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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 OSTI2023

Irreparable Interphase Chemistry Degradation Induced by Temperature Pulse in Lithium–Ion Batteries

While it is widely recognized that the operating temperature significantly affects the energy density and cycle life of lithium-ion batteries, the consequence of electrode-electrolyte interphase chemistry to sudden environmental temperature changes remains inadequately understood. Here, we systematically investigate the effects of a temperature pulse (T pulse) on the electrochemical performance of LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) pouch full cells. By utilizing advanced characterization tools, such as time-of-flight secondary-ion mass spectrometry, we reveal that the T pulse can lead to an irreversible degradation of cathode-electrolyte interphase chemistry and architecture. Despite negligible immediate impacts on the solid-electrolyte interphase (SEI) on graphite anode, aggregated cathode-to-anode chemical crossover gradually degrades the SEI by catalyzing electrolyte reduction decomposition and inducing metallic dead Li formation because of insufficient cathode passivation after the T pulse. Consequently, pouch cells subjected to the T pulse show an inferior cycle stability to those free of the T pulse. Furthermore, this work unveils the effects of sudden temperature changes on the interphase chemistry and cell performance, emphasizing the importance of a proper temperature management in assessing performance.

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

Anomalous Role of Carbon in Pd‐Catalyzed Selective Hydrogenation

Carbonaceous species, including subsurface carbidic carbon and surface carbon, play crucial roles in heterogeneous catalysis. Many reports suggested the importance of subsurface carbon in the selective hydrogenation of alkynes over Pd‐based catalysts. However, the role of surface carbon has been largely overlooked. Here, we demonstrate that subsurface carbon in Pd is not responsible for the selectivity in acetylene hydrogenation. In contrast, the structure of surface carbonaceous species plays a decisive role in hydrogenation selectivity. Electron microscopy and spectroscopy evidence, along with theoretical modelling, reveal that partial graphitization of surface carbonaceous species results in unique spatial confinement of surface reaction intermediates, thus altering the reaction energy landscape in favour of ethylene desorption as opposed to over‐hydrogenation. This mechanism for selectivity control is analogous to enzyme catalysis, where the active centers selectively attract reactants and release products. Similar mechanism may be present in CO/CO 2 hydrogenation and alkane dehydrogenation reactions.

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

New Insights into Structural Evolution of LiNiO 2 Revealed by Operando Neutron Diffraction

LiNiO 2 (LNO) represents the end member in the compositional space of the LiNi 1-x-y Mn x Co y O 2 (as x and y approach zero) cathode system. Despite its high theoretical specific capacity (275 mAh/g), LNO suffers from phase transitions with large volume change and unfavorable reactions upon electrochemical cycling, which restricts its practical use in the application of lithium-ion batteries. While the contributing factor to the structural instability is commonly linked to the undesired volume collapse associated with the H2-H3 phase transition, detailed analysis of structural evolution following the entire route of phase transitions (H1-M-H2-H3) in real time under battery operating conditions remains a challenging task. In this work, we employ operando neutron diffraction to study the structural changes (crystal lattice, Li/Ni–O bond length, O–Ni–O bond angles, and LiO 2 /NiO 2 layer thickness) of LNO cathode in a home-built Li x NiO 2 || graphite full cell during Li + de-/intercalation. In particular, the anomalous increase(decrease) of Ni–O(Li–O) bond length at high SOC (>~85 %) in the H3 phase is discussed in the context of O 2- (2p)→Ni 4+ (3d) negative charge transfer.

25 ENERGY STORAGE↗
DOE OSTI2020

Hydrazone-Linked Heptazine Polymeric Carbon Nitrides for Synergistic Visible-Light-Driven Catalysis

Heptazine-based conjugated polymeric carbon nitrides (PCNs) are promising metal-free photocatalysts, yet their synthesis is challenging due to the electron-deficiency and insolubility of heptazine units. Indeed, heptazine-containing polymers have only been prepared through nucleophilic substitution with amines by using toxic cyameluric chloride as the starting material. Herein, we report the novel and environmentally friendly method for preparing heptazine-based mesoporous PCNs with hydrazone links formed through a simple Schiff base condensation of melem-NH 2 and aldehydes. Unlike cyameluric chloride, melem-NH 2 is non-toxic, stable, and can be readily obtained from melem and hydrazine in solution. We demonstrate that the hydrazone linkages and the heptazine units synergistically enhance the photocatalytic activity of PCNs in visible-light-driven aerobic oxidation of benzyl alcohol to benzaldehyde. In particular, the polymer constructed from melem-NH2 and p-phthalaldehyde shows 17 times more activity than graphitic carbon nitride (g-C 3 N 4 ).

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

Degradation Diagnostics from the Subsurface of Lithium-Ion Battery Electrodes

Despite the long-established rocking-chair theory of lithium-ion batteries (LIBs), developing novel characterization methodology with higher spatiotemporal resolution facilitates a better understanding of the solid electrolyte interphase studies to shape the reaction mechanisms. In this work, we develop a Xenon ion plasma focused ion beam (Xe + PFIB)-based characterization technique to probe the cross-sectional interface of both ternary cathode and graphite anode electrodes, with the focus on revealing the chemical composition and distribution underneath the electrode surface by in-depth analysis of secondary ions. Particularly, the lithium fluoride is detected in the pristine cathode prior to contact with the electrolyte, reflecting that the electrode degradation is in the form of the loss of lithium inventory during electrode preparation. This degradation is related to the hydrolysis of the cathode material and the decomposition of the PVDF binder. Here, through the quantitative analysis of the transition-metal degradation products, manganese is found to be the dominant element in the newly formed inactive fluoride deposition on the cathode, while no transition metal signal can be found inside the anode electrode. These insights at high resolution implemented via a PFIB-based characterization technique not only enrich the understanding of the degradation mechanism in the LIBs but also identify and enable a high-sensitivity methodology to obtain the chemical survey at the subsurface, which will help remove the capacity-fade observed in most LIBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Solvent-Free Manufacturing of Lithium-Ion Battery Electrodes via Cold Plasma

Slurry casting has been used to fabricate lithium-ion battery electrodes for decades, which involves toxic and expensive organic solvents followed by high-cost vacuum drying and electrode calendering. This work presents a new manufacturing method using a nonthermal plasma to create inter-particle binding without using any polymeric binding materials, enabling solvent-free manufacturing electrodes with any electrochemistry of choice. The cold-plasma-coating technique enables fabricating electrodes with thickness (>200 μm), high mass loading (>30 mg cm -2 ), high peel strength, and the ability to print lithium-ion batteries in an arbitrary geometry. This crosscutting, chemistry agnostic, platform technology would increase energy density, eliminate the use of solvents, vacuum drying, and calendering processes during production, and reduce manufacturing cost for current and future cell designs. Here, lithium iron phosphate and lithium cobalt oxide were used as examples to demonstrate the efficacy of the cold-plasma-coating technique. It is found that the mechanical peel strength of cold-plasma-coating-manufactured lithium iron phosphate is over an order of magnitude higher than that of slurry-casted lithium iron phosphate electrodes. Full cells assembled with a graphite anode and the cold-plasma-coating-lithium iron phosphate cathode offer highly reversible cycling performance with a capacity retention of 81.6% over 500 cycles. For the highly conductive cathode material lithium cobalt oxide, an areal capacity of 4.2 mAh cm -2 at 0.2 C is attained. We anticipate that this new, highly scalable manufacturing technique will redefine global lithium-ion battery manufacturing providing significantly reduced plant footprints and material costs.

25 ENERGY STORAGE↗
DOE OSTI2020

Effect of Anode Porosity and Temperature on the Performance and Lithium Plating During Fast-Charging of Lithium-Ion Cells

Twenty-four single-layer approximate to 32 mAh pouch cells are tested to determine the effect of electrode porosity on lithium plating. Twelve cells contain a graphite electrode that is 26% porous, and 47% for the other twelve. The cells are cycled using a 6-C charge and a C/2 discharge protocol at temperatures in the range of 20-50 degrees C. A macro-homogeneous electrochemical model and microstructure analysis tool set are used to help interpret experimental observations for the effect of anode porosity and ambient temperature on fast-charging performance. Additionally, comparison between the two also highlights gaps in current theoretical understanding that need to be addressed. In post-test examination, lithium plating is seen in all cells, regardless of porosity. Elevated temperature is shown to reduce the amount of lithium plating and improve initial fast-charge capacity, but also changes the rate of other, less well-understood degradation mechanisms. Apparent kinetic rate laws, At + Bt 1/2 , where A and B are constants, can be fit to most of the capacity loss and resistance increase data. The relative magnitudes of A and B change with temperature and porosity. The capacity loss data at 50 degrees C from the high-porosity cells are fit by a logistics rate law.

25 ENERGY STORAGE↗
DOE OSTI2023

Characterizing the seismic response of a molten salt nuclear reactor

Abstract One Generation IV nuclear reactor, which uses a fluoride salt as a coolant, graphite reflector blocks as a moderator, and circulating buoyant TRISO pebbles as fuel is at an advanced stage of development. To characterize the seismic behavior of components of this reactor, validate numerical models for analysis, and develop recommendations for design, a set of earthquake‐simulator experiments on a scaled model of the reactor vessel and its internals was executed on a six‐degree‐of‐freedom earthquake simulator. The model was seismically isolated at its base using two types of spherical sliding bearings. The scaled model involved representations of the prototype reactor vessel, core barrel, reflector blocks, coolant, and spherical fuel pebbles. The material and geometric properties of different test components were selected based on a dynamic similitude scaling analysis and an approximate length scale of 0.4. Four sets of three‐component earthquake motions were used as inputs for testing. Instrumentation on the test specimen recorded the dynamic responses of the outer vessel, core barrel, and reflector‐block assembly, the hydrodynamic responses (sloshing and hydrodynamic pressure) of the liquid coolant, pebble consolidation under earthquake shaking, and the behavior of the isolation systems. This paper describes the design of the experiments and presents key results from the tests. The dynamic responses of the outer vessel, core barrel, and the reflector blocks revealed that the components responded as a unit for the intense shaking used in the experiments. The sloshing response of the fluid in a thin annulus near the perimeter of the vessel was heavily damped. The change in the packing fraction of the pebble bed under repeated, intense 3D earthquake shaking was less than 3%. Seismically isolating the vessel substantially reduced demands on its internal components.

Engineering↗
DOE OSTI2022

Raman signatures of detonation soot

Soot generated from the detonation of nine explosives was investigated with Raman microspectroscopy and high-resolution transmission electron microscopy (HRTEM). The first order bands, located at approximately 1,580 (G), 1,350 (D1), 1,620 cm –1 (D2), 1,500 (D3), and 1,200 (D4), are used to provide information on the carbon allotropes and defects. The intensity ratios and the full-width at half-maximum provide an indication of the disorder in the material. The Raman spectra of soot acquired from the detonation of nine explosives showed differences which can be used to identify the precursor explosive. Overall, most differences in the spectra were correlated with the presence of amorphous carbon in the soot. In additional to identification of distinct bands in the spectra via deconvolution, principal component analysis was also used to differentiate the different types of soot. HRTEM performed on soot samples with different explosive precursors identified several distinct allotropes of carbon such as nanodiamonds, carbon onions, graphite fibers, and amorphous carbon.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2020

Coefficient of Thermal Expansion during Ratchet Growth of TATB Compactions

Triamino trinitrobenzene (TATB) is an insensitive high explosive, meaning that it is quite immune from accidental detonation and only performs in appropriately engineered configurations. While this is advantageous for applications, the TATB crystal is graphitic and possesses significant thermal and mechanical anisotropy. Compactions of TATB crystals, with or without binder, have been shown to have oriented TATB crystals that relate to the pressing geometry and process, and this TATB texture necessarily imparts microscale and macroscale anisotropy to the compaction. By a mechanism not fully understood, thermal cycling results in irreversible volume expansion (also called ratchet growth) of the compaction likely by creating stress points on the microscale. Changes in density caused by thermal cycling can certainly effect the explosive performance. Our past characterization of the ratchet growth phenomenon has focused on the magnitude of the irreversible strain as measured before and after a thermal cycle. Finally, in the work presented here, we analyze the evolving thermal expansion behavior during the ascending and descending temperature ramps, providing further insight into the material changes taking place during the ratchet growth phenomenon.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2022

Coefficient of Thermal Expansion Evolution during Ratchet Growth of PBX 9502 and Neat TATB

The Plastic-Bonded Explosive (PBX) 9502 is comprised of the insensitive high explosive TATB (triamino trinitrobenzine) crystals coated in FK-800 polymer binder and isostatically pressed. The TATB crystals have a graphitic, plate-like morphology and possess significant thermal and mechanical anisotropy. Compactions of neat TATB or TATB-based composites (like PBX 9502) have been shown to have TATB crystals that are oriented during the pressing process giving rise to TATB texture and resulting in micro- and macro-scale anisotropy of the compaction. Thermal cycling of the compactions results in irreversible volume expansion (or ratchet growth) likely by creating stress points on the microscale. However, the actual mechanism behind this expansion is not fully understood. Previous characterization of the ratchet growth phenomenon has focused on the magnitude of the irreversible strain as measured before and after a thermal cycle. In the work presented here, we analyze the evolving thermal expansion behavior during the ascending and descending temperature ramps and compare differences observed due to the presence/absence of binder in the compaction.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2025

Layers Can Be Deceiving: A Hopping Model for Small Molecule Diffusion in TATB Crystal

Sorption of small molecule gases in materials can play a significant role in their long‐term stability and compatibility within multi‐material assemblies. While many material properties of the insensitive high explosive TATB (1,3,5‐triamino‐2,4,6‐trinitrobenzene) are well understood, very little is known regarding its permeability to gases. TATB crystal exhibits a graphitic‐like layered packing structure that evokes a mental schema in which the layers form nanoscopic channels, but it is unclear whether this structure promotes gas transport. Here, we use molecular dynamics (MD) simulations to predict transport of small molecules through TATB single crystal. An approach to fit classical force fields is developed to model TATB interactions with H 2 O, He, Ne, and Ar, which is then combined with steered MD to probe gas transport along selected directions in the crystal. We find that small molecule transport occurs via a hopping mechanism that exhibits distinct jumps between interstitial sites and is substantially faster normal to the layers as compared to through them. This result stems from the finding that intralayer junctions between adjacent TATB molecules are the most stable interstitial sites and that energetic barriers are lower for hopping between adjacent layers. An empirical model for diffusion rate based on the MD data shows that the rate decays exponentially with increasing molecular radius and is negligibly small for all molecules larger than He, including common atmospheric gases. These findings have implications for the interpretation of experiments that measure surface area, material response to extreme conditions, and are expected to help constrain models for material aging.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Antimicrobial mechanisms of g‐C 3 N 4 @ ZnO against oomycetes Phytophthora capsici: from its metabolism, membrane structures and growth

Abstract BACKGROUND Phytophthora capsici , a refractory and model oomycete plant pathogen, especially threatens multiple vegetable crops. A limited number of chemical pesticides play a vital role in controlling oomycete plant diseases. However, this approach often leads to excessive use of chemical agent, exacerbates environmental issues and more and more drug‐resistant strains of oomycete. Therefore, it is imperative to devise innovative solutions that can effectively address the infection of oomycete while maintaining high levels of environmental sustainability and low toxicity. RESULTS In this study, g‐C 3 N 4 @ZnO heterostructure was synthesized and characterized. The g‐C 3 N 4 @ZnO showed higher toxicity on Phytophthora capsici than graphitic carbon nitride (g‐C 3 N 4 ) nanosheets and zinc oxide (ZnO) nanoparticles in vitro and in vivo . Except the hyphal growth of Phytophthora capsici , their germination rate of spores, sporangium formation and number of spores were all suppressed by g‐C 3 N 4 @ZnO heterostructure. Furthermore, we found that this g‐C 3 N 4 @ZnO heterostructure has higher photocatalytic activity under visible light, which potentially enhanced the reactive oxygen species (ROS) mediated stress on Phytophthora capsici . Ultrastructural morphology, global changes of gene expression and weighted gene co‐expression network analysis all supported that the anti‐oomycete activity of g‐C 3 N 4 @ZnO was manifested in the destruction of membrane system and inhibition of multiple metabolisms of Phytophthora capsici under visible irradiation, which also could be attributed to the ROS and zinc ion (Zn 2+ ) mediated stress. CONCLUSION This works offers a novel oomycete disease management strategy by using g‐C 3 N 4 @ZnO, which were attributed to the ROS stress, destruction of membrane system and inhibition of multiple metabolisms. © 2023 Society of Chemical Industry.

Cai, Lin↗
DOE OSTI2022

A Low-Voltage Layered Na 2 TiGeO 5 Anode for Lithium-Ion Battery

Titanium-based anode materials have achieved much progress with the wide studies in lithium-ion batteries. However, these known materials usually possess high discharge voltage platforms and limited energy densities. In this work, a titanium-based oxide of Na 2 TiGeO 5 with layered structure, two-dimensional lamellar frame and exposed highly active (001) facet, exhibiting good electrochemical performance in terms of high capacity (410 mAh g –1 with a current density of 50 mA g –1 ), excellent rate capability and cycling stability with no obvious capacity attenuation after 4000 cycles, is reported. The appropriate discharge voltage plateau at around 0.2 V endows the Na 2 TiGeO 5 anode material high security compared with graphite and high energy density compared with spinel Li 4 Ti 5 O 12 . Combining the electrochemical tests and the density functional theory calculations, the Li + storage mechanism of Na 2 TiGeO 5 is elucidated and the conversion reaction process is revealed. More importantly, this study provides a way to develop low-voltage and high-capacity titanium-based anode materials for efficient energy storage.

25 ENERGY STORAGE↗
DOE OSTI2024

Leveraging Curvature on N–Doped Carbon Materials for Hydrogen Storage

Carbon sorbent materials have shown great promise for solid-state hydrogen (H 2 ) storage. Modification of these materials with nitrogen (N) dopants has been undertaken to develop materials that can store H 2 at ambient temperatures. In this work density functional theory (DFT) calculations are used to systematically probe the influence of curvature on the stability and activity of undoped and N-doped carbon materials toward H binding. Specifically, four models of carbon materials are used: graphene, [5,5] carbon nanotube, [5,5] D 5d -C 120 , and C 60 , to extract and correlate the thermodynamic properties of active sites with varying degrees of sp 2 hybridization (curvature). From the calculations and analysis, it is found that graphitic N-doping is thermodynamically favored on more pyramidal sites with increased curvature. In contrast, it is found that the hydrogen binding energy is weakly affected by curvature and is dominated by electronic effects induced by N-doping. These findings highlight the importance of modulating the heteroatom doping configuration and the lattice topology when developing materials for H 2 storage.

08 HYDROGEN↗
DOE OSTI2024

Tunable Magnetic Coupling in Graphene Nanoribbon Quantum Dots

Abstract Carbon‐based quantum dots (QDs) enable flexible manipulation of electronic behavior at the nanoscale, but controlling their magnetic properties requires atomically precise structural control. While magnetism is observed in organic molecules and graphene nanoribbons (GNRs), GNR precursors enabling bottom‐up fabrication of QDs with various spin ground states have not yet been reported. Here the development of a new GNR precursor that results in magnetic QD structures embedded in semiconducting GNRs is reported. Inserting one such molecule into the GNR backbone and graphitizing it results in a QD region hosting one unpaired electron. QDs composed of two precursor molecules exhibit nonmagnetic, antiferromagnetic, or antiferromagnetic ground states, depending on the structural details that determine the coupling behavior of the spins originating from each molecule. The synthesis of these QDs and the emergence of localized states are demonstrated through high‐resolution atomic force microscopy (HR‐AFM), scanning tunneling microscopy (STM) imaging, and spectroscopy, and the relationship between QD atomic structure and magnetic properties is uncovered. GNR QDs provide a useful platform for controlling the spin‐degree of freedom in carbon‐based nanostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Understanding Discharge‐Driven Growth of Cathode Impedance in Ni‐Rich NMC Cathodes

Degradation of LiNi x Mn y Co 1-x-y O 2 (NMC)-based lithium-ion batteries depends strongly on cut-off voltage ranges. In addition to the high upper cut-off voltage, a high depth of discharge (i.e., lower cut-off voltage) significantly worsens cathode impedance growth and capacity fade during long-term cycling. However, there is currently no consensus on the mechanism behind the negative role of a deep discharge. Here, this phenomenon was investigated in graphite||NMC cells with single-crystal cathodes (LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NMC622) or LiNi 0.76 Co 0.14 Mn 0.10 O 2 (NMC76)) using targeted aging protocols (constant high-voltage holds vs. charge–discharge cycling), while monitoring transition-metal (TM) dissolution, cathode-electrolyte interface (CEI) impedance, and NMC surface composition. We demonstrate a correlation between discharge-driven CEI impedance growth and increased TM dissolution. Furthermore, this degradation pathway is more pronounced in lower-Ni NMC622 than in higher-Ni (NMC76) under comparable delithiation states at charge, with both compositions undergoing the H2→H3 phase transition. X-ray photoelectron spectroscopy (XPS) reveals NMC composition-dependent evolution of surface lattice oxygen and restructured surface layer composition between charged and discharged states. These findings add mechanistic depth to the role of discharge as an active driver of interfacial degradation and provide new insights into its composition dependence.

25 ENERGY STORAGE↗
DOE OSTI2023

Improving the Mechanical Properties of Cast Aluminum Via Ultrasonication-Induced Microstructural Refinement

One barrier to the broader use of cast aluminum alloys in automotive applications is their poor mechanical properties, especially compared to wrought materials. This study investigates the use of ultrasound to refine the microstructure of cast aluminum alloys during solidification and thus improve their mechanical properties. An A356 aluminum alloy (Al-Si-Mg) with added Fe (to mimic a recycle-grade alloy) was cast in a graphite mold with the simultaneous application of ultrasound. Tensile specimens were extracted from the castings and heat treated to a T6 temper. Ultrasonication during casting transformed the morphology of primary aluminum grains from dendritic (~140 microns in size) to globular (~36 microns in size), increased the ultimate tensile strength by 10 %, and tripled the ductility compared to casting without ultrasound. This improvement in strength and ductility demonstrates the potential for ultrasonic processing to improve the performance of cast aluminum alloys without altering their chemistry or additional post-processing.

Aluminum, Solidification, Ultrasound, Grain refinm↗