Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “oxide electrolyte”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 55 records · Page 3

Performance Testing of Molten Regolith Electrolysis with Transfer of Molten Material for the Production of Oxygen and Metals on the Moon

Previously, we have demonstrated the production of oxygen by electrolysis of molten regolith simulants at temperatures near 1600 C. Using an inert anode and suitable cathode, direct electrolysis (no supporting electrolyte) of the molten silicate is carried out, resulting in the production of molten metallic products at the cathode and oxygen gas at the anode. Initial direct measurements of current efficiency have confirmed that the process offer potential advantages of high oxygen production rates in a smaller footprint facility landed on the moon, with a minimum of consumables brought from Earth. We now report the results of a scale-up effort toward the goal of achieving production rates equivalent to 1 metric ton O2/year, a benchmark established for the support of a lunar base. We previously reported on the electrochemical behavior of the molten electrolyte as dependent on anode material, sweep rate and electrolyte composition in batches of 20-200g and at currents of less than 0.5 A. In this paper, we present the results of experiments performed at currents up to 10 Amperes) and in larger volumes of regolith simulant (500 g - 1 kg) for longer durations of electrolysis. The technical development of critical design components is described, including: inert anodes capable of passing continuous currents of several Amperes, container materials selection, direct gas analysis capability to determine the gas components co-evolving with oxygen. To allow a continuous process, a system has been designed and tested to enable the withdrawal of cathodically-reduced molten metals and spent molten oxide electrolyte. The performance of the withdrawal system is presented and critiqued. The design of the electrolytic cell and the configuration of the furnace were supported by modeling the thermal environment of the system in an effort to realize a balance between external heating and internal joule heating. We will discuss the impact these simulations and experimental findings have on the design of a suitable prototype for lunar applications

Sibille, Laurent↗

Developing Stable Critical Materials and Microstructure for High-Flux and Efficient Hydrogen Production through Reversible Solid Oxide Cells

Reversible Solid Oxide Cells (RSOCs), which operate as either Solid Oxide Fuel Cells (SOFCs) or Solid Oxide Electrolytic Cells (SOECs), hold great promise for clean, high-efficiency energy conversion and hydrogen production. However, their commercial potential is hindered by stability issues arising from temperature-induced materials degradation. While substantial progress has been made in developing durable, reduced-temperature SOFCs - bringing them closer to commercial deployment, SOECs still exhibit substantially higher degradation rates at both the cell and stack levels under practical operating conditions.

08 HYDROGEN↗

Electrochemical Investigation of Moisture Byproducts in Molten Calcium Chloride

Residual water in molten CaCl 2 reacts to form different byproducts, such as HCl, which can impact the corrosivity of the salt and efficiency of electrochemical operations, such as electrolytic oxide reduction and electrorefining. The ability to detect and quantify these byproducts electrochemically can provide feedback on the efficacy of vacuum drying and other purification methods, as well as the impact of these byproducts on process operations. An electrochemical signal’s association with the production of H 2 is verified and characterized using cyclic voltammetry (CV) and residual gas analysis. CV estimated a 2-electron exchange process associated with H 2 production. CV detected trace quantities of an oxidized species containing hydrogen in the salt on the order of 10 ppm. Different salt handling methods were compared for their impact on the hydrogen electrochemical signal. It was found that 30 min of exposure of CaCl 2 in a beaker to low-humidity air (<20%) had minimal impact on the H 2 production signal.

Electrochemistry↗

Capacity Gain in Li-Ion Cells with Silicon-Containing Electrodes

Silicon-containing lithium-ion batteries can exhibit capacity gain early in life, which makes forecasting future cell behavior difficult. We have observed these anomalous trends even in conditions where known mechanisms, such as overhang equalization and excessive electrolyte oxidation, are unlikely to be significant. Here, we combine simulations and experiments to analyze four cases that can produce increased capacity in Si cells. Three of these pathways relate to “break-in” processes, where improved mass and charge transport can lead to increased access to active electrode domains and decreased cell impedance. The fourth case occurs at high levels of prelithiation, when the positive electrode (PE) is completely replenished with Li + at the end of cell discharge. We show that the commonality among these mechanisms is that the underlying transformations change the potentials experienced by electrodes at the end of half-cycles, increasing the Li + inventory available to the cell. A quantitative framework to describe these effects is presented, enabling these ideas to be extended to other battery systems.

25 ENERGY STORAGE↗

A method for making an alkaline battery electrode plate

A method is described for making an alkaline battery electrode plate where the desired active substances are filled into a nickel foam substrate. In this substrate an electrolytic oxidation reduction occurs in an alkaline solution containing lithium hydroxide.

Chida, K.↗

Characterization of Oxygen Anode Film Studies

Annual report on the Anode Films project. The objectives of this project are to: * Characterize the films that develop on the anode during electrolytic oxide reduction (OR) of UO2 fuel * Develop operando methods to remove these films and preclude their formation

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A structural and electrochemical study of perfluoropolyether-poly(ethylene oxide) solid polymer electrolytes

Solid polymer electrolytes offer attractive safety, processability, and interfacial adhesion for enabling high–energy solid-state lithium batteries, but they are often limited by narrow oxidative stability windows and low lithium-ion transference numbers. In an attempt to broaden the electrochemical stability window and increase lithium-ion transference number of poly(ethylene oxide) (PEO)-based solid polymer electrolytes, we produce an optically clear, crosslinked membrane of PEO and perfluoropolyether (PFPE) using a mixed solvent method and subsequently infuse the membrane with a lithium salt. Structural and thermal analyses reveal nanoscale phase separation between fluorocarbon and hydrocarbon domains with characteristic spacings of 7–8 nm and an elevated glass transition for the hydrocarbon phase. Consistent with this, PFPE-containing membranes exhibit substantially lower ionic conductivity than PEO analogs (dry and plasticized). The transference number and electrochemical stability are similar to pure PEO. These results demonstrate that fluorination implemented as segregated nanoscale domains does not deliver the anticipated transport or stability benefits; instead, phase separation increases tortuosity and suppresses hydrocarbon-phase dynamics. The work underscores the importance of fluorine placement and morphology control, guiding the design of partially fluorinated solid polymer electrolytes toward architectures that avoid detrimental nanoscale phase separation.

Carden, Peyton [ORNL] (ORCID:0000000162296538)↗

Colloidal Behavior of Plutonium Oxide in Concentrated Electrolyte Solutions

The Hanford Site in Washington State manages legacy high-level radioactive waste streams that display major chemistry and engineering challenges, including the high salt levels and pH values that correspond to conditions under which many classical concepts describing chemical reactivity cannot be applied. One particular challenge that needs to be tackled at Hanford is that Pu concentrations, [Pu], in the soluble phases of the tank wastes are higher than expected based on the solubility of crystalline PuO2, which is widely accepted to be caused by the formation of PuO2 colloid, consisting of nano- to submicron-sized particles (PuO2 NPs). Fundamental research underpinning the behavior of PuO2 NPs under conditions not only relevant to the Hanford tank waste but at high ionic strength in general is needed to reliably predict the chemical reactivity of PuO2 NPs and develop engineering solutions to safely and efficiently process high-level radioactive waste into forms suitable for long-term storage. In this work, we study the behavior of PuO2 NPs (particle size ~100 nm) under high ionic strength conditions by reacting it with highly concentrated (up to 5 M) salt solutions. We explore different electrolyte compositions to elucidate the impact of different anions (NO3-, Cl-, ClO4-, SO42-, C2O42-, CO32-) on the stability of PuO2 NP in the acidic and alkaline pH regime. PuO2 NP aggregation and precipitation as function electrolyte concentration is tracked by a combination of liquid scintillation counting, dynamic light scattering for determination of particle size distributions, and zeta potentials as a proxy for particle charge. At acidic pH, electrolytes containing non-coordinating anions, such as NaNO3, NaCl, and NaClO4 mostly stabilize PuO2 NPs over a large electrolyte concentration range, showing only subtle differences in their reactivity. Other electrolyte anions show a more pronounced effect on the PuO2 NP stability: SO42-, binds directly to the particles’ surface, reverses the particle charge, and precipitates the PuO2 NPs efficiently even at intermediate sulfate concentrations (>0.1 M). In contrast, C2O42- is found to lead to high [Pu] in solution, in the milli-molar range, even at mildly acidic pH (~4). Thermodynamic modeling of the dissolved Pu concentrations using PHREEQC is unable to predict the observed [Pu] in the acidic pH regime, supporting the influence of colloids in maintaining elevated [Pu]. It is noteworthy that the current thermodynamic databases do not include constants for colloidal Pu phases and cannot accurately predict many of the high ionic strength solutions relevant to this work. The mechanisms and models responsible for these observations will need further investigation in the future. At high pH values (~12), PuO2 NPs exhibits classical sol-gel chemistry, meaning that upon destabilization of the colloidal sol, for example by addition of concentrated NaOH, highly porous and viscid PuO2 coagulates are formed that consist of a three-dimensional network likely held together by physical interactions. The PuO2 NP coagulate shows no significant reversibility of the aggregation when contacted with concentrated brines; however, PuO2 NPs can be efficiently resuspended in solution by addition of diluted electrolytes, alkaline solutions containing high amounts of carbonate, or simple addition of water. Especially carbonate is shown to stabilize PuO2 NPs in solution at high pH, characterized by stable colloidal suspensions that are resistant against sedimentation during centrifugation. Thermodynamic modeling of the carbonate system was able to predict an increasing dissolved Pu concentration with increasing carbonate concentration. However, the model was profoundly sensitive to the fixed redox potential and does not include any thermodynamic constants for colloidal Pu species.

Neumann, Julia↗

Suppressing Atmospheric Degradation of Sulfide-Based Solid Electrolytes via Ultrathin Metal Oxide Layers

Sulfide-based solid-state electrolytes (SSEs) are promising materials with superior Li-ion conductivity; however, their poor atmospheric stability limits commercial manufacturing at scale. Here, we investigate the impact of ultrathin metal oxide layers deposited via atomic layer deposition (ALD) on the stability of Li 6 PS 5 Cl (LPSCl). Al 2 O 3 layers grown directly on LPSCl particles significantly stabilize the surface chemistry and Li-ion transport properties relative to uncoated material upon exposure to both an ambient atmosphere (22% relative humidity, RH) and humidified O 2 (100% RH). Detailed investigations indicate that coatings impede the surface and bulk degradation kinetics of exposed materials, even for coatings as thin as ∼1 Å. Furthermore, this suggests that stabilization is due to more than just a physical barrier. Shifts in valence band edge positions of coated LPSCl indicate that ALD coatings alter the surface electronic structure and resulting oxidation tendency of underlying LPSCl, suggesting new avenues to improving the environmental stability of sulfide SSEs.

Atmospheric chemistry↗

Fuel-Cell Power Source Based on Onboard Rocket Propellants

The use of onboard rocket propellants (dense liquids at room temperature) in place of conventional cryogenic fuel-cell reactants (hydrogen and oxygen) eliminates the mass penalties associated with cryocooling and boil-off. The high energy content and density of the rocket propellants will also require no additional chemical processing. For a 30-day mission on the Moon that requires a continuous 100 watts of power, the reactant mass and volume would be reduced by 15 and 50 percent, respectively, even without accounting for boiloff losses. The savings increase further with increasing transit times. A high-temperature, solid oxide, electrolyte-based fuel-cell configuration, that can rapidly combine rocket propellants - both monopropellant system with hydrazine and bi-propellant systems such as monomethyl hydrazine/ unsymmetrical dimethyl hydrazine (MMH/UDMH) and nitrogen tetroxide (NTO) to produce electrical energy - overcomes the severe drawbacks of earlier attempts in 1963-1967 of using fuel reforming and aqueous media. The electrical energy available from such a fuel cell operating at 60-percent efficiency is estimated to be 1,500 Wh/kg of reactants. The proposed use of zirconia-based oxide electrolyte at 800-1,000 C will permit continuous operation, very high power densities, and substantially increased efficiency of conversion over any of the earlier attempts. The solid oxide fuel cell is also tolerant to a wide range of environmental temperatures. Such a system is built for easy refueling for exploration missions and for the ability to turn on after several years of transit. Specific examples of future missions are in-situ landers on Europa and Titan that will face extreme radiation and temperature environments, flyby missions to Saturn, and landed missions on the Moon with 14 day/night cycles.

Ganapathi, Gani↗

Low temperature electrolytes for lithium/silver vanadium oxide cells

Combinations of methyl formate (MF) and propylene carbonate (PC) using salt concentrations of 0.6 to 2.4 M, with lithium hexafluoroarsenate and lithium tetrafluoroborate in a five to one molar ratio, were investigated as electrolytes in lithium/silver vanadium oxide batteries. The composition of the electrolyte affected cell performance at low temperature, self-discharge and abuse resistance as characterized by short circuit and crush testing. The electrolyte that provided the best combination of good low temperature performance, low cell self-discharge and abuse resistance was 0.6 M salt in 10:90 PC/MF.

Tuhovak, Denise R.↗

Formulations for Stronger Solid Oxide Fuel-Cell Electrolytes

Tests have shown that modification of chemical compositions can increase the strengths and fracture toughnesses of solid oxide fuel-cell (SOFC) electrolytes. Heretofore, these solid electrolytes have been made of yttria-stabilized zirconia, which is highly conductive for oxygen ions at high temperatures, as needed for operation of fuel cells. Unfortunately yttria-stabilized zirconia has a high coefficient of thermal expansion, low resistance to thermal shock, low fracture toughness, and low mechanical strength. The lack of strength and toughness are especially problematic for fabrication of thin SOFC electrolyte membranes needed for contemplated aeronautical, automotive, and stationary power-generation applications. The modifications of chemical composition that lead to increased strength and fracture toughness consist in addition of alumina to the basic yttria-stabilized zirconia formulations. Techniques for processing of yttria-stabilized zirconia/alumina composites containing as much as 30 mole percent of alumina have been developed. The composite panels fabricated by these techniques have been found to be dense and free of cracks. The only material phases detected in these composites has been cubic zirconia and a alumina: this finding signifies that no undesired chemical reactions between the constituents occurred during processing at elevated temperatures. The flexural strengths and fracture toughnesses of the various zirconia-alumina composites were measured in air at room temperature as well as at a temperature of 1,000 C (a typical SOFC operating temperature). The measurements showed that both flexural strength and fracture toughness increased with increasing alumina content at both temperatures. In addition, the modulus of elasticity and the thermal conductivity were found to increase and the density to decrease with increasing alumina content. The oxygen-ion conductivity at 1,000 C was found to be unchanged by the addition of alumina.

Bansal, Narottam P.↗

The Role of Catholyte Modulation in Suppressing the Initial Capacity Fade of Zinc Electrolytic Manganese Dioxide Coin Cells

Despite its potential for zinc–manganese oxide batteries, electrolytic manganese dioxide (EMD) can experience capacity fade due to a deficiency in the Mn 2+ supply at the cathode electrolyte interphase (CEI) from side reactions, even in the presence of an electrolyte additive. In this work, electrolyte loading modulation at the cathode electrolyte interface (CEI) was correlated with Zn∥EMD cell capacity retention and cycling performance, as a proposed measure to curb the initial capacity fade observed in EMD. Initial galvanostatic charge/discharge cycling, with varied electrolyte loading, revealed severe capacity fade (from ~188 to 10 mAh g –1 for the highest loading of 200 μL) within the first 15 cycles. Such a decrease in cell capacity is correlated with the formation of a Mn 4+ deposit on the current collector and consequently, the Mn 2+ depletion at CEI, as was supported by elemental and Raman analyses. Interestingly, confinement of the electrolyte to the CEI at a lower (≤15 μL) electrolyte loading mitigated Mn 4+ side-deposition, maintaining the cell capacity at >80% over the first 15 cycles. Interfacial Mn supply/depletion could be monitored via voltammetric analysis based on changes of the Zn 2+ insertionreduction peak. Additional galvanostatic experiments corroborated the voltammetric interpretation and the proposed degradation pathway in the studied cell conditions. The outcomes of this work provide practical insight into coin-cell design and configuration strategies for developing Zn∥EMD batteries.

25 ENERGY STORAGE↗