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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 19 records

Implementing hydrogen oxidation reaction on Pt for controlling counter electrode processes

The search for active, stable, and durable materials for electrochemical energy technologies requires increasing levels of precision to establish true structure-function relationships and guide materials design from atomic and molecular scale. This increases the level of control required over the experimental system for proper materials evaluation. The choice of counter electrode material become crucial, as Pt dissolution at high voltages may cause contamination to the working electrode, especially when studying reductive processes in reactions such as oxygen reduction reaction (ORR), H 2 evolution reaction (HER), and the CO 2 reduction reaction. The learnings from “old school” electrochemistry groups lead us to leverage H 2 reactions over Pt to construct a counter electrode system with controlled potential that eliminates Pt ion contamination concerns. In here we discuss the construction of such Pt|H 2 counter electrode where key experimental aspects such as the H 2 flow rate and effective distribution determines the maximum current this counter electrode can accommodate before switching to high voltage and triggering Pt dissolution. Lastly, we demonstrate the use of the Pt|H 2 counter electrode in aqueous electrolytes during HER occurring on the working electrode at varying currents, showing that the Pt content in the cell remains below parts per trillion (ppt) up to 10 mA, and below 50 ppt at 100 mA up to 1 h of constant current hold. This work provides a guide to the implementation of Pt|H 2 counter electrodes to improve the precision of electrochemical experiments in search of highly active, selective, and durable materials for energy technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Simulation and measurement of melting effects on metal sheets caused by direct lightning strikes

Direct lightning strikes melt metal parts of various systems, like fuel and propellant tanks of rockets and airplanes, at the point of strike. Responsible for this melting are the impulse current and, if occurring, the long duration current, both carrying a remarkable charge Q. For studying these meltings the simulation in the laboratory has to be based on the parameters of natural lightnings. International standards exist defining certain threat levels of natural lightnings and giving possible generator circuits for the simulation. The melting caused by both types of lightning currents show different appearance. Their characteristics, their differences in melting and heating of metal sheets are investigated. Nevertheless the simulation of lightning in the laboratory is imperfect. While natural lightning is a discharge without a counter electrode, the simulation always demands a close counter electrode. The influence of this counter electrode is studied.

Kern, Alexander

Enhanced performance of Bi 2 S 3 /TiO 2 heterostructure composite films for solar cell applications

Day to day energy production is shifting towards renewable energy sources as these sources become more economically viable while being less polluting to operate; solar energy has become one of the major sources of renewable energy. However, it currently relies on ultra-pure silicon ingots to produce commercial silicon photovoltaics, which prevents the cost of electricity being produced to compete with non-renewable energy production. A viable low-cost alternative for silicon based cells would be dye-sensitized solar cells (DSSCs), which are easier and cheaper to manufacture as they do not require expensive and delicate raw materials to make. Moreover, they could be made semi-flexible which allows for a greater variety of applications. A DSSC consists of three components, a photo-electrode, an electrolyte and a counter-electrode. When exposed to incident light, the complex photosensitizers in the photoelectrode release electrons which are transported to the external load, leaving the photoelectrode in an oxidized state. The electrons are collected by the counter electrode and used to reduce the electrolyte. This charged electrolyte then reduces the positively charged photoelectrode, allowing the process to begin again. To improve the efficiency of this process, we explore the use of bismuth sulfide (Bi 2 S 3 ) and titanium oxide (TiO 2 ) composite as photoelectrode material and investigate their impact on the efficiency of DSSC.

14 SOLAR ENERGY

Electrochemical stability and corrosion behavior of Ni-Cr alloy in molten LiCl-KCl salt

This study investigated the electrochemical properties and potential-dependent stability of Cr(II) and Ni(II) in a eutectic LiCl-KCl molten salt at 500 °C under an argon atmosphere using a three-electrode cell configuration with a glassy carbon working electrode, Ag/Ag + reference electrode, and graphite counter electrode. Cyclic voltammetry was employed to characterize the Cr(0)/Cr(II)/Cr(III) and Ni(0)/Ni(II) redox transitions, yielding diffusion coefficients of 0.50 (±0.01) × 10 −5 cm 2 s −1 for Cr(II) and 0.91 (±0.16) × 10 −5 cm 2 s −1 for Ni(II) at 500 °C. The redox stability domains of these species provided insight into the corrosion mechanisms of a Ni-Cr alloy (80–20 wt %) in LiCl-KCl salt. The measured open circuit potential of the alloy corresponded to the range of potentials where the Ni(0) and Cr(II) species are stable, indicating a preferential dissolution of Cr. Immersion testing of the alloy for 336 h confirmed significant Cr depletion (or Ni-enrichment) at the surface layer, corroborating Cr dealloying as the dominant corrosion reaction under open circuit conditions. Additionally, the application of a small anodic overpotential (0.11 V) resulted in selective Cr dissolution while a large anodic overpotential (0.25 V) resulted in co-dissolution of both Cr and Ni. Furthermore, these results demonstrate that the corrosion mechanisms of a Ni-Cr alloy in LiCl-KCl depend upon the applied potential, and thus the redox conditions of the molten salt should be carefully controlled in the design of a redox buffer to mitigate corrosion in molten salt environments.

22 GENERAL STUDIES OF NUCLEAR REACTORS

Electrochemical amperometric gas sensors for environmental monitoring and control

Theoretical considerations and experimental results regarding a unique class of vapor sensors are presented, and the sensors are compared to semiconductor-based sensors. The electrochemical sensors are based on nonaquaeous electrolytes, and gas-detection selectivity achieved by applying a known potential to the sensing electrode using a reference electrode and a counter electrode. Results are given regarding the detection of oxygen and carbon dioxide using one cell, the detection of 3-percent carbon dioxide in nitrogen, and the detection of carbon dioxide in air at percentages ranging from 3 to 6. The sensors are found to be effective in the detection of toxic chemical species including CO, NO2, and formaldehyde; the sensors are further found to require minimal power, operate over long periods of time, and function over a wide temperature range.

Venkatasetty, H. V.

Next-Generation Microshutter Arrays for Large-Format Imaging and Spectroscopy

A next-generation microshutter array, LArge Microshutter Array (LAMA), was developed as a multi-object field selector. LAMA consists of small-scaled microshutter arrays that can be combined to form large-scale microshutter array mosaics. Microshutter actuation is accomplished via electrostatic attraction between the shutter and a counter electrode, and 2D addressing can be accomplished by applying an electrostatic potential between a row of shutters and a column, orthogonal to the row, of counter electrodes. Microelectromechanical system (MEMS) technology is used to fabricate the microshutter arrays. The main feature of the microshutter device is to use a set of standard surface micromachining processes for device fabrication. Electrostatic actuation is used to eliminate the need for macromechanical magnet actuating components. A simplified electrostatic actuation with no macro components (e.g. moving magnets) required for actuation and latching of the shutters will make the microshutter arrays robust and less prone to mechanical failure. Smaller-size individual arrays will help to increase the yield and thus reduce the cost and improve robustness of the fabrication process. Reducing the size of the individual shutter array to about one square inch and building the large-scale mosaics by tiling these smaller-size arrays would further help to reduce the cost of the device due to the higher yield of smaller devices. The LAMA development is based on prior experience acquired while developing microshutter arrays for the James Webb Space Telescope (JWST), but it will have different features. The LAMA modular design permits large-format mosaicking to cover a field of view at least 50 times larger than JWST MSA. The LAMA electrostatic, instead of magnetic, actuation enables operation cycles at least 100 times faster and a mass significantly smaller compared to JWST MSA. Also, standard surface micromachining technology will simplify the fabrication process, increasing yield and reducing cost.

Moseley, Samuel

Precious metal oxygen-evolving anodes for electrolytic reduction of metal oxides in molten LiCl-Li 2 O electrolyte

Understanding the electrochemical stability of oxygen-evolving anode materials in molten salt electrolytes is essential to enable decarbonized electrolytic reduction of metal oxides (e.g., used nuclear oxide fuels). Here, this work investigated three precious metals (Ir, Ru, and Pt) as oxygen-evolving anodes in molten LiCl-Li 2 O (99.0-1.0 wt%) at 650 °C. For consistent measurements, this work employed a three-electrode cell comprised of a two-phase Li-Bi (65-35 at%) reference electrode and a NiO counter electrode. Anodic polarization behavior of each anode was investigated via cyclic voltammetry (CV) and chronoamperometry. The onset potential for oxygen evolution was observed at E > 2.9 V (vs. Li/Li + ) for the Ir and Ru anodes and anodic current density was as high as 1.0 A cm -2 at 3.23 V. The dimensional stability of each anode was evaluated from long-term electrolysis experiments (10.0-32.1 h) at 3.23 V. Rapid consumption of the Pt anode was observed after the application of 26,453 C cm -2 with a reduction in diameter of about 15.8% due to the formation of a non-protective Li 2 PtO 3 compound. The formation of this compound was also observed during CV measurements as additional anodic waves at potentials more negative than that of oxygen evolution. In contrast, both the Ir and Ru anodes exhibited excellent dimensional stability with a reduction in diameter or thickness of less than 1.5% even after applying greater charge density of ~41,100 C cm -2 , demonstrating superior stability during oxygen evolution in the LiCl-Li 2 O electrolyte.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Electrochemical Recovery of Rare-Earth Elements from Coal Fly Ash Using Ionic Liquids as both Extractant and Electrolyte

Rare-earth elements (REEs) are critical for medical technologies, electronics, and clean energy. Coal fly ash (CFA), a byproduct of coal combustion, offers a promising alternative REE source. However, efficient extraction and separation of REEs from CFA remain challenging due to the complex composition of CFA. This study introduces a sustainable method for REE recovery using a recyclable ionic liquid, betainium bis(trifluoromethylsulfonyl)imide ([Hbet]- [Tf 2 N]), which serves both as the extractant from CFA and as the electrolyte in electrodeposition. In the first stage, [Hbet][Tf 2 N] preferentially extracts REEs from CFA through leaching. In the second stage, the REE-enriched ionic liquid undergoes electrochemical deposition using amperometry techniques, where REEs are reduced and deposited onto the electrode. The deposition experiments were conducted from −0.5 to −2.0 V vs a Pt quasireference electrode in a three-electrode setup comprising titanium as the working electrode and platinum as both the reference and counter electrodes. Varying the applied potential enabled potential-dependent preferential REE deposition. At −0.5 V, neodymium (Nd) showed preferential recovery, reaching 25% with a separation factor of 37 over other REEs. In contrast, applying a more negative potential increased overall deposition, yielding ∼50% Nd recovery and 10−20% recovery for the remaining REEs. After recovery, the ionic liquid was regenerated and reused for a subsequent electrochemical recovery cycle. Overall, this study demonstrates a feasible approach for REE recovery from CFA waste, with potential to enhance resource utilization within the REE supply chain.

coal fly ash

YBa2Cu3O(7-delta)/Au/Nb sandwich geometry SNS weak links on c-axis oriented YBa2Cu3O(7-delta)

Sandwich geometry superconductor/normal metal/superconductor structures have been fabricated on LaAlO3 and cubic zirconia with laser-ablated, c-axis-oriented YBa2Cu3O(7-delta) base electrodes, 100-600 A of Au, and Nb counter electrodes, all formed in situ without breaking vacuum. Junctions range in size from 5 to 50 micron on a side. Four probe I-V measurements at 4.2 K show RnA products as low as 6 x 10 to the -9th sq cm and critical current densities up to 5.2 kA/sq cm. AC Josephson steps were observed with the application of 10-GHz radiation. The temperature dependence of Jc and the observation of the AC Josephson effect suggest that true supercurrents are present and that they do indeed represent the characteristics of the YBa2Cu3O(7-delta)/Au/Nb structure. The best results were obtained when the devices were annealed at about 450 C in O2 for 30 min after Au deposition.

Foote, M. C.

A portable hypergolic oxidizer vapor sensor for NASA's Space Shuttle program

The design and performance characteristics of an electrochemical NO2 sensor selected by NASA for the space shuttle program is described. The instrument consists of a sample pump, an electrochemical cell, and control and display electronics. The pump pushes the sample through the electrochemical cell where the vapors are analyzed and an output proportional to the NO2 concentration is produced. The output is displayed on a panel meter, and is also available at a recorder jack. The electrochemical cell is made up of a polypropylene chamber covered with teflon membrane faceplates. Plantinum electrodes are bonded to the faceplates, and the sensing and counter electrodes are potentiostatically controlled at -200 mV with respect to the reference electrode. The cell is filled with electrolyte, consisting of 13.5 cc of 23% solution of KOH.

Helms, W. R.

Nucleation-promoting and growth-limiting synthesis of disordered rock-salt Li-ion cathode materials

Disordered rock-salt oxides and oxyfluorides are promising positive electrode materials for high-performance lithium-ion batteries free of nickel and cobalt. However, conventional synthesis methods rely on post-synthesis pulverization to achieve cycling-appropriate particle sizes, offering limited control over particle microstructure and crystallinity. This accelerates degradation and complicates secondary particle processing. Here we present a synthesis strategy that enhances nucleation while suppressing particle growth and agglomeration across various disordered rock-salt compositions, including lithium–manganese–titanium oxide, lithium–manganese–niobium oxide, and lithium–nickel–titanium oxide systems. Applied to Li 1.2 Mn 0.4 Ti 0.4 O 2 , this method yields highly crystalline, well-dispersed sub-200 nm particles that form homogeneous electrode films with stable cycling behavior. Tested in cells with lithium metal as the counter electrode, these electrodes deliver ~200 mAh/g with 85% capacity retention relative to the first cycle after 100 cycles (20 mA/g, 1.5–4.8 V), and an average discharge voltage loss of 4.8 mV per cycle, compared to 38.6% retention and 7.5 mV loss per cycle for electrodes derived from pulverized solid-state particles. This approach suggests a route to enhance the performance and durability of disordered rock-salt electrodes for sustainable lithium-ion batteries.

Batteries

Expansion of the nickel electrode

To observe a reasonable amount of expansion, months or years in acutal batteries are required. Therefore, the technique of electrode bending was developed. Active material is taken off a sample electrode on one side, and left only on the other side with a cadmium counter electrode. With this configuration, if the active material expands, the electrode will bend convex - concave towards this direction. This very small bending may be easily detected with light deflection. A laser beam was used to project it on the screen through a mirror attached on the electrode, thus making a very sensitive measurement of a very small expansion.

Lim, H. S.

Method Producing an SNS Superconducting Junction with Weak Link Barrier

A method of producing a high temperature superconductor Josephson element and an improved SNS weak link barrier element is provided. A YBaCuO superconducting electrode film is deposited on a substrate at a temperature of approximately 800 C. A weak link barrier layer of a nonsuperconducting film of N-YBaCuO is deposited over the electrode at a temperature range of 520 C. to 540 C. at a lower deposition rate. Subsequently a superconducting counter-electrode film layer of YBaCuO is deposited over the weak link barrier layer at approximately 800 C. The weak link barrier layer has a thickness of approximately 50 A and the SNS element can be constructed to provide an edge geometry junction.

Hunt, Brian D.

Linking Pressure to Electrochemical Evolution in Solid-State Conversion Cathode Composites

Conversion-type cathodes, such as sulfur, FeS 2 , and FeF 3 , offer high theoretical capacities in solid-state lithium batteries but are hindered by substantial volume changes during cycling, leading to interfacial contact loss, crack formation, and microstructural degradation. Here, we investigate the relationships between electrochemical, mechanical, and structural evolution in solid-state electrode composites with these three active materials. Using real-time stack-pressure monitoring, synchrotron X-ray absorption spectroscopy, and electrokinetic modeling, we elucidate how stress evolution is linked to reversible and irreversible redox reactions. Nonlinear stack pressure evolution in cells with sulfur, FeS 2 , and FeF 3 electrode composites is found to arise from material-specific volume changes, the balance of volume change between the working and counter electrode, and the formation of distinct reaction intermediates. The three materials exhibit distinct stack pressure evolution, which is closely related to the different reaction processes in the materials, as demonstrated with X-ray absorption spectroscopy measurements. Through mesoscale modeling, we relate the experimental measurements to species evolution at the particle scale and track the dynamic coexistence of intermediate phases. Our findings highlight the importance of designing for volume changes of a given active material in solid-state battery systems.

batteries

Thin-film ultraviolet detector and spectrometer

Typical metal-insulator-metal detector device is formed on quartz substrate. Base electrode is 3 to 6 nm aluminum layer, overcoated with 3 to 6 nm aluminum oxide or aluminum nitride, and capped with counter electrode of gold, lead, magnesium, or aluminum. Photoelectric yield data are given for Al-AlN-Au structure.

Lewicki, G. W.

Portable Apparatus for Electrochemical Sensing of Ethylene

A small, lightweight, portable apparatus based on an electrochemical sensing principle has been developed for monitoring low concentrations of ethylene in air. Ethylene has long been known to be produced by plants and to stimulate the growth and other aspects of the development of plants (including, notably, ripening of fruits and vegetables), even at concentrations as low as tens of parts per billion (ppb). The effects are magnified in plant-growth and -storage chambers wherein ethylene can accumulate. There is increasing recognition in agriculture and related industries that it is desirable to monitor and control ethylene concentrations in order to optimize the growth, storage, and ripening of plant products. Hence, there are numerous potential uses for the present apparatus in conjunction with equipment for controlling ethylene concentrations. The ethylene sensor is of a thick-film type with a design optimized for a low detection limit. The sensor includes a noble metal sensing electrode on a chip and a hydrated solid-electrolyte membrane that is held in contact with the chip. Also located on the sensor chip are a counter electrode and a reference electrode. The sensing electrode is held at a fixed potential versus the reference electrode. Detection takes place at active-triple-point areas where the sensing electrode, electrolyte, and sample gas meet. These areas are formed by cutting openings in the electrolyte membrane. The electrode current generated from electrochemical oxidation of ethylene at the active triple points is proportional to the concentration of ethylene. An additional film of the solid-electrolyte membrane material is deposited on the sensing electrode to increase the effective triple-point areas and thereby enhance the detection signal. The sensor chip is placed in a holder that is part of a polycarbonate housing. When fully assembled, the housing holds the solid-electrolyte membrane in contact with the chip (see figure). The housing includes a water reservoir for keeping the solid-electrolyte membrane hydrated. The housing also includes flow channels for circulating a sample stream of air over the chip: ethylene is brought to the sensing surface predominately by convection in this sample stream. The sample stream is generated by a built-in sampling pump. The forced circulation of sample air contributes to the attainment of a low detection limit.

Manoukian, Mourad

Ca Metal Batteries and Sn Anode Alloying: Resolving Misconceptions in Ca–Sn Alloy Formation

Ca metal anode suffers from surface passivation and struggles to effectively plate and strip in conventional Ca electrolytes, making the development of alloy anode for calcium metal battery essential. This work systematically and carefully evaluates the electrochemical formation and feasibility of the Sn anode and its possibility of alloying with Ca using a combination of cyclic voltammetry, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM/EDS), X-ray diffraction (XRD), and synchrotron transmission X-ray microscopy (TXM). Electrochemical measurements and SEM/EDS analyses indicate apparent Ca alloy formation. However, detailed XRD and TXM characterization reveal substantial lithium-ion involvement when lithium metal is employed as the reference electrode, even in electrolytes with high Ca salt concentrations. These findings highlight a significant risk of misinterpretation: Although limited Ca–Sn alloying may occur, the faster kinetics of Li + can dominate the alloying process, leading to a Li-driven reactions at the Sn anode. In contrast, cells constructed with Ca metal as both reference and counter electrodes exhibit distinct redox features only during the initial cycles, followed by rapid cell failure. The high oxidation currents induce severe Ca passivation, occurring nearly concurrently with Sn dealloying. Overall, this study provides critical insight into the practical limitations and common experimental artifacts associated with Ca metal battery systems and underscores the necessity for rigorous cell design and cautious interpretation when evaluating alloy chemistry in multivalent Ca-based batteries.

36 MATERIALS SCIENCE