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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Oxidation of Ammonia Catalyzed by a Molecular Iron Complex: Translating Chemical Catalysis to Mediated Electrocatalysis

Abstract Ammonia is a promising candidate in the quest for sustainable, clean energy. With its capacity to serve as an energy carrier, the oxidation of ammonia opens avenues for carbon‐neutral approaches to address worldwide growing energy needs. We report the catalytic chemical oxidation of ammonia by an Earth‐abundant transition metal complex, trans ‐ [LFe II (MeCN) 2 ][PF 6 ] 2 , where L is a macrocyclic ligand bearing four N ‐heterocyclic carbene (NHC) donors. Using triarylaminium radical cations in MeCN, up to 182 turnovers of N 2 per Fe were obtained from chemical catalysis with an extremely low loading of the Fe catalyst (0.043 mM, 0.004 mol % catalyst). This chemical catalysis was successfully transitioned to mediated electrocatalysis for the oxidation of ammonia. Molecular electrocatalysis by the Fe catalyst and the mediator ( p ‐MeOC 6 H 4 ) 3 N exhibited a catalytic half‐wave potential ( E cat/2 ) of 0.18 V vs [Cp 2 Fe] +/0 in MeCN, and achieved 9.3 turnovers of N 2 at an applied potential of 0.20 V vs [Cp 2 Fe] +/0 at −20 °C in controlled‐potential electrolysis, with a Faradaic efficiency of 75 %. Based on computational results, the catalyst undergoes sequential oxidation and deprotonation steps to form [LFe IV (NH 2 ) 2 ] 2+ , and thereafter bimetallic coupling to form an N−N bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Elucidating the mechanism underlying the augmented capacity of MoO 2 as an anode material in Li-ion batteries

Transition-metal oxide anode materials have been observed to possess an intriguing surplus of capacity beyond the expected values based on conversion reaction. However, the mechanisms behind this phenomenon have remained contentious and elusive. Here, this study focuses on synthesized nanosized molybdenum dioxide and its electrochemical performance as an anode material for Li-ion batteries. Our findings reveal a substantial increase in capacity upon cycling, achieving approximately 1688 mA h g -1 , nearly double the theoretical capacity, after 700 cycles at a 1C rate. To elucidate the mechanisms underlying this augmented capacity, a comprehensive analysis employing in situ and ex situ X-ray diffraction, X-ray absorption spectroscopy, scanning electron microscopy, and transmission electron microscopy was conducted at various stages of the Li-ion cell cycling. Our results indicate that no conversion reaction occurs during the initial discharge phase, with Li 2 O and Mo remaining undetected. Instead, Li 0.98 MoO 2 is generated upon lithiation. Further materials characterization employing electron energy loss spectroscopy and energy-dispersive X-ray spectroscopy on the cycled electrode suggests the potential formation of a metallic Li-rich layer at the interface of the Li-ion intercalated phase subsequent to the formation of Li 0.98 MoO 2 , contributing to the surplus Li storage. Moreover, electrochemical impedance spectroscopy coupled with ex situ SEM and TEM analyses reveals that alterations in particle size and morphology, along with changes in the solid electrolyte interphase (SEI) resistance, are instrumental in the capacity variation observed upon cycling.

25 ENERGY STORAGE↗
NASA NTRS2000

Effects of Carbon Structure and Surface Oxygen on the Carbon's Performance as the Anode in Lithium-Ion Battery Determined

Four carbon materials (C1, C2, C3, and C4) were tested electrochemically at the NASA Glenn Research Center at Lewis Field to determine their performance in lithium-ion batteries. They were formed as shown in the figure. This process caused very little carbon loss. Products C1 and C3 contained very little oxygen because of the final overnight heating at 540 C. Products C2 and C4, on the other hand, contained small amounts of basic oxide. The electrochemical test involved cycles of lithium intercalation and deintercalation using C/saturated LiI-50/50 (vol %) ethylene carbonate (EC) and dimethyl carbonate (DMC)/Li half cell. The cycling test, which is summarized in the table, resulted in three major conclusions. The capacity of the carbon with a basic oxide surface converges to a constant 1. value quickly (within 4 cycles), possibly because the oxide prevents solvent from entering the carbon structure and, therefore, prolongs the carbon s cycle life. Under certain conditions, the disordered carbon can store more lithium than its 2. precursor. These samples and their precursor can intercalate at 200 mA/g and deintercalate at 3. a rate of 2000 mA/g without significant capacity loss.

Hung, Ching-Cheh↗
NASA NTRS2016

Microorganisms, Organic Carbon, and Their Relationship with Oxidant Activity in Hyper-Arid Mars-Like Soils: Implications for Soil Habitability

Soil samples from the hyper-arid region in the Atacama 23 Desert in Southern Peru (La Joya Desert) were analyzed for total and labile organic carbon (TOC & LOC), phospholipid fatty acids analysis (PLFA), quantitative real time polymerase chain reaction (qRT-PCR), 4',6- diamidino-2-phenylindole (DAPI)-fluorescent microscopy, culturable microorganisms, and oxidant activity, in order to understand the relationship between the presence of organic matter and microorganisms in these types of soils. TOC content levels were similar to the labile pool of carbon suggesting the absence of recalcitrant carbon in these soils. The range of LOC was from 2 to 60 micro-g/g of soil. PLFA analysis indicated a maximum of 2.3 x 10(exp 5) cell equivalents/g. Culturing of soil extracts yielded 1.1 x 10(exp 2)-3.7 x 10(exp 3) CFU/g. qRT-PCR showed between 1.0 x 10(exp 2) and 8 x 10(exp 3) cells/g; and DAPI fluorescent staining indicated bacteria counts up to 5 x 104 cells/g. Arid and semiarid samples (controls) showed values between 10(exp 7) and 10(exp 11) cells/g with all of the methods used. Importantly, the concentration of microorganisms in hyper-arid soils did not show any correlation with the organic carbon content; however, there was a significant dependence on the oxidant activity present in these soil samples evaluated as the capacity to decompose sodium formate in 10 hours. We suggest that the analysis of oxidant activity could be a useful indicator of the microbial habitability in hyper-arid soils, obviating the need to measure water activity over time. This approach could be useful in astrobiological studies on other worlds.

Mars-like soils↗
DOE OSTI2023

Intra-catalyst CH 4 oxidation pathways on a Pd/Al 2 O 3 /CeZrO x -based commercial catalyst and implications on NO x conversion profiles for a natural gas vehicle exhaust under lambda modulation

The performance of a three-way catalyst (TWC) in natural gas-powered vehicles is enhanced by periodic changes in air-to-fuel ratio (λ-modulation). The reaction networks and sequences inside the catalyst that facilitate such enhanced performance have not been extensively investigated. Here, this work applied intra-catalyst measurements (SpaciMS) to analyze the transient spatiotemporal gas concentrations inside a Pd-based TWC to establish relationships between CH 4 , NO x , CO and H 2 conversion pathways. Steam reforming and partial oxidation were revealed to be the main CH 4 conversion routes. The cyclic rich-lean conditions combined with the oxygen storage capacity (OSC) of the TWC generate reduced and oxidized zones that are constantly moving within the catalyst, changing the dominant chemical reactions occurring on the surface. In the reduced zones, OSC is depleted while CH 4 is converted through steam reforming and NO x is converted through reactions with H 2 , CO, and other surface-bound reducing fragments formed by CH 4 conversion. In the oxidized zones, OSC is replenished, CH 4 is converted by partial oxidation, and H 2 , CO, and NH 3 are oxidized. The length of lean-rich phases impacts the catalyst performance significantly; too short or too long of a rich or lean phase can lower the overall conversion of reactive species. An inhibition of CH 4 conversion was observed during the rich phase possibly due to CO-poisoning of active sites. The intra-catalyst measurements revealed that the catalyst consists of three distinct reaction zones and their lengths vary with modulation conditions. Various modulation frequencies, amplitudes, λ-centers, and temperatures were investigated which allowed an understanding of how these parameters affect the reaction zones and catalyst utilization. Understandings from this work can enable adaptive λ-control strategies to optimize the overall TWC performance over a range of vehicle operating conditions.

Lean-Rich cycling↗
NASA NTRS1994

Influence of suspension on the oxidative burst by rat neutrophils

The influence of spaceflight on the oxidative burst of neutrophils is not known. The present study was designed to evaluate the influence of antiorthostatic suspension, a ground-based modeling system designed to simulate certain aspects of weightlessness that occur after spaceflight, on the capacity of rat neutrophils to express the oxidative burst, an important host defense mechanism against microbial pathogens. Rats were suspended in whole body harnesses in the antiorthostatic orientation for a 3- or 7-day period. Control rats were suspended orthostatically or allowed to remain in vivarium cages without the attachment of any suspension materials. After suspension, peripheral blood was harvested and neutrophils were isolated by density gradient centrifugation. The enriched neutrophil preparations were stimulated with N-formyl-methionyl-leucine-phenylalanine and phorbol myristic acid to induce the oxidative burst. It was found that neutrophils isolated from suspended animals released the same levels of superoxide anion as did vivarium control animals that were not suspended, indicating that whole body suspension did not alter this aspect of rat neutrophil function.

Non-NASA Center↗
DOE OSTI2025

Decoupling the capacity fade contributions in polymer electrolyte-based high-voltage solid-state batteries

Polymer electrolyte (PE)-based solid-state batteries (PE-SSBs) made with high-voltage cathodes are known to suffer from severe capacity fade, stemming primarily from the poor oxidative stability of most PEs under high-voltage cycling conditions. PEs also suffer from greater ion-transport limitations compared to liquid or solid electrolytes. However, often, these limitations are collectively stated to be responsible for the observed capacity fade, and it is challenging to decouple the contributions of different factors. Herein, a tunable cell fabrication platform was developed to systematically investigate and decouple the two primary capacity fade drivers (cell impedance growth and kinetic limitations), while keeping the other cell parameters constant. Three PE types with distinct transport characteristics were compared. By utilizing a voltage profile analysis method, the contribution of the cell's internal impedance growth was quantitatively decoupled from the kinetic limitations stemming from the high concentration gradient in the polymer catholyte and slow charge transfer reactions. We demonstrate that the high interfacial impedance did not necessarily correlate with the high capacity fade rate. Kinetic limitations that are not reflected by impedance measurements can play a dominant role in causing cumulative capacity decay.

Ock, Ji-young [Oak Ridge National Laboratory (ORNL↗
DOE OSTI2021

Reaction inhomogeneity coupling with metal rearrangement triggers electrochemical degradation in lithium-rich layered cathode

High-energy density lithium-rich layered oxides are among the most promising candidates for next-generation energy storage. Unfortunately, these materials suffer from severe electrochemical degradation that includes capacity loss and voltage decay during long-term cycling. Present research efforts are primarily focused on understanding voltage decay phenomena while origins for capacity degradation have been largely ignored. Here, we thoroughly investigate causes for electrochemical performance decline with an emphasis on capacity loss in the lithium-rich layered oxides, as well as reaction pathways and kinetics. Advanced synchrotron-based X-ray two-dimensional and three-dimensional imaging techniques are combined with spectroscopic and scattering techniques to spatially visualize the reactivity at multiple length-scales on lithium- and manganese-rich layered oxides. These methods provide direct evidence for inhomogeneous manganese reactivity and ionic nickel rearrangement. Coupling deactivated manganese with nickel migration provides sluggish reaction kinetics and induces serious structural instability in the material. Our findings provide new insights and further understanding of electrochemical degradation, which serve to facilitate cathode material design improvements.

25 ENERGY STORAGE↗
DOE OSTI2022

Exceptional Cycling Performance Enabled by Local Structural Rearrangements in Disordered Rocksalt Cathodes

The capacity of lithium transition-metal (TM) oxide cathodes is directly linked to the magnitude and accessibility of the redox reservoir associated with TM cations and/or oxygen anions, which traditionally decreases with cycling as a result of chemical, structural, or mechanical fatigue. Here, it is shown that a capacity increase over 125% can be achieved upon cycling of high-energy Mn- and F-rich cation-disordered rocksalt oxyfluoride cathodes. This study reveals that in Li 1.2 Mn 0.7 Nb 0.1 O 1.8 F 0.2 , repeated Li extraction/reinsertion utilizing Mn 3+ /Mn 4+ redox along with some degree of O-redox participation leads to local structural rearrangements and formation of domains with off-stoichiometry spinel-like features. The effective integration of these local “structure-domains” within the cubic disordered rocksalt framework promotes better Li diffusion and improves material utilization, consequently increased capacity upon cycling. Finally, this study provides important new insights into materials design strategies to further exploit the rich compositional and structural space of Mn chemistry for developing sustainable, high-energy cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2022

Unconventional Photoconversion from In‐Plane 2D Heterostructures of 2D Transition Metal Carbides/Semiconductors

2D transition metal carbides/nitrides (MXenes) are thought of promising photothermal materials due to their broadband localized surface plasma resonance (LSPR) and attractive electromagnetic interference (EMI) properties. However, the weak oxidation resistance and unclear photothermal mechanism of MXenes impede their photothermal modulations. Herein, the in‐plane 2D Ti 3 C 2 /TiO 2 heterostructures are fabricated by partial oxidation and an unconventional photothermal effect under near infrared irradiation, even if the oxidation compromises the EMI and LSPR capacities, is demonstrated. Such performance is ascribed to the faster transfer of photoexcited electrons across the seamless in‐plane Ti 3 C 2 /TiO 2 heterointerface than the reported out‐of‐plane one, and the 1–2 orders of magnitude faster relaxation processes of electrons than the ground bleaching in the Original MXene. These experimental results are well‐supported by theoretical calculations. The conceptual advances broaden the fundamental understanding of the photoconversion of MXenes, which would be extended into a variety of applications, such as biomedical therapy, photosynthesis, and photovoltaics.

Energy & Fuels↗
DOE OSTI2021

Reversible function switching of Ag catalyst in Mg/S battery with chloride-containing electrolyte

Rechargeable Mg/S batteries suffer from fast capacity decay because of the difficult re-oxidation of MgS. To tackle this problem, we used Ag catalyst in Mg/S cells with Cl- containing electrolyte, and achieved a greatly improved specific capacity of ~1200 mAh•g -1 and a long cycling life of 100 cycles. To understand the mechanism behind this improvement, we employed in-situ synchrotron radiation X-ray diffraction and in-situ X-ray absorption spectroscopy tools to study the reversible phase transitions during charge/discharge cycling. Additionally, the in-situ experiment results revealed that, at deeply charged state, Ag reacted with Cl- in the electrolyte to form the AgCl interfacial layer which prevented the physical contact of Ag with elemental S and avoided the formation of Ag 2 S; at early discharged state, AgCl transformed back to metallic Ag, which guaranteed its catalytic effectiveness for MgS decomposition. This reversible function switching mechanism of Ag catalyst is completely different from that in Mg/S cells using other catalysts or electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2020

Structural Distortion Induced by Manganese Activation in a Lithium-Rich Layered Cathode

The search for batteries with high energy density has highlighted lithium-rich manganese-based layered oxides due to their exceptionally high capacity. Although it is clear that both cationic and anionic redox are present in the charge compensation mechanism, the microstructural evolution of the Li 2 MnO 3 -like phase during anionic redox and its role in battery performance and structural stability are still not fully understood. Here, we systematically probe microstructural evolution using spatially resolved synchrotron X-ray measurements and reveal an underlying interaction between the Li 2 MnO 3 -like domains and bulk rhombohedral structure. Mn ion activation and a previously unobserved structural distortion are discovered at high voltages, and can be related to structural strain present in the Li 2 MnO 3 -like phase upon substantial lithium ion extraction. Moreover, we elucidate a correlation between this structural distortion and irreversible phase transitions by thermally perturbing delithiated samples. These insights highlight a pathway toward achieving high capacity cathode materials required for future commercial applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Improving the oxygen redox reversibility of Li-rich battery cathode materials via Coulombic repulsive interactions strategy

The oxygen redox reaction in lithium-rich layered oxide battery cathode materials generates extra capacity at high cell voltages (i.e., >4.5 V). However, the irreversible oxygen release causes transition metal (TM) dissolution, migration and cell voltage decay. To circumvent these issues, we introduce a strategy for tuning the Coulombic interactions in a model Li-rich positive electrode active material, i.e., Li 1.2 Mn 0.6 Ni 0.2 O 2 . In particular, we tune the Coulombic repulsive interactions to obtain an adaptable crystal structure that enables the reversible distortion of TMO 6 octahedron and mitigates TM dissolution and migration. Moreover, this strategy hinders the irreversible release of oxygen and other parasitic reactions (e.g., electrolyte decomposition) commonly occurring at high voltages. When tested in non-aqueous coin cell configuration, the modified Li-rich cathode material, combined with a Li metal anode, enables a stable cell discharge capacity of about 240 mAh g -1 for 120 cycles at 50 mA g -1 and a slower voltage decay compared to the unmodified Li 1.2 Mn 0.6 Ni 0.2 O 2 .

25 ENERGY STORAGE↗
DOE OSTI2025

Delineating the impact of Ti/Mg substitution in P2-type Na 2/3 Ni 1/3 Mn 2/3 O 2 with an advanced electrolyte for sodium-ion batteries

Sodium layered oxide cathodes are drawing interest globally as a potential alternative to lithium layered oxides, but they suffer from egregious capacity fade and have intrinsically lower capacity. P2-type Na 2/3 Ni 1/3 Mn 2/3 O 2 is a particularly relevant cathode material as it demonstrates an energy density of up to 550 W h kg −1 at high operating potentials, although this can only be maintained for a handful of cycles with industrial electrolytes. Here, a localized saturated electrolyte (LSE) is shown to significantly improve the cycle life of Na 2/3 Ni 1/3 Mn 2/3 O 2 by suppressing the surface reactivity, despite large volume changes during cycling. The demonstrated influence of surface stability on cycle life in this work challenges the prevailing notion of a popular capacity stabilization strategy with titanium/magnesium co-doping, which is primarily thought to improve cycle life via improved structural stability. Single crystals of Na 2/3 Ni 1/3−x Mg x Mn 2/3−2x Ti 2x O 2 (x = 0, 1/48, 1/24, 1/12) materials are cycled with a traditional electrolyte and the LSE to demonstrate that despite eliminating the phase transition with dopants in Na 2/3 Ni 1/4 Mg 1/12 Mn 1/2 Ti 1/6 O 2 , the predominant role of the dopants is in reducing the parasitic oxygen reactivity at the cathode surface. The different roles these dopants play are systematically disambiguated, and this work can guide future research to focus on reducing the parasitic cathode/electrolyte reactivity further.

25 ENERGY STORAGE↗
DOE OSTI2021

Modeling, Design, and Testing of a Novel Biphasic Solvent-Enabled Absorption System for Post-Combustion Carbon Capture

A novel absorption process enabled by a new class of biphasic solvents for post-combustion carbon capture (BiCAP) is presently being developed at the University of Illinois at Urbana-Champaign. The new biphasic solvents are water-lean solvent blends that develop dual liquid phases with the absorbed CO2 highly enriched in one of the phases. These solvents are superior in CO2 capacity and have high thermal and oxidative stability compared to MEA. The BiCAP technology features a unique process configuration of multi-stage CO2 absorption and liquid–liquid phase separation during CO2 absorption, allowing continual separation and removal of the CO2-enriched liquid phase for maintaining low solvent viscosity and a fast absorption rate. A 40 kWe-scale skid has recently been constructed at the Abbott Power Plant in Champaign, IL, to test the BiCAP solvent in continuous operation with a slipstream of real post-combustion flue gas. Along with improvements in the stripping configuration including cold feed bypass, the process is expected to achieve a minimum reboiler duty of 2,210 kJ/kg CO2 captured at a stripper operating pressure of 6 bar.

20 FOSSIL-FUELED POWER PLANTS↗
NASA NTRS1972

Diffusional creep and creep degradation in the dispersion-strengthened alloy TD-NiCr

Dispersoid-free regions were observed in TD-NiCr (Ni-20Cr-2ThO2) after slow strain rate testing in air from 1145 to 1590 K. Formation of the dispersoid-free regions appears to be the result of diffusional creep. The net effect of this creep is the degradation of TD-NiCr to a duplex microstructure. Degradation is further enhanced by the formation of voids and integranular oxidation in the thoria-free regions. These regions apparently provided sites for void formation and oxide growth since the strength and oxidation resistance of Ni-20Cr is much less than Ni-20Cr-2ThO2. This localized oxidation does not appear to reduce the static load bearing capacity of TD-NiCr since long stress rupture lives were observed even with heavily oxidized microstructures. But this oxidation does significantly reduce the ductility and impact resistance of the material. Dispersoid-free bands and voids were also observed for two other dispersion strengthened alloys, TD-NiCrAl and IN-853. Thus, it appears that diffusional creep is charactertistic of dispersion-strengthened alloys and can play a major role in the creep degradation of these materials.

Whittenberger, J. D.↗
NASA NTRS1997

Fuel Cell Power Plant Initiative: Preliminary Design of a Fixed-Base LFP/SOFC Power System - Volume 2

This report documents the preliminary design for a military fixed-base power system of 3 MWe nominal capacity using Westinghouse's tubular Solid Oxide Fuel Cell [SOFC] and Haldor Topsoe's logistic fuels processor [LFP]. The LFP provides to the fuel cell a methane rich sulfur free fuel stream derived from either DF-2 diesel fuel, or JP-8 turbine fuel. Fuel cells are electrochemical devices that directly convert the chemical energy contained in fuels such as hydrogen, natural gas, or coal gas into electricity at high efficiency with no intermediate heat engine or dynamo. The SOFC is distinguished from other fuel cell types by its solid state ceramic structure and its high operating temperature, nominally 1000'C. The SOFC pioneered by Westinghouse has a tubular geometry closed at one end. A power generation stack is formed by aggregating many cells in an ordered array. The Westinghouse stack design is distinguished from other fuel cell stacks by the complete absence of high integrity seals between cell elements, cells, and between stack and manifolds. Further, the reformer for natural gas [predominantly methane] and the stack are thermally and hydraulically integrated with no requirement for process water. The technical viability of combining the tubular SOFC and a logistic fuels processor was demonstrated at 27 kWe scale in a test program sponsored by the Advanced Research Projects Agency [ARPA) and carried out at the Southern California Edison's [SCE] Highgrove generating station near San Bernardino, California in 1994/95. The LFP was a breadboard design supplied by Haldor Topsoe, Inc. under subcontract to Westinghouse. The test program was completely successful. The LFP fueled the SOFC for 766 hours on JP-8 and 1555 hours of DF-2. In addition, the fuel cell operated for 3261 hours on pipeline natural gas. Over the 5582 hours of operation, the SOFC generated 118 MVVH of electricity with no perceptible degradation in performance. The LFP processed military specification JP-8 and DF-2 removing the sulfur and reforming these liquid fuels to a methane rich gaseous fuel. Results of this program are documented in a companion report titled 'Final Report-Solid Oxide Fuel Cell/ Logistic Fuels Processor 27 kWe Power System'.

Veyo, S.E.↗