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48 records · Page 3

Development of a regenerable metal oxide CO removal system

A regenerable metal oxide carbon dioxide (CO2) removal system was developed to replace the current means of a nonreusable chemical, lithium hydroxide, for removing the metabolic CO2 of an astronaut in a space suit. Testing indicates that a viable low-volume metal oxide concept can be used in the portable life support system for CO2 removal during Space Station extravehicular activity (EVA). A canister of nearly the same volume as that used for the Space Shuttle, containing 0.10 cu ft of silver-oxide-based pellets, was tested; test data analysis indicates that 0.18 cu ft of the metal oxide will result in an 8-hour EVA capability. The testing suggests that the metal oxide technology offers a low-volume approach for a reusable CO2 removal concept applicable for at least 40 EVA missions. The development and testing of the breadboard regeneration package is also described.

Cusick, Robert J.↗

Microstructural and compositional evolutions in $γ$-LiAlO 2 pellets during ion irradiation at an elevated temperature

This study reports on the microstructural, phasic and compositional evolutions of γ-LiAlO 2 during ion irradiation. Polycrystalline γ-LiAlO 2 pellets were irradiated sequentially with He + and D 2 + ions to the same combined fluences of up to 3 × 10 17 (He + +D + )/cm 2 at 773 K. The irradiated pellets were characterized using scanning transmission electron microscopy and atom probe tomography. Surface amorphization likely due to radiolysis and planar defects as a possible precursor for formation of precipitates are created at 5 × 10 16 (He + +D + )/cm 2 , followed by the formation of nano-sized precipitates and fractures at higher doses. Spinel-like precipitates of non-stoichiometric LiAl 5 O 8 and gas-filled cavities are observed to grow with increasing dose. Faceted precipitates and rounded cavities appear at 2 × 10 17 (He + +D + )/cm 2 . With further increasing ion fluence to 3 × 10 17 (He + +D + )/cm 2 , amorphization of the precipitates takes place and micron-sized fractures appear. Surface exfoliation could occur at an extremely high ion fluence. There are compositional changes in the γ-LiAlO 2 pellets during the microstructural evolution. In the precipitate and amorphized regions, Li concentrations decrease to ~7 and 3.7 at.% from 25 at.% in γ-LiAlO 2 , respectively. This study reveals a full-cycle microstructural evolution with corresponding compositional changes in γ-LiAlO 2 pellets during ion irradiation at 773 K. In conclusion, the data could help model, assess, and predict the material performance during neutron irradiation in reactors.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Type-I ELM mitigation by continuous lithium granule gravitational injection into the upper tungsten divertor in EAST

Large edge-localized modes (ELMs) were mitigated by gravitational injection of lithium granules into the upper X-point region of the EAST device with tungsten plasma-facing components. The maximum ELM size was reduced by ~ 70% in high βN H-mode plasmas. Large ELM stabilization was sustained for up to about 40 energy confinement times, with constant core radiated power and no evidence of high-Z or low-Z impurity accumulation. The lithium granules injection reduced the edge plasma pedestal density and temperature and their gradients, due to increased edge radiation and reduced recycling from the plasma-facing components. Ideal stability calculations using the ELITE code indicate that the stabilization of large ELMs correlates with improved stability of intermediate-n peeling-ballooning modes, due to reduced edge current resulting from the profile changes. The pedestal pressure reduction was partially offset by a core density increase, which resulted in a modest ~ 7% drop in core stored energy and normalized energy confinement time. We surmise that the remnant small ELMs are triggered by the penetration of multiple Li granules just past the separatrix, similar to small ELMs triggered by deuterium pellet [S. Futatani et al., Nucl. Fusion 54 (2014) 073008]. This study extends previous ELM elimination with Li powder injection [R. Maingi et al., Nucl. Fusion 58 (2018) 024003] in EAST because 1) use of small, dust-like powder and the related potential health hazards were eliminated, and 2) use of macroscopic granules should be more applicable to future devices, due to deeper penetration than dust particles, e.g. inside the separatrix with velocities ~ 10 m/s in EAST.

EAST↗

Active Divertor Heat Flux Control using Impurity Powder Dropper

Divertor plasma-facing components (PFCs) in a tokamak are typically designed to withstand average steady-state heat loads of about 5–10 MW/m 2 , a limit that applies to both solid and liquid lithium (LL) PFCs. Exceeding these design values can result in surface damage to tungsten PFCs or excessive lithium (Li) evaporation in liquid lithium divertor (LLD) PFCs. Since exceeding the divertor heat load limits has serious consequences, it is therefore prudent to develop a tool to reduce the divertor heat load and bring the heat load to within the design limit without affecting the plasma performance. Active low Z impurity injection such as Li has been suggested as a potential solution to mitigate excess heat flux as suggested previously, given that non-coronal radiation can be quite large ~ 20–30 MJ per mole of injected Li. Li is considered desirable for reducing the edge neutral recycling helping to improve plasma energy confinement. In this paper, we model the Impurity Power Dropper (IPD) to investigate its potential of divertor heat flux control. The IPD is typically located at the top of the tokamak device and uses a vertical drift tube of a few meters. In the 2 m drift tube case, the IPD powder is accelerated to ~ 6 m/sec before reaching the plasma with the upper divertor configuration, matching the condition for the in-board side pellet injection case. By modeling the IPD geometry we determined the IPD powder deposition profile, and thus the non-coronal radiation and ionization profiles in time as well. From the enhanced radiation power loss, it is therefore possible to reduce the divertor heat load using the divertor simulation code. In conclusion, the IPD divertor heat flux control can be tested in the facilities with IPD including ST-40, DIII-D, EAST, WEST and NSTX-U.

Active lithium injection↗

Type-I ELM mitigation by continuous lithium granule gravitational injection into the upper tungsten divertor in EAST

Large edge-localized modes (ELMs) were mitigated by gravitational injection of lithium granules into the upper X-point region of the experimental advanced superconducting tokamak (EAST) device with tungsten plasma-facing components. The maximum ELM size was reduced by ~70% in high β N H-mode plasmas. Large ELM stabilization was sustained for up to about 40 energy confinement times, with constant core radiated power and no evidence of high-Z or low-Z impurity accumulation. The lithium granules injection reduced the edge plasma pedestal density and temperature and their gradients, due to increased edge radiation and reduced recycling from the plasma-facing components. Ideal stability calculations using the ELITE code indicate that the stabilization of large ELMs correlates with improved stability of intermediate-n peeling-ballooning modes, due to reduced edge current resulting from the profile changes. The pedestal pressure reduction was partially offset by a core density increase, which resulted in a modest ~7% drop in core stored energy and normalized energy confinement time. We surmise that the remnant small ELMs are triggered by the penetration of multiple Li granules just past the separatrix, similar to small ELMs triggered by deuterium pellet Futatani et al (2014 Nucl. Fusion 54 073008). This study extends previous ELM elimination with Li powder injection Maingi et al (2018 Nucl. Fusion 58 024003) in EAST because (1) use of small, dust-like powder and the related potential health hazards were eliminated, and (2) use of macroscopic granules should be more applicable to future devices, due to deeper penetration than dust particles, e.g. inside the separatrix with velocities ~10 m s -1 in EAST.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Thermally Driven Interfacial Degradation between Li 7 La 3 Zr 2 O 12 Electrolyte and LiNi 0.6 Mn 0.2 Co 0.2 O 2 Cathode

Solid-state batteries offer higher energy density and enhanced safety compared to the present lithium-ion batteries using liquid electrolytes. A challenge to implement them is the high resistances, especially at the solid electrolyte interface with the cathode. Sintering at elevated temperature is needed in order to get good contact between the ceramic solid electrolyte and oxide cathodes and thus to reduce contact resistances. Many solid electrolyte and cathode materials react to form secondary phases. It is necessary to find out which phases arise as a result of interface sintering and evaluate their effect on electrochemical properties. Herein, we assessed the interfacial reactions between LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and Li 7 La 3 Zr 2 O 12 (LLZO) as a function of temperature in air. We prepared model systems by depositing thin-film NMC622 cathode layers on LLZO pellets. The thin-film cathode approach enabled us to use interface-sensitive techniques such as X-ray absorption spectroscopy in the near-edge as well as the extended regimes and identify the onset of detrimental reactions. We found that the Ni and Co chemical environments change already at moderate temperatures, on-setting from 500 °C and becoming especially prominent at 700 °C. By analyzing spectroscopy results along with X-ray diffraction, we identified Li 2 CO 3 , La 2 Zr 2 O 7 , and La(Ni,Co)O 3 as the secondary phases that formed at 700 °C. The interfacial resistance for Li transfer, measured by electrochemical impedance spectroscopy, increases significantly upon the onset and evolution of the detected interface chemistry. Our findings suggest that limiting the bonding temperature and avoiding CO 2 in the sintering environment can help to remedy the interfacial degradation.

36 MATERIALS SCIENCE↗

Doping effect of Al in LLZO

Lithium ion batteries have become a common use in most electronic devices and transportation. However, the use of liquid electrolytes poses a serious safe hazard due to their high flammability. The narrow operating temperature and voltage windows also limit further improvement of the energy density.Solid-state lithium batteries with the use of more stable and safer solid electrolyte have garnered much attention and could be the future choice for battery technology. A promising potential candidate for the solid electrolyte component is the garnet type Li 7 La 3 Zr 2 O 12 (LLZO) ceramic material since it possesses high ionic conductivity at room temperature and enables the use of high capacity lithium anode and high voltage/capacity cathodes.However, to form the stable cubic phase of LLZO and high densification,high sintering temperatures above 1100°C is typically required, which causes Lithium loss of the system.Many studieshave been taken to dop LLZO with various precursors such as Ga, Ta, and Al to stabilize the cubic structure and reduce calcination temperature, while the doping effect on sintering densification is still unclear. In this study Al doping along with ball milling were explored to stabilize the cubic phase of LLZO and improve densification, while reducing the amount of impurity phases. Samples were synthesized from the precursors Li 2 CO 3 , Al 2 O 3 , La 2 O 3 , and ZrO 2 by ball milling followed by heat treatment for 12 hours at 1000°C. XRD with Rietveld fitting was used to determine the two phases of LLZO (cubic, tetragonal) and other possible secondary phases. Furthermore,SEM with top and cross sectional views was conducted to investigate the morphology and microstructure of sintered pellets.

36 MATERIALS SCIENCE↗

A Warm Garage for a Lunar Rover

Approach: One approach to heating a rover during the lunar night is the so-called thermal wadis concept [1]. This involves heating the regolith with solar concentrators and placing the rover on the heated surface for the night. Since the regolith is heated by a relatively weak heat flux, a high thermal conductivity is required for heating a sufficiently large mass of regolith. However, lunar regolith has a low thermal conductivity. Therefore, the concept involves increasing the conductivity by sintering the regolith, which requires a significant energy input and complex procedures. Here we propose an alternative approach where the low thermal conductivity of regolith is an advantage. Specifically, we propose to use a highly exothermic combustible mixture for heat generation. The mixture pellets are placed in the surface layer of regolith and ignited. The combustion forms condensed products and releases heat, which then slowly spreads to the surrounding regolith. Heat can also be transferred, for example, by heat pipes, into radiant heating surfaces installed on the ground. A greenhouse that transmits sunlight during the day and decreases the radiative heat losses during the night can also be installed. Selection of the Heat-generating Mixture: The reactive mixture should have a high specific energy and generate only condensed products since gases could disturb the regolith layer, carry enthalpy out of the system, and lead to an explosion. There are mixtures, (sometimes called pyrolants) that possess very high specific energies. One example is magnesium-Teflon-Viton mixtures used in flares. However, they produce gases and may cause explosions. Other mixtures that include magnesium cannot be used either because of the high vapor pressure of Mg at temperatures well below the combustion temperature. Recently, mixtures that involve lithium peroxide (Li2O2) have been proposedfor using in space power systems [2]. However, they produce lithium oxide (Li2O), which boils at 2800 K at 1 atm and hence at a lower temperature in vacuum. Fortunately, there exist many mixtures that release a lot of heat and form only condensed products during the combustion. Many such mixtures have been used for self-propagating high-temperature synthesis (SHS) of various materials [3, 4]. For the application discussed here, t itanium/boron (1:2 mole ratio) mixture appears to be particularly promising. The specific energy is 4.0 MJ/kg (1.1 kWh/kg), the adiabatic flame temperature is about 3200 K, and the reaction forms solid titanium diboride (TiB2, melting point: 3500 K). The mixture can be ignited easily with a heated tungsten wire, and it has been used widely as a booster to ignite the main mixture in the SHS process.Estimates: Assuming that specific heat of regolith is 500 J/(kg∙K) [5] and all generated heat is transferred to regolith, 12.5 kg of the Ti/B mixture would increase the temperature of 1000 kg of regolith by 100 K. To evaluate the rate of heat transfer in the regolith, a spherical model was analyzed where the heat released by a 12.5 kg Ti/B core propagates by thermal conduction through a 1000 kg regolith shell with no heat loss from its outer surface. At a bulk density of 1500 kg/m3 [5], the radius of the shell was 54 cm, while the radius of the core was about 11 cm. The calculations were conducted using Thermal Desktop SINDA/FLUINT (Cullimore and Ring Technologies) software at two constant values of bulk thermal conductivityk of the regolith: 0.001 and 0.01 W/(m∙K). The results show that after 14.5 days the core lost 31% of the released heat at the lower k and 77% at the higher k. At a distance of 20 cm from the core surface, the temperature of the regolith increased by only 1 K at the lower k and by 132 K at the higher k. In reality, the regolith near the heat source will be melted, so its thermal conductivity will increase significantly. Nevertheless, the conducted estimates indicate that combustion-based heat generators, placed directly in the regolith, could provide heat during a rather long period such as the lunar night.Conclusion: Heat generators based on gasless combustion of highly energetic reactive mixtures could be installed directly in the surface layer of lunar regolith. Because of the low thermal conductivity of the regolith, such generators would keep thermal energy for days and gradually supply heat to a rover/lander.Acknowledgment: The material presented in this work is based upon the work supported by National Aeronautics and Space Administration (NASA) under Grant #80NSSC20K0293.References: [1] Balasubramaniam R. et al. (2011) J. Thermophys. Heat Trans., 25,130−139. [2] Blair R.G. and Vasu S.S. (2022) Conf. Advanced Power Systems for Deep Space Exploration. [3] Varma A. et al. (1998) Adv. Chem. Eng., 24,79−226. [4] Levashov E.A. et al. (2017) Int. Mater. Rev., 62,203−239. [5] Wood-Robinson R. et al. (2019) J. Geophys. Res. Planets, 124, 1989−2011.

lunar↗

On the quality of tape-cast thin films of sulfide electrolytes for solid-state batteries

All-solid-state lithium batteries (ASSLBs) have the potential to increase energy density, improve safety, and allow for lower manufacturing costs compared to conventional, liquid-based Li-ion batteries. The thickness of solid electrolyte (SE) layer dictates the cell-level energy density and it is desirable to make the SE layer as thin as possible while maintaining uniformity and defect-free. Manufacturing a high- quality, thin sulfide SE layer at large-scale, however, is challenging. Previous studies have addressed the compatibility of materials used for manufacturing thin sulfide SE films, paving the way for further investigation of processing conditions and film quality. Here we report a strong correlation between the solid loading of dispersions and the quality of tape-casted thin sulfide SE films. We also demonstrate a method for quantifying the quality of thin SE films by observing both pin-hole defects and larger heterogeneous agglomerations of particles in the films. Our thin sulfide SE films containing ~5 wt% binder are defect-free and show similar ionic conductivity compared to a cold-pressed, binder-free, thick SE pellet, resulting in an ~11X reduction of area specific resistance. Here, this work on the solid loading of the dispersion used in a scalable tape casting process provides insight for manufacturing high-quality, thin sulfide SE films and to increase the cell-level energy density of ASSLB.

36 MATERIALS SCIENCE↗

Multifunctional Coatings on Sulfide‐Based Solid Electrolyte Powders with Enhanced Processability, Stability, and Performance for Solid‐State Batteries

Abstract Sulfide‐based solid‐state electrolytes (SSEs) exhibit many tantalizing properties including high ionic conductivity and favorable mechanical properties for next‐generation solid‐state batteries. Widespread adoption of these materials is hindered by their intrinsic instability under ambient conditions, which makes them difficult to process at scale, and instability at the Li||SSE and cathode||SSE interfaces, which limits cell performance and lifetime. Atomic layer deposition is leveraged to grow thin Al 2 O 3 coatings on Li 6 PS 5 Cl powders to address both issues simultaneously. These coatings can be directly grown onto Li 6 PS 5 Cl particles with negligible chemical modification of the underlying material and enable exposure of powders to pure and H 2 O‐saturated oxygen environments for ≥4 h with minimal reactivity, compared with significant degradation of the uncoated powder. Pellets fabricated from coated powders exhibit ionic conductivities up to 2× higher than those made from uncoated material, with a simultaneous decrease in electronic conductivity and significant suppression of chemical reactivity at the Li‐SSE interface. These benefits result in significantly improved room temperature cycle life at high capacity and current density. It is hypothesized that this enhanced performance derives from improved intergranular properties and improved Li metal adhesion. This work points to a completely new framework for designing active, stable, and scalable materials for next‐generation solid‐state batteries.

36 MATERIALS SCIENCE↗

Microstructural evolution and precipitation in γ-LiAlO 2 during ion irradiation

Polycrystalline γ-LiAlO 2 pellets were sequentially irradiated with 120 keV He + and 80 keV D 2 + ions to the fluences of 1 × 10 17 and 2 × 10 17 (He + + D + )/cm 2 at 573 K. Additional irradiation was performed to a fluence of 2 × 10 17 (He + + D + )/cm 2 at 773 K. The irradiated pellets were characterized using scanning transmission electron microscopy, time-of-flight secondary ion mass spectrometry, and grazing incidence x-ray diffraction. Lattice damage, amorphization, and fractures are observed with no evidence for the formation of secondary-phase precipitates in the pellets irradiated up to an ion fluence of 2 × 10 17 (He + + D + )/cm 2 at 573 K. In contrast, faceted precipitates with sizes larger than 100 nm formed in a pellet irradiated to 2 × 10 17 (He + + D + )/cm 2 at 773 K. Analyses of the diffraction and composition data suggest that the precipitates have a spinel-type structure, likely a non-stoichiometric LiAl 5 O 8 with Li depletion. This could be an intermediate phase with Li atoms at the octahedral and possibly tetrahedral sites as well. It is speculated that as the dose increases, Li loss will continue and the precipitates will approach a composition of alumina primarily in phases of α-Al 2 O 3 and amorphized Al 2 O 3 .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

A simple centrifuge cell method for ex situ quantification of electrical conductivity of slurry electrode materials

We present the design, experimental procedure, and experimental evaluation of a system for fast, simple, and ex situ characterization of electrical conductivity of slurry electrode materials. The system uses a custom-designed electrochemical cell compatible with centrifugation in a swing-bucket centrifuge. The cell features cylindrical graphite electrodes that are partially sheathed so as to expose only 2 mm of the electrode surface to the bottom region of the packed particulate pellet. Also presented is a conduction model that provides a shape factor for estimating effective conductivity. We tested aqueous solutions of carbon black (CB), activated carbon (AC), and mixtures thereof. These particles were dispersed in 0.0 and 0.5 M NaCl solutions. Measurements show that the effective conductivity initially increases linearly with pellet mass and then saturates at higher masses. Notably, CB exhibited a fivefold increase in conductivity than AC at equal pellet masses. CB/AC mixtures at a fixed pellet mass were tested with CB mass fractions of 0 to 100%. Interestingly, the mixture conductivity was found to be a non-monotonic function of CB mass fraction, with a maximum conductivity at about 60 % CB mass fraction. At this maximum, the mixture conductivity is approximately 30 % higher than pure CB. NaCl concentration in the slurry solution had no effects on conductivity. These results highlight the interactions between slurry electrode composition and compaction, offering insights for optimizing slurry electrodes. Furthermore, the system and results may also be applicable to evaluation of particulate materials (including slurries) used for Li-ion batteries, capacitive deionization, fuel cells, and flow electrodes.

Capacitive deionization↗