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NASA NTRS2004

Space Shuttle Upgrades: Long Life Alkaline Fuel Cell

NASA has utilized the alkaline fuel cell technology to provide electrical power for manned launch vehicles such as Gemini, Apollo, and the Space Shuttle. The current Shuttle alkaline fuel cells are procured from UTC Fuel Cells, a United Technologies Company. The alkaline fuel cells are very reliable but the operating life is limited to 2600 hours due to voltage degradation of the individual cells. The main limiting factor in the life of the cells is corrosion of the cell's fiberglass/epoxy frame by the aqueous potassium hydroxide electrolyte. To reduce operating costs, the orbiter program office approved the Long Life Alkaline Fuel Cell (LLAFC) program as a shuttle upgrade in 1999 to increase the operating life of the fuel cell powerplant to 5000 hours. The LLAFC program incorporates improving the cell by extending the length of the corrosion path, which reduces the cell frame corrosion. UTCFC performed analysis to understand the fundamental mechanisms that drive the cell frame corrosion. The analysis indicated that the corrosion path started along the bond line between the cathode and the cell frame. Analysis also showed that the oxygen available at the cathode, the catalyst on the electrode, and the electrode substrate all supported or intensified the corrosion. The new cell design essentially doubled the corrosion path to mitigate the problem. A 10-cell stack was tested for 5000 hours during the development phase of this program to verify improved cell performance. A complete 96-cell stack was then tested for 5000 hours during the full manned-space qualification phase of this program. Additional upgrades to the powerplant under this program are: replacing the aluminum body in the pressure regulator with stainless steel to reduce corrosion, improving stack insulator plate with improved resistance to stress failure and improved temperature capability, and replacing separator plate elastomer seals with a more durable material and improved seal retention.

Kerri McCurdy↗

NASA NTRS2011

Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

Valdez, Thomas I.↗

NASA NTRS2018

Transition Metal Oxides as Cathodes in Li-O2 battery: A First Principles Investigation

Li-O2 batteries have traditionally used carbon based electrodes (graphite, buckypaper) as the cathode of choice due to its good electrical conductivity, stability against non-aqueous electrolytes like Dimethyl ether (DME) and ease of handling. But, the carbon cathode also leads to formation of carbonate by-products that increase overpotentials during charging leading to degradation of cathode and reduction of cyclability. In this work, we investigate some of the well-known oxides as cathodes with focus on the interface between the oxide surfaces and the discharge product: Li2O2, in the Li-O2 battery using first principles computations. Our results show that attention must be paid on choosing the appropriate surface of the oxides. We extend the analysis to suggest other possible oxide chemistries that should be investigated as cathodes in Li-O2 batteries.

Li-O2 battery↗

NASA NTRS1984

Analysis of head-down tilt as an analog of weightlessness using a methematical simulation model

Antiorthostasis or head down tilt of a moderate degree was used as a ground based analog of weightless space flight to study headward fluid shifts, decreased plasma volume, orthostatic intolerance and muscular skeletal degradation. A mathematical model was used to help interpret these observations. The model proved most valuable for these studies was originally developed as a description of the major circulatory, fluid and electrolyte control systems. Two different experimental studies are employed to validate the model. The first is a 24 hour head down tilt study and the second is a 7 day head down bed rest study. The major issues addressed include the reduction in plasma volume, the dynamic changes of venous pressure and cardiac output, the extent of central hypervolemia during long term zero g exposure, the existence of an early diuresis, the mechanisms which alter the renal regulating hormones during the short term and long term periods, the significance of potassium loss on other zero g responses, and the role of transcapillary filtration in adjusting fluid shifts. The use of mathematical models as an interpretive and analysis technique for experimental research for space life science is illustrated.

Leonard, J. I.↗

NASA NTRS2012

Bayesian Framework Approach for Prognostic Studies in Electrolytic Capacitor under Thermal Overstress Conditions

Electrolytic capacitors are used in several applications ranging from power supplies for safety critical avionics equipment to power drivers for electro-mechanical actuator. Past experiences show that capacitors tend to degrade and fail faster when subjected to high electrical or thermal stress conditions during operations. This makes them good candidates for prognostics and health management. Model-based prognostics captures system knowledge in the form of physics-based models of components in order to obtain accurate predictions of end of life based on their current state of heal th and their anticipated future use and operational conditions. The focus of this paper is on deriving first principles degradation models for thermal stress conditions and implementing Bayesian framework for making remaining useful life predictions. Data collected from simultaneous experiments are used to validate the models. Our overall goal is to derive accurate models of capacitor degradation, and use them to remaining useful life in DC-DC converters.

Kulkarni, Chetan S.↗

NASA NTRS1973

Hydrogen depolarized carbon dioxide concentrator performance improvements and cell pair structural tests

The investigations and testing associated with the CO2 removal efficiency and voltage degradation of a hydrogen depolarized carbon oxide concentrator are reported. Also discussed is the vibration testing of a water vapor electrolysis cell pair. Performance testing of various HDC cell pairs with Cs2CO3 electrolyte provided sufficient parametric and endurance data to size a six man space station prototype CO2 removal system as having 36 HDC cell pairs, and to verify a life capability exceeding six moths. Testing also demonstrated that tetramethylammonium carbonate is an acceptable HDC electrolyte for operating over the relative humidity range of 30 to 90 percent and over a temperature range of 50 to 80 F.

Huddleston, J. D.↗

NASA NTRS1993

Electrochemical impedance spectroscopy of lithium-titanium disulfide rechargeable cells

The two-terminal alternating current impedance of Li/TiS2 rechargeable cells was studied as a function of frequency, state-of-charge, and extended cycling. Analysis based on a plausible equivalent circuit model for the Li/TiS2 cell leads to evaluation of kinetic parameters for the various physicochemical processes occurring at the electrode/electrolyte interfaces. To investigate the causes of cell degradation during extended cycling, the parameters evaluated for cells cycled 5 times were compared with the parameters of cells cycled over 600 times. The findings are that the combined ohmic resistance of the electrolyte and electrodes suffers a tenfold increase after extended cycling, while the charge-transfer resistance and diffusional impedance at the TiS2/electrolyte interface are not significantIy affected. The results reflect the morphological change and increase in area of the anode due to cycling. The study also shows that overdischarge of a cathode-limited cell causes a decrease in the diffusion coefficient of the lithium ion in the cathode.

Narayanan, S. R.↗

NASA NTRS2011

Nutrition Research: Basis for Station Requirements

Prior to the Shuttle program, all understanding of nutritional needs in space came from Skylab metabolic research. Because Shuttle flights were short, most less than 14 days, research focused on major nutritional issues: energy (calories), protein and amino acids, water and electrotypes, with some more general physiology studies that related to iron and calcium. Using stable isotope tracer studies and diet intake records, we found that astronauts typically did not consume adequate calories to meet energy expenditure. To monitor energy and nutrient intake status and provide feedback to the flight surgeon and the astronauts, the International Space Station (ISS) program implemented a weekly food frequency questionnaire and routine body mass measurements. Other Shuttle investigations found that protein turnover was higher during flight, suggesting there was increased protein degradation and probably concurrent increase in protein synthesis, and this occurred even in cases of adequate protein and caloric intake. These results may partially explain some of the loss of leg muscle mass. Fluid and electrolyte flight studies demonstrated that water intake, like energy intake, was lower than required. However, sodium intakes were elevated during flight and likely related to other concerns such as calcium turnover and other health-related issues. NASA is making efforts to have tasty foods with much lower salt levels to reduce sodium intake and to promote fluid intake on orbit. Red blood cell studies conducted on the Shuttle found decreased erythrogenesis and increased serum ferritin levels. Given that the diet is high in iron there may be iron storage health concerns, especially related to the role of iron in oxidative damage, complicated by the stress and radiation. The Shuttle nutrition research lead to new monitoring and research on ISS. These data will be valuable for future NASA and commercial crewed missions.

Lane, Helen W.↗

NASA NTRS1984

Design, development, performance, and reconditioning of Ni-Cd batteries using polyropylene separators

A performance assessment is made for the Viking Mars Lander Program's sealed, sterilizable, 8-ampere hour Ni-Cd batteries, which use a nonwoven polypropylene separator material. Attention is given to separator wettability, the optimization of electrolyte quantity, and the reduction of plate carbonate, in view of thermal considerations and other environmental design and test requirements generated by mission characteristics. Life data based on mission experience identify, in addition to performance and degradation behavior, a series of shallow discharge reconditioning cycles and an intensive program of deep discharge reconditioning.

Britting, A. O., Jr.↗

NASA NTRS2010

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600 C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Shchetkovskiy, Anatoliy↗

NASA NTRS2010

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Shchetkovskiy, Anatoliy↗

NASA NTRS1992

Citraturic response to oral citric acid load

It is possible that some orally administered citrate may appear in urine by escaping oxidation in vivo. To determine whether this mechanism contributes to the citraturic response to potassium citrate, we measured serum and urinary citrate for 4 hours after a single oral load of citric acid (40 mEq.) in 6 normal subjects. Since citric acid does not alter acid-base balance, the effect of absorbed citrate could be isolated from that of alkali load. Serum citrate concentration increased significantly (p less than 0.05) 30 minutes after a single oral dose of citric acid and remained significantly elevated for 3 hours after citric acid load. Commensurate with this change, urinary citrate excretion peaked at 2 hours and gradually decreased during the next 2 hours after citric acid load. In contrast, serum and urinary citrate remained unaltered following the control load (no drug). Differences of the citratemic and citraturic effects between phases were significant (p less than 0.05) at 2 and 3 hours. Urinary pH, carbon dioxide pressure, bicarbonate, total carbon dioxide and ammonium did not change at any time after citric acid load, and did not differ between the 2 phases. No significant difference was noted in serum electrolytes, arterialized venous pH and carbon dioxide pressure at any time after citric acid load and between the 2 phases. Thus, the citraturic and citratemic effects of oral citric acid are largely accountable by provision of absorbed citrate, which has escaped in vivo degradation.

Non-NASA Center↗

NASA NTRS1992

Capacity retention in hydrogen storage alloys

Results of our examination of the properties of several candidate materials for hydrogen storage electrodes and their relation to the decrease in H-storage capacity upon open-circuit storage over time are reported. In some of the alloy samples examined to date, only about 10 percent of the hydrogen capacity was lost upon storage for 20 days, while in others, this number was as high as 30 percent for the same period of time. This loss in capacity is attributed to two separate mechanisms: (1) hydrogen desorbed from the electrode due to pressure differences between the cell and the electrode sample; and (2) chemical and/or electrochemical degradation of the alloy electrode upon exposure to the cell environment. The former process is a direct consequence of the equilibrium dissociation pressure of the hydride alloy phase and the partial pressure of hydrogen in the hydride phase in equilibrium with that in the electrolyte environment, while the latter is related to the stability of the alloy phase in the cell environment. Comparison of the equilibrium gas-phase dissociation pressures of these alloys indicate that reversible loss of hydrogen capacity is higher in alloys with P(eqm) greater than 1 atm than in those with P(eqm) less than 1 atm.

Anani, A.↗

NASA NTRS1998

Lifetime Modeling of Tin Electrodes for AMTEC Cells

In order to model the lifetime of the electrochemical cell in an Alkali Metal Thermal to Electric Converter (AMTEC), studies of TiN Electrodes on Beta-alumina solid electrolytes (BASE) have been made to determine the performace parameters over time. The first of a series of experiments in which TiN electrodes are studied in a Vapor Exposure Test Cell is described here, with preliminary results from electrochemical measurements made on the cell. The TiN electrodes tested here perform well, with minimal degradation over 1000 hours of operation at 850 degree C.

Electrochemical↗

NASA NTRS1990

Space Electrochemical Research and Technology Conference, 2nd, Cleveland, OH, Apr. 11-13, 1989, Proceedings

Attention is given to topics of advanced concepts, hydrogen-oxygen fuel cells and electrolyzers, nickel electrodes, and advanced rechargeable batteries. Papers are presented on human exploration mission studies, advanced rechargeable sodium batteries with novel cathodes, advanced double-layer capacitors, recent advances in solid-polymer electrolyte fuel cell technology with low platinum loading electrodes, electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications, and the corrosion testing of candidates for the alkaline fuel cell cathode. Other papers are on a structural comparison of nickel electodes and precursor phases, the application of electrochemical impedance spectroscopy for characterizing the degradation of Ni(OH)2/NiOOH electrodes, advances in lightweight nickel electrode technology, multimission nickel-hydrogen battery cell for the 1990s, a sodium-sulfur battery flight experiment definition study, and advances in ambient-temperature secondary lithium cells.

O'Donnell, Patricia M.↗

NASA NTRS2000

Storage Characteristics of Lithium Ion Cells

Lithium ion cells are being developed under the NASA/Air Force Consortium for the upcoming aerospace missions. First among these missions are the Mars 2001 Lander and Mars 2003 Lander and Rover missions. Apart from the usual needs of high specific energy, energy density and long cycle life, a critical performance characteristic for the Mars missions is low temperature performance. The batteries need to perform well at -20 C, with at least 70% of the rated capacity realizable at moderate discharge rates (C/5). Several modifications have been made to the lithium ion chemistry, mainly with respect to the electrolyte, both at JPL' and elsewhere to achieve this. Another key requirement for the battery is its storageability during pre-cruise and cruise periods. For the Mars programs, the cruise period is relatively short, about 12 months, compared to the Outer Planets missions (3-8 years). Yet, the initial results of our storage studies reveal that the cells do sustain noticeable permanent degradation under certain storage conditions, typically of 10% over two months duration at ambient temperatures, attributed to impedance buildup. The build up of the cell impedance or the decay in the cell capacity is affected by various storage parameters, i.e., storage temperature, storage duration, storage mode (open circuit, on buss or cycling at low rates) and state of charge. Our preliminary studies indicate that low storage temperatures and states of charge are preferable. In some cases, we have observed permanent capacity losses of approx. 10% over eight-week storage at 40 C, compared to approx. 0-2% at O C. Also, we are attempting to determine the impact of cell chemistry and design upon the storageability of Li ion cells.

Ratnakumar, B. V.↗

NASA NTRS2004

Increasing the Thermal Stability of Aluminum Titanate for Solid Oxide Fuel Cell Anodes

Solid-oxide fuel cells (SOFCs) show great potential as a power source for future space exploration missions. Because SOFCs operate at temperatures significantly higher than other types of fuel cells, they can reach overall efficiencies of up to 60% and are able to utilize fossil fuels. The SOFC team at GRC is leading NASA's effort to develop a solid oxide fuel cell with a power density high enough to be used for aeronautics and space applications, which is approximately ten times higher than ground transport targets. layers must be able to operate as a single unit at temperatures upwards of 900'C for at least 40,000 hours with less than ten percent degradation. One key challenge to meeting this goal arises from the thermal expansion mismatch between different layers. The amount a material expands upon heating is expressed by its coefficient of thermal expansion (CTE). If the CTEs of adjacent layers are substantially different, thermal stresses will arise during the cell's fabrication and operation. These stresses, accompanied by thermal cycling, can fracture and destroy the cell. While this is not an issue at the electrolyte-cathode interface, it is a major concern at the electrolyte-anode interface, especially in high power anode-supported systems. electrolyte are nearly identical. Conventionally, this has been accomplished by varying the composition of the anode to match the CTE of the yittria-stabilized zirconia (YSZ) electrolyte (approx.10.8x10(exp -6/degC). A Ni/YSZ composite is typically used as a base material for the anode due to its excellent electrochemical properties, but its CTE is about 13.4x10(exp -6/degC). One potential way to lower the CTE of this anode is to add a small percentage of polycrystalline Al2TiO5, with a CTE of 0.68x10(exp -6/degC, to the Ni/YSZ base. However, Al2TiO5 is thermally unstable and loses its effectiveness as it decomposes to Al2O3 and TiO2 between 750 C and 1280 C. be used as additives to increase the thermal stability of Al2TiO5 in SOFC operating conditions without adversely affecting the electrochemical properties of the SOFC anode. Three candidate materials were chosen through an extensive literature review: MgO, Fe2O3, and ZrTiO4. Although all three have been shown to prevent Al2TiO5 decomposition under various conditions, their effectiveness in the temperature range and atmosphere of the SOFC has not yet been evaluated. Several batches of Al2TiO5 with varying amounts of additives were prepared, exposed to reducing and oxidizing atmospheres at elevated temperatures, and the resulting decomposition of Al2TiO5 was measured. The most promising additives were further evaluated with the goal of ultimately preparing low CTE anodes that are chemically compatible to current systems. Adding minor constituents to stabilize Al2TiO5 could ultimately preserve its low CTE for the life of the fuel cell and improve the cell's long-term performance without a drop in anode conductivity. Further, these low CTE filler additions could allow the use of new sulfur tolerant anode materials, improving the viability of SOFCs for future aeronautics and space applications. Every SOFC consists of a cathode and an anode separated by an electrolyte, These three One way to avoid this problem is to design the cell such that the CTEs of the anode and The objective of this summer research project was to evaluate several materials that could

Bender, Jeffrey B.↗

NASA NTRS2018

A Fast Monte Carlo Method for Model-Based Prognostics Based on Stochastic Calculus

This work proposes a fast Monte Carlo method to solve differential equations utilized in model-based prognostics. The methodology is derived from the theory of stochastic calculus, and the goal of such a method is to speed up the estimation of the probability density functions describing the independent variable evolution over time. In the prognostic scenarios presented in this paper, the stochastic differential equations describe variables directly or indirectly related to the degradation of a monitored system. The method allows the estimation of the probability density functions by solving the deterministic equation and approximating the stochastic integrals using samples of the model noise. By so doing, the prognostic problem is solved without the Monte Carlo simulation based on Euler's forward method, which is typically the most time consuming task of the prediction stage. Three different prognostic scenarios are presented as proof of concept: (i) life prediction of electrolytic capacitors, (ii) remaining time to discharge of Lithium-ion batteries, and (iii) prognostic of cracked structures under fatigue loading. The paper shows how the method produces probability density functions that are statistically indistinguishable from the distributions estimated with Euler's forward Monte Carlo simulation. However, the proposed solution is orders of magnitude faster when computing the time-to-failure distribution of the monitored system. The approach may enable complex real-time prognostics and health management solutions with limited computing power.

Corbetta, M.↗