann device architectures has led to an intense focus on insulator‐to‐metal (IMT) and the converse metal‐to‐insulator (MIT) transitions. Studies of electric field‐driven IMT in the prototypical VO 2 thin‐film channel devices are largely focused on the electrical and elastic responses of the films, but the response of the corresponding TiO 2 substrate is often overlooked, since it is nominally expected to be electrically passive and elastically rigid. Here, in‐operando spatiotemporal imaging of the coupled elastodynamics using X‐ray diffraction microscopy of a VO 2 film channel device on TiO 2 substrate reveals two new surprises. First, the film channel bulges during the IMT, the opposite of the expected shrinking in the film undergoing IMT. Second, a microns thick proximal layer in the substrate also coherently bulges accompanying the IMT in the film, which is completely unexpected. Phase‐field simulations of coupled IMT, oxygen vacancy electronic dynamics, and electronic carrier diffusion incorporating thermal and strain effects suggest that the observed elastodynamics can be explained by the known naturally occurring oxygen vacancies that rapidly ionize (and deionize) in concert with the IMT (MIT). Fast electrical‐triggering of the IMT via ionizing defects and an active “IMT‐like” substrate layer are critical aspects to consider in device applications.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Advances in Neutron Radiography: Application to Additive Manufacturing Inconel 718

Reactor-based neutron radiography is a non-destructive, non-invasive characterization technique that has been extensively used for engineering materials such as inspection of components, evaluation of porosity, and in-operando observations of engineering parts. Neutron radiography has flourished at reactor facilities for more than four decades and is relatively new to accelerator-based neutron sources. Recent advances in neutron source and detector technologies, such as the Spallation Neutron Source (SNS) at the Oak Ridge National Laboratory (ORNL) in Oak Ridge, TN, and the microchannel plate (MCP) detector, respectively, enable new contrast mechanisms using the neutron scattering Bragg features for crystalline information such as average lattice strain, crystalline plane orientation, and identification of phases in a neutron radiograph. Additive manufacturing (AM) processes or 3D printing have recently become very popular and have a significant potential to revolutionize the manufacturing of materials by enabling new designs with complex geometries that are not feasible using conventional manufacturing processes. However, the technique lacks standards for process optimization and control compared to conventional processes. Residual stresses are a common occurrence in materials that are machined, rolled, heat treated, welded, etc., and have a significant impact on a component s mechanical behavior and durability. They may also arise during the 3D printing process, and defects such as internal cracks can propagate over time as the component relaxes after being removed from its build plate (the base plate utilized to print materials on). Moreover, since access to the AM material is possible only after the component has been fully manufactured, it is difficult to characterize the material for defects a priori to minimize expensive re-runs. Currently, validation of the AM process and materials is mainly through expensive trial-and-error experiments at the component level, whereas in conventional processes the level of confidence in predictive computational modeling is high enough to allow process and materials optimization through computational approaches. Thus, there is a clear need for non-destructive characterization techniques and for the establishment of processing- microstructure databases that can be used for developing and validating predictive modeling tools for AM.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Advanced Microscopy and Spectroscopy for Probing and Optimizing Electrode-Electrolyte Interphases in High Energy Lithium Batteries (Final Scientific/Technical Report)

The earliest developed LiCoO 2 layered oxide cathode material sparked the development of other layered cathode materials, dominating the positive electrode materials for lithium ion batteries. Within the practical operating conditions of today, the current generation layered oxide materials do not meet the future energy storage demands of 350 Wh kg -1 at cell level. Li-rich layered oxide (LRLO) materials have the potential to meet the high energy demands. Unlike the classical layered oxides, LRLO materials exhibit capacities that go beyond conventional topotactic mechanistic theoretical values. Despite its high capacities, this material has several challenges (voltage fading, structural instability, sluggish kinetics, cathode electrolyte interphase instability, etc.) that must be overcome in order to reach commercialization. In the past five years, our research group has made great progress on developing advanced characterization techniques coupled with atomic scale modeling to properly characterize the dynamic phenomena that govern the performance limitations of LRLO materials. Furthermore, our efforts have guided the material synthesis and surface modification to improve capacity retention. By carefully controlling the oxygen activities through the creation of uniform oxygen vacancies, we were able to avoid structural decomposition in LRLO. Our materials deliver a discharge capacity as high as 306 mAh g -1 with an initial coulombic efficiency of 90.6%. Furthermore, they do not exhibit obvious capacity decay with a reversible capacity over 300 mAh g -1 after 100 cycles at 0.1 C-rate. Our approach demonstrates the critical needs for advanced diagnosis and characterization. It is through the in-depth understanding of these high voltage cathode materials at atomistic and molecular level and their dynamic changes during the operation of batteries; we can successfully formulate strategies to further optimize this class of cathode materials, especially for the voltage instabilities. The diagnostic tools developed here can also be leveraged to study anode materials such as Li metal anode. The challenge of probing Li metal is the low dose tolerance (high beam sensitivity) of Li metal. We will have to apply cryogenic method (low-temperature) and low-dose electron microscopy and specialized camera to enable the characterization of the lithium metal.

25 ENERGY STORAGE↗
DOE OSTI2025

In-situ/operando study of Cu-based nanocatalysts for CO 2 electroreduction using electrochemical liquid cell TEM

The structure of a nanocatalyst during electrocatalytic reactions often deviates from its pristine structure due to intrinsic properties, or physical and chemical adsorption at the catalytic surfaces. Taking Cu-based catalysts for CO 2 electroreduction reactions (CO 2 RR) as an example, they often experience segregation, leaching, and alloying during reactions. With the recent breakthrough development of high-resolution polymer electrochemical liquid cells, in-situ electrochemical liquid cell transmission electron microscopy (EC-TEM) alongside other advanced microscopy techniques, has become a powerful platform for revealing electrocatalysts restructuring at the atomic level. Considering the complex reactions involving electrified solid-liquid interfaces and catalyst structural evolution with intermediates, systematic studies with multimodal approaches are crucial. In this article, we demonstrate a research protocol for the study of electrocatalysts structural evolution during reactions using the in-situ EC-TEM platform. Using Cu and CuAg nanowire catalysts for CO 2 RR as model systems, we describe the experimental procedures and findings. We highlight the platform’s crucial role in elucidating atomic-scale pathways of nanocatalyst restructuring and identifying catalytic active sites, as well as avoiding potential artifacts to ensure unbiased conclusions. Using the multimodal characterization toolbox, we provide the opportunity to correlate the structure of a working catalyst with its performance. Finally, we discuss advancements as well as the remaining gap in elucidating the structural-performance relationship of working catalysts. We expect this article will assist in establishing guidelines for future investigations of complex electrochemical reactions, such as CO 2 RR and other catalytic processes, using the in-situ EC-TEM platform.

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

Elucidating the Role of Electric Fields in Fe Oxidation via an Environmental Atom Probe

We quantify the effects of intensely applied electric fields on the Fe oxidation mechanism. The specimen are pristine Fe single crystals exposing a variety of surface structures identified by field ion microscopy. These crystals are simultaneously exposed to low pressures of pure oxygen gas, on the order of 10 −7 mbar, while applying intense electric fields on their surface of several tens of volts per nanometer. The local composition of the different surface structures is probed directly and in real time using an Environmental Atom Probe and successfully compared with first principles-based models. We found that rough Fe{244} and Fe{112} facets are more reactive toward oxygen than compact Fe{024} and Fe{011} facets. Results demonstrate that the influence of an electric field on the oxidation kinetics depends on the timescales that are involved as the system evolves toward equilibrium. The initial oxidation kinetics show that strong increases in electric fields facilitate the formation of an oxide. However, as one approaches equilibrium, high field values mitigate this formation. Ultimately, this study elucidates how high externally applied electric fields can be used to dynamically exploit reaction dynamics at the nanoscale towards desired products in a catalytic reaction at mild reaction conditions.

09 BIOMASS FUELS↗