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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Controlling dendrite propagation in solid-state batteries with engineered stress

Metal-dendrite penetration is a mode of electrolyte failure that threatens the viability of metal-anode-based solid-state batteries. Whether dendrites are driven by mechanical failure or electrochemical degradation of solid electrolytes remains an open question. If internal mechanical forces drive failure, superimposing a compressive load that counters internal stress may mitigate dendrite penetration. Here, we investigate this hypothesis by dynamically applying mechanical loads to growing dendrites in Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 solid electrolytes. Operando microscopy reveals marked deflection in the dendrite growth trajectory at the onset of compressive loading. For sufficient loading, this deflection averts cell failure. Using fracture mechanics, we quantify the impact of stack pressure and in-plane stresses on dendrite trajectory, chart the residual stresses required to prevent short-circuit failure, and propose design approaches to achieve such stresses. For the materials studied here, we show that dendrite propagation is dictated by electrolyte fracture, with electronic leakage playing a negligible role.

25 ENERGY STORAGE↗
NASA NTRS1982

Quantum-chemical modeling of smectite clays

A self-consistent charge extended Hueckel program is used in modeling isomorphic substitution of Al(3+) by Na(+), K(+), Mg(2+), Fe(2+), and Fe(3+) in the octahedral layer of a dioctahedral smectite clay, such as montmorillonite. Upon comparison of the energies involved in the isomorphic substitution, it is found that the order for successful substitution is as follows: Al(3+), Fe(3+), Mg(2+), Fe(2+), Na(+), which is equivalent to Ca(2+), and then K(+). This ordering is found to be consistent with experimental observation. The calculations also make it possible to determine the possible penetration of metal ions into the clay's 2:1 crystalline layer. For the cases studied, this type of penetration can occur at elevated temperatures into regions where isomorphic substitution has occurred with metal ions that bear a formal charge of less than 3+. The computed behavior of the electronic structure in the presence of isomorphic substitution is found to be similar to behavior associated with semiconductors.

Aronowitz, S.↗
DOE OSTI2021

Mechanism of Metal Intercalation under Graphene through Small Vacancy Defects

Metal intercalation under graphene has attracted extensive experimental and theoretical research because of its capability to manipulate the electronic structure and properties of graphene. However, the pathways and mechanisms of intercalation are still not well understood. Here, we systematically investigate the intercalation process of metal atoms through graphene vacancies using first-principles calculations. We show that the energy barrier for metal atom penetration through the vacancies in graphene is small as long as the size of the vacancy is larger than a mono-vacancy. However, metal atoms are strongly bonded to the vacancy so that the detachment energy of a metal atom from the vacancy is extremely high. This inhibits the diffusion of the metal atom into the gallery beneath the surface to complete the intercalation process. On the other hand, our calculation results show that the detachment energy of a metal atom from a metal dimer at small vacancy defects is significantly reduced, making intercalation much easier. Therefore, the key step limiting the intercalation process is the detachment of the metal atoms from vacancy defects. This finding from our study provides useful insight into the defect-assisted intercalation mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

The effect of aspect ratio on the mechanical behavior of Li metal in solid-state cells

The Li metal anode is necessary for solid-state batteries to dramatically exceed the energy density of state-of-the-art conventional Li-ion batteries. To enable the Li metal anode, the mechanical properties of Li metal under compression in a commercially relevant cell configuration must be determined. This work examines the compression creep behavior of Li metal coupled with a relevant model solid-state electrolyte (Li 6.5 La 3 Ta 0.5 Zr 1.5 O 12 ) and current collector (Ni) as a function of applied stress (1–10 MPa) and Li foil thickness (100–700 μm). At 1 MPa applied stress, the strain rate of all Li foil thicknesses under compression was almost four orders of magnitude lower than what is predicted from tensile creep tests. Steady-state creep behavior was observed for Li foil ≥350 μm at 5 MPa and ≥250 μm at 10 MPa. Conversely, sustained creep deformation was not observed for 100 and 150 μm Li foils at any applied stress. It is suggested that friction at the Li/LLZO and Li/Ni interfaces leads to the formation of hydrostatic stress that controls Li deformation at low aspect ratios. Finally, these results have implications for battery pack stack pressure requirements, particularly relating to void formation during stripping and Li metal filament penetration during plating.

25 ENERGY STORAGE↗
DOE OSTI2020

Studies of surface adsorbate electronic structure and femtochemistry at the fundamental length and time scales. Final report

The electronic structure and ultrafast (10-15 s-femtosecond timescale) electron dynamics were investigated for clean and atom/molecule covered metal surfaces. The studies were performed by scanning tunneling microscopy (STM) to measure the structure of adsorbed atoms and molecules on metal surfaces, and to investigate their electronic properties. The electronic structure of the observed molecular networks was calculated by electronic structure theory in collaboration with Prof. Jin Zhao, who is a long-time collaborator, a Professor at the University of Science and Technology of China, and holds an Adjunct Professorship at the University of Pittsburgh. We also investigated the electronic properties of C60 molecules when they are templated by corrugated black phosphorous surfaces. We found unexpected charge delocalization that is enabled by the templating. This research was done in collaboration with Professor Min Feng at the Wuhan University, and who also holds an Adjunct Professorship at the University of Pittsburgh. Moreover, the electronic structure and electron dynamics in metal surfaces were investigated by time-resolved photoemission electron spectroscopy. The focus of ultrafast spectroscopy has been on the plasmonic response of silver surfaces. One direction has been to develop multidimensional (energy, momentum, and time) photoelectron spectroscopy of the coherent response of solid surfaces. This method was applied to study the collective electron excitations known generally as plasmons, which screen optical fields from penetration into metals. Although this collective response has been known for more than 60 years and is used extensively to deposit optical energy into metals, how this happens is poorly known. We investigated the plasmonic response of silver at the point where the dielectric response passes through zero and bulk plasmon is excited by light. We discovered that the plasmon excitation decays by exciting electrons from the Fermi level of a metal, which is contrary to what is believed in the plasmonic science community. This research has been performed in collaboration with Dr. Marcel Reutzel, who was a postdoctoral fellow working on this research at the University of Pittsburgh, and now has a faculty position at the University of Göttingen in Germany. Prof. Branko Gumhalter from the Institute of Physics in Zagreb contributed on the theory of plasmonic decay processes. Furthermore, we investigated the Floquet engineering of electronic bands in metals leading to multiphoton photoemission and above threshold photoemission. Finally, we demonstrated that it is possible to change the electronic structure of metals by application of optical fields. Our studies indicated that this happens on subfemtosecond time scale and could potentially be used in ultrafast information processing and quantum computation. Related document information

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Mixed Cationic and Anionic Redox in Ni and Co Free Chalcogen-Based Cathode Chemistry for Li-Ion Batteries

Mixed cationic and anionic redox cathode chemistry is emerging as conventional cationic-redox of transition metal based layered oxides are reaching their theoretical capacity limit. However, these anionic redox in transition metal oxide-based cathodes attained by taking excess lithium has resulted in stability issues due to weak metal - oxygen ligand covalency. Here, we present an alternative approach of improving metal - ligand covalency by introducing less electronegative chalcogen ligand (sulfur) in the cathode structural framework where the metal dband penetration into ligand p-band thereby utilizing reversible mixed anionic and cationic redox chemistry. Through this design strategy, we report possibility of developing a new family of layered cathode materials when partially filled d orbital redox couples like Fe 2+/3+ are introduced in the Li-ion conducting phase (Li 2 SnS 3 ). Further, the electron energy loss spectroscopy (EELS) and X-ray absorption near-edge structure (XANES) analysis are used to qualitatively identify the charge contributors at the metal and ligand sites during Li + extraction. The detailed high-resolution transmission electron microscopy (HR-TEM) and high annular dark field-scanning transmission electron microscopy (HAADF-STEM) investigation reveal the multi redox induced structural modifications and its surface amorphization with nanopore formation during cycling. Findings from this study will shed light on designing Ni and Co free chalcogen cathodes and various functional materials in the chalcogen based dual anionic and cationic redox cathode avenue.

25 ENERGY STORAGE↗
DOE OSTI2025

Stress engineering for crack and dendrite prevention in solid electrolytes via ion implantation

Solid-state batteries represent a promising technology that offers safer and more densely packed energy storage. A primary cause of failure in solid-state cells is the penetration of metal dendrites through the solid electrolyte. Here, we report that fluorine-ion implantation can enhance the mechanical resistance of solid electrolyte Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 to dendrite propagation by inducing residual compressive stress in the subsurface of the electrolyte. Ion implantation modifies subsurface residual stress and also alters the electrolyte’s surface, resulting in multifunctional enhancement. The combined chemical and mechanical effects of ion implantation enable reversible lithium metal stripping and plating at elevated current densities while enhancing air stability and mitigating the formation of a harmful carbonate layer at the surface. This study provides new insights into a scalable dendrite-suppression strategy for designing solid-state batteries suitable for cycling at room temperature and low stack pressures.

25 ENERGY STORAGE↗
NASA NTRS1968

Meteoroid hazard near moon.

Meteoroid hazard in near moon environment, measuring rate of penetration of metal skin with Lunar Orbiters

Grew, G. W.↗
NASA NTRS2002

FSW of Tapered Thickness Welds using an Adjustable Pin Tool

This viewgraph presentation describes the advantages of tapered thickness welds in FSW (friction stir welding), the structure of FSW welds, the adjustable pin tool used in FSW. Other topics described include compliance and temperature measurement in a FSW system, loads and torque upon the pin tool and its ability to penetrate different metals, and the results and metallurgy of FSW welds.

Adams, Glynn↗
NASA NTRS1975

The Effect of a Planetary Surface Penetrator on the Soil Column Surrounding the Impacting Body

A prototype penetrator instrument was impacted into a dry lake bed. Laboratory studies of the soil surrounding the penetrator revealed that the soil was contaminated by paint and metal from the penetrator's casing. Paint pigment rich in titanium and sulfur was found in the adjacent soil. The highly mobile paint pigment migrated onto viewing ports in the penetrator's exterior. Bulk analysis of the soil adjacent to the impactor showed a significant increase in both elements, as well as the presence of metal chips from the casing and nose cone. It is recommended that great care be taken in the use of coating materials and the metal alloys selected for the penetrator's exterior, or the accuracy of any experiment requiring an uncontaminated in situ sample may be adversely affected.

Blanchard, Maxwell B.↗
NASA NTRS1993

A study of metal-ceramic wettability in SiC-Al using dynamic melt infiltration of SiC

Pressure-assisted infiltration with a 2014 Al alloy of plain and Cu-coated single crystal platelets of alpha silicon carbide was used to study particulate wettability under dynamic conditions relevant to pressure casting of metal-matrix composites. The total penetration length of infiltrant metal in porous compacts was measured at the conclusion of solidification as a function of pressure, infiltration time, and SiC size for both plain and Cu-coated SiC. The experimental data were analyzed to obtain a threshold pressure for the effect of melt intrusion through SiC compacts. The threshold pressure was taken either directly as a measure of wettability or converted to an effective wetting angle using the Young-Laplace capillary equation. Cu coating resulted in partial but beneficial improvements in wettability as a result of its dissolution in the melt, compared to uncoated SiC.

Asthana, R.↗
NASA NTRS2011

A Comparison of the Capability of Sensitivity Level 3 and Sensitivity Level 4 Fluorescent Penetrants to Detect Fatigue Cracks in Various Metals

In April 2008, NASA-STD-5009 established a requirement that only sensitivity level 4 penetrants are acceptable for NASA Standard Level liquid penetrant inspections. Having NASA contractors change existing processes or perform demonstration tests to certify sensitivity level 3 penetrants posed a potentially huge cost to the Agency. This study was conducted to directly compare the probability of detection (POD) of sensitivity level 3 and level 4 penetrants using both Method A and Method D inspection processes. POD demonstration tests were performed on 6061-Al, Haynes 188 and Ti-6Al-4V crack panel sets. The study results strongly support the conclusion that sensitivity level 3 penetrants are acceptable for NASA Standard Level inspections.

Parker, Bradford H.↗
NASA NTRS1997

Internal and Surface Phenomena in Heterogenous Metal Combustion

The phenomenon of gas dissolution in burning metals was observed in recent metal combustion studies, but it could not be adequately explained by the traditional metal combustion models. The research reported here addresses heterogeneous metal combustion with emphasis on the processes of oxygen penetration inside burning metal and its influence on the metal combustion rate, temperature history, and disruptive burning. The unique feature of this work is the combination of the microgravity environment with a novel micro-arc generator of monodispersed metal droplets, ensuring repeatable formation and ignition of uniform metal droplets with a controllable initial temperature and velocity. Burning droplet temperature is measured in real time with a three wavelength pyrometer. In addition, particles are rapidly quenched at different combustion times, cross-sectioned, and examined using SEM-based techniques to retrieve the internal composition history of burning metal particles. When the initial velocity of a spherical particle is nearly zero, the microgravity environment makes it possible to study the flame structure, the development of flame nonsymmetry, and correlation of the flame shape with the heterogeneous combustion processes.

Dreizin, Edward L.↗
DOE OSTI2024

Thermal barrier systems and methods for access delay

Protective barrier includes a soft metal that inhibits or delays thermal or grinding attack tool penetration. The soft metal, which may be disposed between other layers and otherwise delays thermal attack by expanding or “puffing” during attack. The soft metal can inhibit mechanical attack by rapid ablation and wear of a cutting wheel or blade. The protective barrier may additionally include an oxide or carbide layer.

Brooks, Scott H.↗
NASA NTRS1995

Internal and surface phenomena in metal combustion

Combustion of metals has been widely studied in the past, primarily because of their high oxidation enthalpies. A general understanding of metal combustion has been developed based on the recognition of the existence of both vapor-phase and surface reactions and involvement of the reaction products in the ensuing heterogeneous combustion. However, distinct features often observed in metal particle combustion, such as brightness oscillations and jumps (spearpoints), disruptive burning, and non-symmetric flames are not currently understood. Recent metal combustion experiments using uniform high-temperature metal droplets produced by a novel micro-arc technique have indicated that oxygen dissolves in the interior of burning particles of certain metals and that the subsequent transformations of the metal-oxygen solutions into stoichiometric oxides are accompanied with sufficient heat release to cause observed brightness and temperature jumps. Similar oxygen dissolution has been observed in recent experiments on bulk iron combustion but has not been associated with such dramatic effects. This research addresses heterogeneous metal droplet combustion, specifically focusing on oxygen penetration into the burning metal droplets, and its influence on the metal combustion rate, temperature history, and disruptive burning. A unique feature of the experimental approach is the combination of the microgravity environment with a novel micro-arc Generator of Monodispersed Metal Droplets (GEMMED), ensuring repeatable formation and ignition of uniform metal droplets with controllable initial temperature and velocity. The droplet initial temperatures can be adjusted within a wide range from just above the metal melting point, which provides means to ignite droplets instantly upon entering an oxygen containing environment. Initial droplet velocity will be set equal to zero allowing one to organize metal combustion microgravity experiments in a fashion similar to usual microgravity liquid fuel droplet combustion studies. In addition, the internal compositions of rapidly quenched metal particles will be analyzed using SEM technique. Such compositions are similar to those existing during the combustion and provide new insight on metal combustion processes. The results of this experimental work will be used to model the fundamental mechanisms of metal combustion. Preliminary experimental results on Al and Zr particle combustion at normal gravity are discussed here.

Dreizin, Edward L.↗