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At least 811 records · Page 45
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

A Non-aqueous H 3 PO 4 Electrolyte Enables Stable Cycling of Proton Electrodes

A non-aqueous proton electrolyte is devised by dissolving H 3 PO 4 into acetonitrile. The electrolyte exhibits unique vibrational signatures from stimulated Raman spectroscopy. Such an electrolyte exhibits unique characteristics compared to aqueous acidic electrolytes: 1) higher (de)protonation potential for a lower desolvation energy of protons, 2) better cycling stability by dissolution suppression, and 3) higher Coulombic efficiency owing to the lack of oxygen evolution reaction. Two non-aqueous proton full cells exhibit better cycling stability, higher Coulombic efficiency, and less self-discharge compared to the aqueous counterpart.

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

Structure and lithium insertion in oxides of molybdenum

Oxides of molybdenum, MoO x , have a rich structural chemistry arising from the accommodation of oxygen deficiency as MoO 3 is reduced and varied redox behavior arising from the ability of Mo to take on several different oxidation states. We review MoO 3 , MoO 2 , and all the reduced Mo oxides with intermediate compositions for their performance as Li-ion battery electrode materials. These reduced oxides are perhaps the most structurally diverse in the field of energy storage materials, taking on structures ranging from ones with crystallographic shear to bronze-like structures and distorted rutile. The crystal structure can have a significant impact on the performance of battery materials, which makes the reduced Mo oxides a promising domain of study. Electrochemical studies of these oxides from as early as 1971 to as recently as 2022 are compiled, and characteristics of capacity, capacity retention, and rate performance are compared. We find that certain oxides indeed display promising and highly reversible capacities for Li + storage. Typical redox voltages for Mo oxides lie in a regime that hinders maximizing energy density when they are paired with higher-voltage cathodes or lower-voltage anodes. The possibility of decreasing the redox voltage in the future will expand the promise of these materials while offering an alternative to more critical elements such as Nb.

25 ENERGY STORAGE↗
DOE OSTI2025

Recent Developments in Lithium-Manganese-Nickel Oxide Electrochemistry: The Alchemy of LiMn 0.5 Ni 0.5 O 2

Efforts have been underway for some time at Argonne National Laboratory to design structurally integrated and stabilized lithium-manganese-nickel-oxide cathode materials. The goal has been to find a cobalt-free, high-capacity cathode for a Li-ion battery that is competitive, both cost- and energy-wise, with lithium-nickel-manganese-cobalt-oxide (NMC) and lithium-iron-phosphate (LFP) products. This brief synopsis highlights the remarkable alchemy of LiMn 0.5 Ni 0.5 O 2 resulting from its well-known, slightly disordered layered structure and the recently discovered lithiated spinel phase and totally disordered rock-salt configurations. All three arrangements share a structurally compatible cubic-close-packed oxygen array. The lithiated spinel and layered components provide an intersecting network of two- and three-dimensional channels that facilitate Li + -ion transport, while a minor amount of an extensively disordered rock-salt component likely serves to enhance the structural and electrochemical stability of the electrode. The synopsis also encompasses the historical development of lithiated spinel electrode materials and structurally integrated systems.

Thackeray, Michael M. [Argonne National Laboratory↗
DOE OSTI2020

High accuracy in-situ direct gas analysis of Li-ion batteries

Cycling of lithium-ion batteries containing Ni-rich NMC cathodes at high voltage involves intense gas generation. From the safety standpoint, it is critical to understand how different gas species respond to changes of upper cut-off voltages. In this manuscript, we introduce a novel experimental set up for real-time analysis of gas generation in prismatic pouch cells. In a typical experiment, a lithium-ion pouch cell is directly connected to a quadruple mass spectrometer by glass capillary. Pressure difference helps move the generated gases to the mass spectrometer column for full analysis. The gaseous species are probed during both formation cycle and aging cycles in Li-ion pouch cells comprising NMC811 cathode and graphite anode. The gases are generated upon the creation of the solid electrolyte interphase on graphite during the first formation charge. Besides ethylene gas, C 2 H 4 , whose occurrence is related to the decomposition of ethylene carbonate, a minor solvent decomposition happened at a lower voltage is demonstrated to be associated with residue water on the electrode. For aging cycles, three upper cut-off voltages have been selected to investigate the gas evolution behavior upon charging to 4.2, 4.4 and 4.6 V. Higher upper cut-off voltages do not affect the amount of O 2 measured as a part of the generated oxygen could have reacted with electrolytes. Quite similar and low amounts of O 2 remain in the cells upon charging to the selected cut-off voltages. On the other hand, the generation of CO 2 has been found to be very sensitive to upper cut-off voltage. During similar aging cycles, 6167 nmol $g_{NMC}^{-1}$ of CO 2 is generated at 4.6 V, versus 1650 nmol $g_{NMC}^{-1}$ of CO 2 at 4.4 V, versus 91 nmol $g_{NMC}^{-1}$ of CO 2 at 4.2 V.

25 ENERGY STORAGE↗
DOE OSTI2020

Oligomeric Ruthenium Polypyridyl Dye for Improved Stability of Aqueous Photoelectrochemical Cells

Water-splitting dye-sensitized photoelectrochemical cells rely on molecular sensitizers to harvest light energy and drive the catalytic reactions necessary to generate hydrogen and oxygen from water. The desorption of sensitizer molecules from the semiconductor–aqueous electrolyte interface is a significant barrier to the practical implementation of these cells. To address this problem, we synthesized an oligomeric ruthenium dye ([RuP] n ) that has dramatically improved stability as a photosensitizer for TiO 2 electrodes over the pH range of interest (4–7.8) for DSPECs. Additionally, the efficiency of photoelectrochemical charge separation is known to depend on the rate of cross-surface hole diffusion between dye molecules. The oligomeric dye ([RuP] n ) shows an order of magnitude faster cross-surface hole diffusion than the commonly used monomeric [Ru(bpy) 2 (4,4-PO 3 H 2 ) 2 bpy] 2+ (RuP) sensitizer. Finally, the enhanced stability of the polymeric dye also enables the use of intensity-modulated photovoltage spectroscopy to measure the recombination rate of photogenerated electrons and holes as a function of electrolyte pH.

14 SOLAR ENERGY↗
NASA NTRS1978

Water electrolysis system - H2 and O2 generation

An oxygen generation system design based on the static feed water electrolysis concept is described. The system is designed to generate 4.20 kg/d of oxygen to satisfy the metabolic needs of a three-person crew, to compensate for spacecraft leakage, and to provide the oxygen required by the electrochemical depolarized CO2 concentrator. The system has a fixed hardware weight of 75 kg, occupies a volume of 0.11 cu m, and requires only 1.1 kw of electrical power. The static feed electrolysis concept is discussed, and experimental data on the high-performance electrode are presented.

Schubert, F. H.↗
NASA NTRS2011

Amperometric Solid Electrolyte Oxygen Microsensors with Easy Batch Fabrication

An amperometric solid electrolyte oxygen (O2) microsensor using a novel and robust structure has been developed with a detection range of 0.025 to 21 percent of O2 concentration. The microsensor has a simple structure with a sensing area of 1.10 0.99 mm(exp 2), and is operated by applying voltage across the electrodes and measuring the resulting current flow at a temperature of 600 C.

Hunter, Gary W.↗
DOE OSTI2025

Titanium nitride prepared by the urea-glass synthesis gives an active electrocatalyst for the oxygen reduction reaction

Rock-salt-structured titanium nitride (TiN) has emerged as a leading earth-abundant electrocatalyst for the oxygen reduction reaction (ORR). We compare TiN prepared in three ways starting from urea: the urea–glass method, by a direct reaction between urea and titanium(IV) chloride, and through a discrete monomeric complex. In the urea-glass route, a new-found [Ti 4 (µ-O) 6 (OC(NH 2 ) 2 ) 12 ] 4+ oxo-bridged titanium–urea precursor can be synthesized in a single-pot reaction at room temperature starting from titanium(IV) chloride, urea, and ethanol with a urea-to-titanium ratio of 6. Subsequent annealing of the polymeric gel that results at 750 °C in an N 2 atmosphere yields phase-pure, TiN particles on the 100 µm size scale. TiN can be deposited as an ink with PiperlON®anion exchange dispersion onto a glassy carbon rotating disk electrode (RDE), and of the three synthesis methods, the urea-glass method gives the most active ORR catalyst. The onset potential for ORR activity is −131 mV vs. Hg/HgO, and Koutecký–Levich analysis of linear-sweep voltammetry recorded at varying rotation rates supports a two-electron reduction pathway to H 2 O 2 , with a rate constant of 0.0172 cm s −1 . The higher activity is ascribed to a more oxygen-rich surface—boh defect sites and active oxygen species—afforeded by the oxo-bridged precursor, corrorborated by X-ray photoelectron spectroscopy (XPS) analysis.

Xie, Wanrui [University of Michigan, Ann Arbor, MI↗
NASA NTRSDate not supplied

Suborbital Lunar Gravity Experiment of an Electrodynamic Regolith Conveyor

NASA’s Swamp Works Electrostatics and Surface Physics Laboratory (ESPL) is planning to test a 4-phase electrodynamic regolith conveyor in simulated lunar gravity on a suborbital flight in 2023. A 4-phase electrodynamic regolith conveyor could convey regolith without the risk of rotating or vibratory actuation, which could jam or require regular maintenance due to the abrasive nature of lunar regolith. Another advantage of electrodynamic conveying is the reduction of conveying power, which is important considering the limited scale of available early-stage lunar power systems. The current state of the art(SOA) for lunar regolith conveying is based on recent NASA system studies for oxygen production plants. These plant designs require conveying rates around 100 kg/hr, to produce 10 mT/yr of oxygen from the regolith. To accomplish this, conventional augers and vibratory spiral conveyors have been identified as the SOA or the leading candidates due to their extensive use in the terrestrial material handling industry. At NASA KSC, the use of dynamic electric fields, generated by alternating high voltage on electrodes, has been developed as a dust mitigation solution known as the Electrodynamic Dust Shield (EDS). The EDS is being developed for lenses, solar panels, radiators, fabric and seals. ESPL researchers have shown the ability to move thin layers (~ a few mm) of dust with mW of power. In Academia, researchers have shown the ability to electrodynamically convey regolith up to ~1 kg/hr with a4-phase EDS and electromagnetically convey particles that would suggest a lunar regolith conveying rate of ~25 kg/hr. This paper will describe the design and expected operation of a 4-phase electrodynamic regolith conveyor in lunar gravity. This paper will also describe how an electrodynamic conveyor could be scaled for transporting ISRU relevant flow rates.

Aaron D S Olson↗
NASA NTRSDate not supplied

Design and Testing of a Prototype Electrodynamic Regolith Conveyor for Lunar ISRU

NASA’s Swamp Works Electrostatics and Surface Physics Laboratory (ESPL) is developing a 4-phaseelectrodynamic regolith conveyor (ERC) that could convey regolith without the risk of rotating or vibratory actuation, which could jam or require regular maintenance due to the abrasive nature of lunar regolith. Another goal of electrodynamic conveying is the reduction of conveying power, which is important considering the limited capacity of early-stage lunar power systems. The current state of the art(SOA) for lunar regolith conveying is based on recent NASA system studies for oxygen production plants. These plant designs require conveying rates around 100 kg/hr, to produce 10 mT/yr of oxygen from the regolith. To accomplish this, conventional augers and vibratory spiral conveyors have been identified as the SOA or the leading candidates due to their extensive use in the terrestrial material handling industry. At NASA KSC, the use of dynamic electric fields, generated by alternating high voltage on electrodes, has been developed as a dust mitigation solution known as the Electrodynamic Dust Shield (EDS). The EDS is being developed for lenses, solar panels, radiators, fabric and seals and is scheduled for a technology demonstration mission on the Moon in 2023. ESPL researchers have shown the ability to move thin layers (~ a few mm) of dust with mW of power. In Academia, researchers have shown the ability to electrodynamically convey regolith up to ~1 kg/hr with a 4-phase EDS and electromagnetically convey particles that would suggest a lunar regolith conveying rate of ~25 kg/hr. This paper will describe the design and testing of a prototype ERC that could scale to support transporting regolith at ISRU relevant flow rates.

Aaron D S Olson↗
NASA NTRSDate not supplied

Design and Testing of a Prototype Electrodynamic Regolith Conveyor For Lunar ISRU

NASA’s Kennedy Space Center’s (KSC) Swamp Works Electrostatics and Surface Physics Laboratory (ESPL) is developing a 4-phase Electrodynamic Regolith Conveyor (ERC) that could convey regolith without the risk of rotating or vibratory actuation, which could jam or require regular maintenance due to the abrasive nature of lunar regolith. Another goal of electrodynamic conveying is the reduction of conveying power, which is important considering the limited capacity of early-stage lunar power systems. The current state of the art (SOA) for lunar regolith conveying is based on recent NASA system studies for oxygen production plants. These plant designs require conveying rates around 100 kg/hr, to produce 10 mT/yr of oxygen from the regolith. To accomplish this, conventional augers and vibratory spiral conveyors have been identified as the SOA or the leading candidates due to their extensive use in the terrestrial material handling industry. At NASA KSC, the use of dynamic electric fields, generated by alternating high voltage on electrodes, has been developed as a dust mitigation solution known as the Electrodynamic Dust Shield (EDS). The EDS is being developed for lenses, solar panels, radiators, fabric and seals and is scheduled for a technology demonstration mission on the Moon in 2023. ESPL researchers have shown the ability to move thin layers (a few mm) of dust with mW of power. In Academia, researchers have shown the ability to electrodynamically convey regolith up to 1 kg/hr with a 4-phase EDS. This paper will describe the design and testing of a prototype ERC that could scale to support transporting regolith at ISRU relevant flow rates.

Conveyor↗
NASA NTRSDate not supplied

Design and Testing of a Prototype Electrodynamic Regolith Conveyor for Lunar ISRU

NASA’s Kennedy Space Center’s (KSC) Swamp Works Electrostatics and Surface Physics Laboratory (ESPL) is developing a 4-phase Electrodynamic Regolith Conveyor (ERC) that could convey regolith without the risk of rotating or vibratory actuation, which could jam or require regular maintenance due to the abrasive nature of lunar regolith. Another goal of electrodynamic conveying is the reduction of conveying power, which is important considering the limited capacity of early-stage lunar power systems. The current state of the art (SOA) for lunar regolith conveying is based on recent NASA system studies for oxygen production plants. These plant designs require conveying rates around 100 kg/hr, to produce 10 mT/yr of oxygen from the regolith. To accomplish this, conventional augers and vibratory spiral conveyors have been identified as the SOA or the leading candidates due to their extensive use in the terrestrial material handling industry. At NASA KSC, the use of dynamic electric fields, generated by alternating high voltage on electrodes, has been developed as a dust mitigation solution known as the Electrodynamic Dust Shield (EDS). The EDS is being developed for lenses, solar panels, radiators, fabric and seals and is scheduled for a technology demonstration mission on the Moon in 2023. ESPL researchers have shown the ability to move thin layers (a few mm) of dust with mW of power. In Academia, researchers have shown the ability to electrodynamically convey regolith up to 1 kg/hr with a 4-phase EDS. This paper will describe the design and testing of a prototype ERC that could scale to support transporting regolith at ISRU relevant flow rates.

Lunar↗
DOE OSTI2020

Exploiting Metal–Ligand Cooperativity to Sequester, Activate, and Reduce Atmospheric Carbon Dioxide with a Neutral Zinc Complex

As atmospheric levels of carbon dioxide (CO 2 ) continue to increase, there is an immediate need to balance the carbon cycle. Current approaches require multiple processes to fix CO 2 from the atmosphere or flue gas and then reduce it to value-added products. The zinc(II) catalyst Zn(DMTH) (DMTH = diacetyl-2-(4-methyl-3-thiosemicarbazonate)-3-(2-pyridinehydrazonato)) reduces CO 2 from air to formate with a faradaic efficiency of 15.1% based on total charge. The catalyst utilizes metal–ligand cooperativity and redox-active ligands to fix, activate, and reduce CO 2 . Our approach provides a new strategy that incorporates sustainable earth-abundant metals that are oxygen and water tolerant.

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

Direct Integration of Strained-Pt Catalysts into Proton-Exchange-Membrane Fuel Cells with Atomic Layer Deposition

The design and fabrication of lattice-strained platinum catalysts achieved by removing a soluble core from a platinum shell synthesized via atomic layer deposition, is reported. The remarkable catalytic performance for the oxygen reduction reaction (ORR), measured in both half-cell and full-cell configurations, is attributed to the observed lattice strain. By further optimizing the nanoparticle geometry and ionomer/carbon interactions, mass activity close to 0.8 A mg Pt -1 @0.9 V iR-free is achievable in the membrane electrode assembly. Nevertheless, active catalysts with high ORR activity do not necessarily lead to high performance in the high-current-density (HCD) region. More attention shall be directed toward HCD performance for enabling high-power-density hydrogen fuel cells.

25 ENERGY STORAGE↗
DOE OSTI2020

Critical Practices in Rigorously Assessing the Inherent Activity of Nanoparticle Electrocatalysts

Accurate activity measurements for electrocatalytic materials are the backbone of impactful electrocatalyst research. Inherent to accurate measurements is the correct accounting of the active catalyst sites and the design of experiments to ensure that these sites are participating in the measured reaction. Improvements in electrocatalyst activity for fuel cell reactions (hydrogen oxidation and oxygen reduction) are essential for the widespread adoption of this carbon-neutral energy source. Activities for these half-reactions can be reported in a variety of ways including specific activities, mass activities, volumetric activities, and half-wave potentials. These values are traditionally measured with a rotating disk electrode (RDE) in which the electrocatalyst is supported on a porous active layer film attached to the RDE. To accurately measure electrocatalyst activity with an RDE, two major sources of errors must be addressed: (i) accurate electrochemical surface area (ECSA) quantification and (ii) fast diffusion of reactants through the active layer film. In this contribution, we first aim to detail through RDE experiments and mass transport modeling the potential errors that can be observed when these factors are not properly addressed. We then present recommendations and discuss techniques for properly constructing electrocatalyst thin films and characterizing the ECSA on monometallic and novel alloy electrocatalysts. These practices, when adopted, ensure greater confidence and reliability in reports of electrocatalyst activity.

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

Inclusion of Biological Targets in the Analysis of Electrical Characteristics of Non-Thermal Plasma Discharge

In Plasma Medicine studies, the effect of non-thermal plasma (NTP) on biological targets is typically correlated with the amount of stable reactive oxygen and nitrogen species produced in a liquid medium. The effect of NTP and the response of the biological target on cellular redox mechanisms is overlooked in these investigations. Additionally, the influence of electrical properties of cells on the physical properties of NTP is neglected. Therefore, we used a floating electrode dielectric barrier discharge plasma to explore the impact of cell structure, size, and viability of the biological target on the physical properties of NTP. Lissajous figures were used to determine circuit capacitance and energy per cycle during NTP exposure of different cell suspensions. We show that both, structural integrity and active enzymic processes of cells change the electrical properties of NTP. Correlations were also drawn between NTP-produced hydrogen peroxide and nitrite with measured capacitance. Our studies indicate that the observed changes between different cell suspensions may be due to a feedback loop between the biological target and the NTP source. In future studies, a more detailed analysis is needed to improve the control of clinical NTP devices.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1984

Preparation and evaluation of advanced catalysts for phosphoric acid fuel cells

The platinum electrocatalysts were characterized for their crystallite sizes and the degree of dispersion on the carbon supports. One application of these electrocatalysts was for anodic oxidation of hydrogen in hot phosphoric acid fuel cells, coupled with the influence of low concentrations of carbon monoxide in the fuel gas stream. In a similar way, these platinum on carbon electrocatalysts were evaluated for oxygen reduction in hot phosphoric acid. Binary noble metal alloys were prepared for anodic oxidation of hydrogen and noble metal-refractory metal mixtures were prepared for oxygen reduction. An exemplar alloy of platinum and palladium (50/50 atom %) was discovered for anodic oxidation of hydrogen in the presence of carbon monoxide, and patent disclosures were submitted. For the cathode, platinum-vanadium alloys were prepared showing improved performance over pure platinum. Preliminary experiments on electrocatalyst utilization in electrode structures showed low utilization of the noble metal when the electrocatalyst loading exceeded one weight percent on the carbon.

Stonehart, P.↗
DOE OSTI2023

Platinum group metal-free (PGM-free) integrated tandem junction photoelectrochemical (PEC) water splitting devices (Final Technical Report)

This project involves using solar light, a photoabsorber, and a catalyst to split water and produce hydrogen. The Department of Energy (DOE) targets for integrated photoelectrochemical (PEC) cells emphasize cost (electrode cost < $200/m 2 ), performance (> 15% solar to hydrogen (STH) efficiency), and stability (> 6 months electrode lifetime), but most approaches skew toward one specific metric. This project exploited interfacial integration of platinum group metal-free (PGM-free) catalysts on the high performance and high value tandem solar cells to attain or exceed the DOE benchmark STH energy conversion efficiency and durability. This was investigated in two thrusts by developing two PEC devices for direct comparison: the first is a high-performance monolithic device based on state-of-the-art GaInP 2 /GaAs tandem solar cells developed at National Renewable Energy Laboratory (NREL), and the second is a high-value device based on earth-abundant wide band gap photoabsorber materials including oxynitride and hybrid organic-inorganic perovskite (HOIP) coupled with commercial narrow band gap silicon (Si). Both these devices were paired with electrocatalysts developed for this purpose at Rutgers University by adapting them to thin films on the photoabsorbers. These catalysts are based on the hydrogen evolution reaction (HER) catalysts (Ni 5 P 4 ), oxygen evolution reaction (OER) catalysts (LiCo 2 O 4 ) previously developed at Rutgers for high-efficiency electrolyzers. For using the high-performance tandem solar cell and Ni 5 P 4 catalysts, we achieved a durability of > 200 h at a STH efficiency of > 10%. For using the high-value wide band gap single junction solar cells on n + Si, we achieved 0.73 mA/cm 2 at 1.23V vs reversible hydrogen electrode (RHE) and -15.9 mA/cm 2 at 0V vs RHE using the oxynitride- and HOIP-based photoelectrodes, respectively. After comparing their photocurrent densities, we down selected the HOIP photoabsorber to couple Si for fabrication of a tandem photocathode. However, due to the COVID-19 pandemic, both the laboratories at Rutgers and NREL were locked down for three months and reopened only partially in 2020. The HOIP/Si tandem photocathode using robust nickel phosphide thin film catalysts cannot be developed within the project period, which is expected to achieve a STH efficiency of > 20%. Also, the low-cost LiCo 2 O 4 OER catalysts need to replace the benchmark IrO 2 for evaluation. Finally, techonomic analysis of full high-performance and high-value integrated PEC devices needs to be carried out for comparison in terms of cost.

08 HYDROGEN↗