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Carbon-free high-performance cathode for solid-state Li-O 2 battery
The development of a cathode for solid-state lithium-oxygen batteries has been hindered in practice by a low capacity and limited cycle life despite their potential for high energy density. Here, a previously unexplored strategy is proposed wherein the cathode delivers a specific capacity of 200 milliampere hour per gram over 665 discharge/charge cycles, while existing cathodes achieve only ~50 milliampere hour per gram and ~100 cycles. A highly conductive ruthenium-based composite is designed as a carbon-free cathode by first-principles calculations to avoid the degradation associated with carbonaceous materials, implying an improvement in stability during the electrochemical cycling. In addition, water vapor is added into the main oxygen gas as an additive to change the discharge product from growth-restricted lithium peroxide to easily grown lithium hydroxide, resulting in a notable increase in capacity. Thus, the proposed strategy is effective for developing reversible solid-state lithium-oxygen batteries with high energy density.
Carbon dioxide and water vapor production at rest and during exercise. A report on data collection for the Crew and Thermal Systems Division
The current environmental control device in the shuttle uses lithium hydroxide (LiOH) filter canisters to remove carbon dioxide (CO2) from the cabin air, requiring several bulky filter canisters that can only be used once and must be changed frequently. To alleviate a stowage problem and decrease launch weight, the Crew and Thermal Systems Division (CTSD) at the NASA Johnson Space Center has been researching a system to be used on future shuttle missions. This system uses two beds of solid amine material to absorb CO2 and water, later desorbing them to space vacuum. In this way the air scrubbing medium is regenerable and reusable. To identify the efficacy of this regenerable CO2 removal system (RCRS), CTSD began investigations in the shuttle mockup. The purpose of this investigation was to support the CTSD program by determining mean levels of carbon dioxide and water vapor production in normal, healthy males and females age-matched with the astronaut corps. Subjects' responses were measured at rest and during exercise at intensity levels equivalent to normal shuttle operation activities. The results were used to assess the adjustments made to RCRS and are reported as a reference for future investigations in shuttle environmental control.
Director's Discretionary Fund Report for Fiscal Year 1996
Topics covered include: Waterproofing the Space Shuttle tiles, thermal protection system for Reusable Launch Vehicles, computer modeling of the thermal conductivity of cometary ice, effects of ozone depletion and ultraviolet radiation on plants, a novel telemetric biosensor to monitor blood pH on-line, ion mobility in polymer electrolytes for lithium-polymer batteries, a microwave-pumped far infrared photoconductor, and a new method for measuring cloud liquid vapor using near infrared remote sensing. Also included: laser-spectroscopic instrument for turbulence measurement, remote sensing of aircraft contrails using a field portable imaging interferometer, development of a silicon-micromachined gas chromatography system for determination of planetary surface composition, planar Doppler velocimetry, chaos in interstellar chemistry, and a limited pressure cycle engine for high-speed output.
T-111 Rankine system corrosion test loop, volume 1
Results are given of a program whose objective was to determine the performance of refractory metal alloys in a two loop Rankine test system. The test system consisted of a circulating lithium circuit heated to 1230 C maximum transferring heat to a boiling potassium circuit with a 1170 C superheated vapor temperature. The results demonstrate the suitability of the selected refractory alloys to perform from a chemical compatibility standpoint.
A regenerable CO2 and humidity control system for Shuttle
A regenerable CO2 and humidity control system is presently being developed for potential use on Shuttle as an alternate to the baseline Lithium Hydroxide (LiOH) system. The system utilizes a sorbent material (designated 'HS-C') to adsorb CO2 and water vapor from the cabin atmosphere and desorb the CO2 and water vapor overboard when exposed to a space vacuum. Past development programs concentrated on material development and breadboard system fabrication and testing. The present program calls for the design of a flight prototype system capable of integration into the Shuttle vehicle and the development of major components. This paper will show that a regenerable system utilizing HS-C material trades even with the shuttle LiOH system for the baseline four-man, seven-day mission and offers increased savings up to 448 kg for a seven-man, 30-day mission.
The development and testing of a regenerable CO2 and humidity control system for Shuttle
A regenerable CO2 and humidity control system is presently being developed for potential use on Shuttle as an alternate to the baseline lithium hydroxide (LiOH) system. The system utilizes a sorbent material (designated 'HS-C') to adsorb CO2 and water vapor from the cabin atmosphere and desorb the CO2 and water vapor overboard when exposed to a space vacuum. Continuous operation is achieved by utilizing two beds which are alternately cycled between adsorption and desorption. This paper presents the significant hardware development and test accomplishments of the past year. A half-size breadboard system utilizing a flight configuration canister was successfully performance tested in simulated Shuttle missions. A vacuum desorption test provided considerable insight into the desorption phenomena and allowed a significant reduction of the Shuttle vacuum duct size. The fabrication and testing of a flight prototype canister and flight prototype vacuum valves have proven the feasibility of these full-size, flight-weight components.
Composition-Nanoarchitecture-Performance Analysis of High Energy Density Electrodeposited Silicon for Lithium-Ion Battery Anodes
Electrodeposition of silicon (Si) was previously demonstrated as a promising method for fabricating 3D-structured lithium-ion battery anodes. However, the relationship between the electrochemical performance and chemical composition of the relatively impure electrodeposited silicon is not well understood. Here, we report the electrodeposition of a Si-dominant active material (EDEP-Si) onto 3D-structured nickel (Ni) scaffolds and systematically compare the electrochemical properties, elemental composition, atomistic Si coordination, and molecular structure of EDEP-Si with high-purity amorphous Si grown via static chemical vapor deposition. Despite the considerable amount of carbon (9–11 at %) and oxygen (42–44 at %) present in EDEP-Si, the cycling stability and high reversible specific capacity are remarkably similar to those of CVD-Si on a silicon basis (~2400 mA h/g-Si after 100 cycles). The primary difference is that EDEP-Si exhibits reduced cycling efficiency over the first 10–20 cycles. Reactions between carbon and, more importantly, oxygen in EDEP-Si with lithium are likely responsible for the reduced early cycle performance and lower capacity of the total deposit. Finally, our observations suggest ultrapure Si is not necessary for high electrochemical access to reversible charge storage, although limiting the presence of incorporated impurity species would improve energy density and first cycle efficiency.
Stable Anode–Free All–Solid–State Lithium Battery through Tuned Metal Wetting on the Copper Current Collector
A stable anode-free all-solid-state battery (AF-ASSB) with sulfide-based solid-electrolyte (SE) (argyrodite Li 6 PS 5 Cl) is achieved by tuning wetting of lithium metal on “empty” copper current-collector. Lithiophilic 1 µm Li 2 Te is synthesized by exposing the collector to tellurium vapor, followed by in situ Li activation during the first charge. The Li 2 Te significantly reduces the electrodeposition/electrodissolution overpotentials and improves Coulombic efficiency (CE). During continuous electrodeposition experiments using half-cells (1 mA cm –2 ), the accumulated thickness of electrodeposited Li on Li 2 Te–Cu is more than 70 µm, which is the thickness of the Li foil counter-electrode. Full AF-ASSB with NMC811 cathode delivers an initial CE of 83% at 0.2C, with a cycling CE above 99%. Additionally, cryogenic focused ion beam (Cryo-FIB) sectioning demonstrates uniform electrodeposited metal microstructure, with no signs of voids or dendrites at the collector-SE interface. Electrodissolution is uniform and complete, with Li 2 Te remaining structurally stable and adherent. By contrast, an unmodified Cu current-collector promotes inhomogeneous Li electrodeposition/electrodissolution, electrochemically inactive “dead metal,” dendrites that extend into SE, and thick non-uniform solid electrolyte interphase (SEI) interspersed with pores. Density functional theory (DFT) and mesoscale calculations provide complementary insight regarding nucleation-growth behavior. Unlike conventional liquid-electrolyte metal batteries, the role of current collector/support lithiophilicity has not been explored for emerging AF-ASSBs.
Liquid metal walls
Here, the plasma performance of fusion devices depends strongly on the chosen wall materials. Solid plasma-facing components (PFCs) are predominantly used in present devices, and are the most investigated candidates for fusion designs. High-Z materials such as tungsten (W) are the leading solid PFC material candidates. To date, a material choice that scales to steady-state reactor conditions has not been identified. Moreover, if plasma transient events such as edge-localized modes and disruptions cannot be altogether avoided or sufficiently mitigated, the projected peak heat and particle loads far exceed the power exhaust capabilities of solids. Liquid metal (LM) PFCs represent an intrinsic self-healing boundary that are both resilient to surface damage from transients, and that could handle high steady-state heat and particle fluxes. Flowing LM PFCs can be designed to remove “slag,” the buildup of material erosion due to plasma-material interactions, including charge exchange sputtering in the main chamber. Further, LM offer the prospect to manage hydrogenic species otherwise retained in the PFCs, which is important from a safety and inventory standpoint. The two most promising LMs are lithium (Li) and tin (Sn), although Sn–Li eutectics may be considered. While Sn offers a higher temperature window with low vapor pressure and low hydrogen retention, Li offers the prospect of enhanced energy confinement and higher acceptable core contamination limits, and this section focuses on Li PFCs. An LM PFC development research program developed LM PFC concepts for a nuclear fusion device via engineering design calculations, single-effect experiments, and staged prototypical experiments. A self-consistent design window was identified with liquid Li flow speeds ~5–10 m/s; plasma contamination was negligible for predicted Li evolution rates. While these preconceptual designs hold promise, there is substantial R&D needed to advance the technical readiness levels of LM PFCs for application to fusion power plants.
Liquid lithium wetting and percolation in a porous tungsten/liquid Li plasma facing component (PFC)
This work explores the concept of a hybrid material system designed to protect the plasma from high-Z material emission while also protecting an underlying high-Z wall material from erosion by integrating a low-Z component in the liquid phase. Plasma-surface interaction properties of a porous tungsten (W)-liquid metal hybrid system, having the favorable bulk thermomechanical properties of W while serving as a scaffold for a liquid metal with self-healing and radiative vapor shielding characteristics, are examined. W-substrates with 70% density of bulk W and 1–5 μm sized pores have been fabricated with 50-nm W powders using spark plasma sintering. Enhanced lithium (Li) wettability, driven by percolation through the porous W architecture, is demonstrated with in-situ liquid Li drop measurements. Finally, results show complete wetting of liquid Li at 250 °C in the porous W, 100 °C lower temperature than what has been observed on traditional W surfaces. In operando ion beam analysis of Li films deposited on porous W substrates provides microscopic evidence of Li percolation into the substrate and a first look at D retention up to a depth of 100 nm after plasma exposure at a flux of 10 20 m –2 s –1 , 250 eV/amu D + plasma to a fluence of 1.16 × 10 23 m –2 at a temperature of 200 °C.
Breadboard CO2 and humidity control system
A regenerable CO2 and humidity control system is being developed for potential use on shuttle as an alternate to the baseline lithium hydroxide (LiOH)/condensing heat exchanger system. The system utilizes a sorbent material, designated HS-C, to adsorb CO2 and water vapor from the cabin atmosphere. The material is regenerated by exposing it to space vacuum. A half-size breadboard system, utilizing a flight representative HS-C canister, was designed, built, and performance tested to shuttle requirements for total CO2 and total humidity removal. The use of a new chemical matrix material allowed significant optimization of the system design by packing the HS-C chemical into the core of a heat exchanger which is manifolded to form two separate and distinct beds. Breadboard system performance was proven by parametric testing and simulated mission testing over the full range of shuttle crew sizes and metabolic loadings. Vacuum desorption testing demonstrated considerable savings in previously projected shuttle vacuum duct sizing.
Spacesuit Evaporator-Absorber-Radiator (SEAR)
For decades advanced spacesuit developers have pursued a regenerable, robust nonventing system for heat rejection. Toward this end, this paper investigates linking together two previously developed technologies, namely NASA s Spacesuit Water Membrane Evaporator (SWME), and Creare s Lithium Chloride Absorber Radiator (LCAR). Heat from a liquid cooled garment is transported to SWME that provides cooling through evaporation. This water vapor is then captured by solid LiCl in the LCAR with a high enthalpy of absorption, resulting in sufficient temperature lift to reject heat to space by radiation. After the sortie, the LCAR would be heated up and dried in a regenerator to drive off and recover the absorbed evaporant. A engineering development prototype was built and tested in vacuum conditions at a sink temperature of 250 K. The LCAR was able to stably reject 75 W over a 7-hour period. A conceptual design of a full-scale radiator is proposed. Excess heat rejection above 240 W would be accomplished through venting of the evaporant. Loop closure rates were predicted for various exploration environment scenarios.
Liquid lithium divertor analysis using coupled plasma material interaction model
A liquid lithium divertor can improve performance of future fusion devices by creating efficient power exhaust and improving the energy confinement via pumping of the hydrogen isotopes. In addition, significantly higher heat fluxes can be handled if controlled vapor shielding is used to redistribute the divertor heat flux over a wider area. Design and optimization of such a system calls for an analysis model which includes a strong two-way coupling between the plasma and divertor material. The incoming plasma heat and particle flux will affect the divertor surface temperature, which is a defining factor of the lithium evaporative and sputtered flux going into the plasma. Results of the coupled model based on the plasma edge code SOLPS-ITER and the computational fluid dynamics (CFD) code ANSYS-CFX will be presented for different configurations. An analytical slab flow model is used as a heat transfer boundary condition for SOLPS, defining particle flux from the wall via calculation of the surface temperature. At the final step, results of the SOLPS analysis are verified using a 3D CFD magnetohydrodynamics (MHD) analysis which uses heat and particle flux from SOLPS as a boundary condition. In addition to plasma heat flux, both analytical and CFD temperature models include several plasma material interaction effects, such as lithium evaporation, condensation and sputtering based on deuterium target flux. New adatom sputtering model based on the available experimental data is presented. Analytical model is expanded to include free surface axisymmetric configurations. Results of parametric studies of the divertor configurations with different lithium inlet temperature and velocity will be presented leading to the optimal design resulting in the lowest possible lithium contamination in the core.
Formation of lithium-metal-carbon protecting layer and removal of lithium carbonate on lithium metal
A process for forming a lithium-metal-carbon film on a lithium metal structure. A metal-ligand complex is exposed to the metal ligand, such as for 5-30 seconds in a chemical vapor transfer reactor at a temperature of 100-180° C.
Design and Analysis of Liquid Lithium Plasma Facing Components
In this study, liquid metal (LM) on plasma-facing components (PFCs) creates a renewable protective cover enhancing power exhaust and protecting the solid substrate. Additionally, energy confinement improvement through particle pumping can be achieved in the case of liquid lithium (LL). A new variant of PFCs was recently introduced at Princeton Plasma Physics Laboratory (PPPL) where a porous wall is used to stabilize the LM surface, while using magnetohydrodynamic (MHD) drive to push the LM flow inside the component. This arrangement allows efficient heat exhaust, and enhanced control of the LM surface temperature, leading to spatial control of evaporation and condensation of LL on the plasma interface. This feature is particularly attractive when vapor shielding is introduced to allow heat flux redistribution. This system has the advantage that as the heat flux increases, the evaporation rate will increase, while decreasing heat flux will decrease the evaporation rate of lithium, ideally creating a feedback effect which could self-regulate the amount of lithium evaporated. Analytical and numerical models for LL PFCs were developed in PPPL. To calculate the target temperature distribution for the case of evaporation from the divertor, we apply an iterative process allowing two-way coupling between the fluid-kinetic analysis of plasma using SOLPS-ITER code and the flow and heat transfer analysis of the PFC using an analytical model. In the last stage, the results are validated using computational fluid dynamics (CFD) analysis with customized version of the CFX code from ANSYS. CFX was modified at PPPL to allow MHD analysis at the high magnetic field typical for fusion applications. Results of the analysis for NSTX-U tokamak conditions will be presented.
Heat-pipe transient model for space applications
A two-dimensional model is developed for simulating heat pipes transient performance following changes in the input/rejection power or in the evaporator/condenser temperatures. The model employs the complete form of governing equations and momentum and energy jump conditions at the liquid-vapor interface. Although the model is capable of handling both cylindrical and rectangular geometries, the results reported are for a circular heat pipe with liquid lithium as the working fluid. The model incorporates a variety of other working fluids, such as water, ammonia, potassium, sodium and mercury, and offers combinations of isothermal, isoflux, convective and radiative heating/cooling conditions in the evaporator and condenser regions of the heat pipe. Results presented are for lithium heat pipes with exponential heating of the evaporator and isothermal cooling of the condenser.
NASA Tech Briefs, June 2006
Topics covered include: Magnetic-Field-Response Measurement-Acquisition System; Platform for Testing Robotic Vehicles on Simulated Terrain; Interferometer for Low-Uncertainty Vector Metrology; Rayleigh Scattering for Measuring Flow in a Nozzle Testing Facility; "Virtual Feel" Capaciflectors; FETs Based on Doped Polyaniline/Polyethylene Oxide Fibers; Miniature Housings for Electronics With Standard Interfaces; Integrated Modeling Environment; Modified Recursive Hierarchical Segmentation of Data; Sizing Structures and Predicting Weight of a Spacecraft; Stress Testing of Data-Communication Networks; Framework for Flexible Security in Group Communications; Software for Collaborative Use of Large Interactive Displays; Microsphere Insulation Panels; Single-Wall Carbon Nanotube Anodes for Lithium Cells; Tantalum-Based Ceramics for Refractory Composites; Integral Flexure Mounts for Metal Mirrors for Cryogenic Use; Templates for Fabricating Nanowire/Nanoconduit- Based Devices; Measuring Vapors To Monitor the State of Cure of a Resin; Partial-Vacuum-Gasketed Electrochemical Corrosion Cell; Theodolite Ring Lights; Integrating Terrain Maps Into a Reactive Navigation Strategy; Reducing Centroid Error Through Model-Based Noise Reduction; Adaptive Modeling Language and Its Derivatives; Stable Satellite Orbits for Global Coverage of the Moon; and Low-Cost Propellant Launch From a Tethered Balloon