Development of a CO2-H2O solid oxide electrolyte electrolysis system Annual report
Development of aerospace life support system for oxygen production from carbon dioxide
Smart, W. H.↗
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Solid polymer electrolyte water electrolysis system development
Solid polymer electrolyte technology used in a water electrolysis system (WES) to generate oxygen and hydrogen for manned space station applications was investigated. A four-man rated, low pressure breadboard water electrolysis system with the necessary instrumentation and controls was fabricated and tested. A six man rated, high pressure, high temperature, advanced preprototype WES was developed. This configuration included the design and development of an advanced water electrolysis module, capable of operation at 400 psig and 200 F, and a dynamic phase separator/pump in place of a passive phase separator design. Evaluation of this system demonstrated the goal of safe, unattended automated operation at high pressure and high temperature with an accumulated gas generation time of over 1000 hours.
Source record↗
Development of Advanced Lithium-Ion Rechargeable Cells with Improve Low Temperature Performance
Due to future plans to explore Mars and the outer planets, NASA has interest in developing lithium-ion rechargeable batteries that are capable of operating at low temperatures. To address these problems, we have initiated reserach focused upon the development of advanced electrolyte systems for lithium-ion cells with improved low temperature performance.
Lithium↗
Organic solvents, electrolytes, and lithium ion cells with good low temperature performance
Multi-component organic solvent systems, electrolytes and electrochemical cells characterized by good low temperature performance are provided. In one embodiment, an improved organic solvent system contains a ternary mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate. In other embodiments, quaternary systems include a fourth component, i.e, an aliphatic ester, an asymmetric alkyl carbonate or a compound of the formula LiOX, where X is R, COOR, or COR, where R is alkyl or fluoroalkyl. Electrolytes based on such organic solvent systems are also provided and contain therein a lithium salt of high ionic mobility, such as LiPF.sub.6. Reversible electrochemical cells, particularly lithium ion cells, are constructed with the improved electrolytes, and preferably include a carbonaceous anode, an insertion type cathode, and an electrolyte interspersed therebetween.
Smart, Marshall C.↗
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.↗
Fuel cell and system for supplying electrolyte thereto with wick feed
An electrolyte distribution and supply system for use with a fuel cell having a means for drawing electrolyte therein is formed by a set of containers of electrolyte joined to respective fuel cells in a stack of such cells. The electrolyte is separately stored so as to provide for electrical isolation between electrolytes of the individual cells of the stack. Individual storage compartments are coupled by tubes containing wicking fibers, the ends of the respective tubes terminating on the means for drawing electrolyte in each of the respective fuel cells. Each tube is heat shrunk to tightly bind the fibers therein.
Cohn, J. Gunther↗
Development of Electrolytic Oxygen Recovery System for Advanced Life Support
The oxygen (O2) recovery system for the International Space Station (ISS) can recover approximately 50 percent of O2 from metabolic carbon dioxide (CO2). Increasing the O2 recovery rate and closing the open loop for future long duration crewed missions in space beyond Low Earth Orbit (LEO) is essential. There are several developmental efforts underway to increase the recovery rate. However, most of these technologies result in a complex, heavy, and power consuming system. The desired exploration O2 recovery system would be reliable and efficient with maximum O2 recovery. Marshall Space Flight Center (MSFC) is currently investigating an electrolytic O2 recovery approach that will increase the O2 recovery to greater than 70 percent as well as lowering the complexity, mass, and power consumption than most other technologies currently under development. The electrolytic O2 recovery system consists of a Microfluidic Electrochemical Reactor (MFECR) that is based on the electrochemical reduction of CO2 to O2 and ethylene (C2H4) using water (H2O) as precursor and operates at standard condition with a theoretical recovery rate of 73 percent. In 2016, NASA’s Game Changing Development Program awarded the University of Texas Arlington (UTA) a grant to initiate the development of the MFECR. Since 2019, MSFC and UTA have been collaborating with the current goals of increasing the O2 recovery efficiency, advancing the technology readiness to a Technology Readiness Level (TRL) 4, and maturing the system to process CO2 of one crew-member. Based on the results from UTA’s initial efforts, the following were identified as key areas of improvement in order to maximize O2 recovery for the system: further development of the anode material and cathode catalyst, model-based cell design optimization, and the addition of a separation system and fuel cell. This paper will present the current developmental efforts of the electrolytic system including MFECR design and overall system enhancements as well as results from single cell stack testing.
Brittany R Brown↗
Supercapacitor Electrolyte Solvents with Liquid Range Below -80 C
A previous NASA Tech Brief ["Low-Temperature Supercapacitors" (NPO-44386) NASA Tech Briefs, Vol. 32, No 7 (July 2008), page 32] detailed ongoing efforts to develop non-aqueous supercapacitor electrolytes capable of supporting operation at temperatures below commercially available cells (which are typically limited to charging and discharging at > or equal to -40 C). These electrolyte systems may enable energy storage and power delivery for systems operating in extreme environments, such as those encountered in the Polar regions on Earth or in the exploration of space. Supercapacitors using these electrolytes may also offer improved power delivery performance at moderately low temperatures (e.g. -40 to 0 C) relative to currently available cells, offering improved cold-cranking and cold-weather acceleration capabilities for electrical or hybrid vehicles. Supercapacitors store charge at the electrochemical double-layer, formed at the interface between a high surface area electrode material and a liquid electrolyte. The current approach to extending the low-temperature limit of the electrolyte focuses on using binary solvent systems comprising a high-dielectric-constant component (such as acetonitrile) in conjunction with a low-melting-point co-solvent (such as organic formates, esters, and ethers) to depress the freezing point of the system, while maintaining sufficient solubility of the salt. Recent efforts in this area have led to the identification of an electrolyte solvent formulation with a freezing point of -85.7 C, which is achieved by using a 1:1 by volume ratio of acetonitrile to 1,3-dioxolane
Brandon, Erik↗
A Survey of Alternative Oxygen Production Technologies
Utilization of the Martian atmosphere for the production of fuel and oxygen has been extensively studied. The baseline fuel production process is a Sabatier reactor, which produces methane and water from carbon dioxide and hydrogen. The oxygen produced from the electrolysis of the water is only half of that needed for methane-based rocket propellant, and additional oxygen is needed for breathing air, fuel cells and other energy sources. Zirconia electrolysis cells for the direct reduction of CO2 arc being developed as an alternative means of producing oxygen, but present many challenges for a large-scale oxygen production system. The very high operating temperatures and fragile nature of the cells coupled with fairly high operating voltages leave room for improvement. This paper will survey alternative oxygen production technologies, present data on operating characteristics, materials of construction, and some preliminary laboratory results on attempts to implement each. Our goal is to significantly improve upon the characteristics of proposed zirconia cells for oxygen production. To achieve that goal we are looking at electrolytic systems that operate at significantly lower temperatures, preferably below 31C to allow the incorporation of liquid CO2 in the electrolyte. Our preliminary results indicate that such a system will have much higher current densities and have simpler cathode construction than a porous gas feed electrode system. Such a system could be achieved based on nonaqueous electrolytes or ionic liquids. We are focusing our research on the anode reaction that will produce oxygen from a product generated at the cathode using CO2 as the feed. Operation at low temperatures also will open up the full range of polymer and metal materials, allowing a more robust system design to withstand the rigors of flight, landing, and long term unattended operation on the surface of Mars.
Lueck, Dale E.↗
Development of High Conductivity Lithium-Ion Electrolytes for Low Temperature Cell Applications
NASA has continued interest in developing power sources which are capable of operating at low temperatures (-20 C and below) to enable future missions, such as the Mars Rover and Lander. Thus, under a program sponsored by the Mars Exploration Program, we have been involved in developing Li-ion batteries with improved low temperature performance. To accomplish this task, the focus of the research has been upon the development of advanced electrolyte systems with improved low temperature properties. This had led to the identification of a carbonate-based electrolyte, consisting of 1.0 M LiPF6 in EC + DEC + DMC (33:33:34), which has been shown to have excellent performance at -20 C in Li-ion AA-size prototype cells. Other groups are also actively engaged in developing electrolytes which can result in improved low temperature performance of Li-ion cells, including Polystor, Yardney, and Covalent. In addition to developing cells capable of operation at -20 C, there is continued interest in systems which can successfully operate at even lower temperatures (less than -30 C) and at high discharge rates (greater than C/2). Thus, we are currently focusing upon developing advanced electrolytes which are highly conductive at low temperatures and will result in cells capable of operation at -40 C. One approach to improve the low temperature conductivity of ethylene carbonate-based electrolytes involves adding co-solvents which will decrease the viscosity and extend the liquid range. Candidate solvent additives include formates, acetates, cyclic and aliphatic ethers, lactones, as well as other carbonates. Using this approach, we have prepared a number of electrolytes which contain methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), ethyl proprionate (EP), and 1,2-dimethoxyethane (DME), some of which have been characterized and reported. Other groups have also reported electrolytes based on mixtures of carbonates and acetates. In the present study, electrolytes which have been identified to have good low temperature conductivity and stability were incorporated into lithium-graphite cells for evaluation. Using various electrochemical methods, including ac impedence and DC micropolarization techniques, the film formation characteristics of graphite electrodes in contact with various lectrolyte formulations was investigated.
Smart, M. C.↗
Solid electrolyte oxygen regeneration system
A program to design, develop, fabricate and assemble a one-man, self-contained, solid electrolyte oxygen regeneration system (SX-1) incorporating solid electrolyte electrolyzer drums was completed. The SX-1 is a preprototype engineering model designed to produce 0.952 kg (2.1 lb)/day of breathable oxygen (O2) from the electrolysis of metabolic carbon dioxide (CO2) and water vapor. The CO2 supply rate was established based on the metabolic CO2 generation rate for one man of 0.998 kg (2.2 lb)/day. The water supply rate (0.254 kg (0.56 lb)/day) was designed to be sufficient to make up the difference between the 0.952 kg (2.1 lb)/day O2 generation specification and the O2 available through CO2 electrolysis, 0.726 kg (1.6 lb)/day. The SX-1 was successfully designed, fabricated and assembled. Design verification tests (DVT) or the CO Disproportionators, H2 separators, control instrumentation, monitor instrumentation, water feed mechanism were successfully completed. The erratic occurrence of electrolyzer drum leakage prevented the completion of the CO2 electrolyzer module and water electrolyzer module DVT's and also prevented the performance of SX-1 integrated testing. Further development work is required to improve the solid electrolyte cell high temperature seals.
Shumar, J. W.↗
Improved Wide Operating Temperature Range of LiNiCoAiO2-based Li-ion Cells with Methyl Propionate-based Electrolytes
Demonstration of wide operating temperature range Li-ion electrolytes Methyl propionate-based wide operating temperature range electrolytes were demonstrated to provide dramatic improvement of the low temperature capability of Quallion prototype Li-ion cells (MCMB-LiNiCoAlO2). Some formulations were observed to deliver over 60% of the room temperature capacity using a 5C rate at - 40oC !! Represents over a 4-fold improvement over the baseline electrolyte system. Demonstrated operational capability of a number of systems over a wide temperature range (-40 to +70 C) Demonstrated reasonably good long term cycle life performance at high temperature (i.e., at +40deg and +50 C) A number of formulations containing electrolytes additives (i.e., FEC, VC, LiBOB, and lithium oxalate) have been shown to have enhanced lithium kinetics at low temperature and promising high temperature resilience. Demonstrated good performance in larger capacity (12 Ah) Quallion Li-ion cells with methyl propionate-based electrolytes. Current efforts focused upon performing life studies and the impact upon low temperature capability.
Li-ion electrolytes↗
Electrolytes for Use in High Energy Lithium-Ion Batteries with Wide Operating Temperature Range
Objectives of this work are: (1) Develop advanced Li -ion electrolytes that enable cell operation over a wide temperature range (i.e., -30 to +60C). (2) Improve the high temperature stability and lifetime characteristics of wide operating temperature electrolytes. (3) Improve the high voltage stability of these candidate electrolytes systems to enable operation up to 5V with high specific energy cathode materials. (4) Define the performance limitations at low and high temperature extremes, as well as, life limiting processes. (5) Demonstrate the performance of advanced electrolytes in large capacity prototype cells.
voltage stability↗
Improved Wide Operating Temperature Range of Li-Ion Cells
Future NASA missions aimed at exploring the Moon, Mars, and the outer planets require rechargeable batteries that can operate over a wide temperature range (-60 to +60 C) to satisfy the requirements of various applications including landers, rovers, penetrators, CEV, CLV, etc. This work addresses the need for robust rechargeable batteries that can operate well over a wide temperature range. The Department of Energy (DoE) has identified a number of technical barriers associated with the development of Liion rechargeable batteries for PHEVs. For this reason, DoE has interest in the development of advanced electrolytes that will improve performance over a wide range of temperatures, and lead to long life characteristics (5,000 cycles over a 10-year life span). There is also interest in improving the high-voltage stability of these candidate electrolyte systems to enable the operation of up to 5 V with high specific energy cathode materials. Currently, the state-of-the-art lithium-ion system has been demonstrated to operate over a wide range of temperatures (-40 to +40 C); however, the rate capability at the lower temperatures is very poor. In addition, the low-temperature performance typically deteriorates rapidly upon being exposed to high temperatures. A number of electrolyte formulations were developed that incorporate the use of electrolyte additives to improve the high-temperature resilience, low-temperature power capability, and life characteristics of methyl propionate (MP)-based electrolyte solutions. These electrolyte additives include mono-fluoroethylene carbonate (FEC), lithium oxalate, vinylene carbonate (VC), and lithium bis(oxalate borate) (LiBOB), which have previously been shown to result in improved high-temperature resilience of all carbonate-based electrolytes. These MP-based electrolytes with additives have been shown to have improved performance in experiments with MCMB-LiNiCoAlO2 cells.
Smart, Marshall C.↗
A program to develop a high-energy density primary battery with a minimum of 200 watt hours per pound of total battery weight third quarterly report, jan. - mar. 1965
Electrochemical study of prospective electrode- electrolyte systems for high-energy primary battery with minimum of 200 watt hours per pound of total battery weight
ELECTRODE↗
Evaluation of Carbon Dioxide Sensors for the Constellation Space Suit Life Support System for Surface Exploration
This paper presents the findings of the trade study to evaluate carbon dioxide (CO2) sensing technologies for the Constellation (Cx) space suit life support system for surface exploration. The trade study found that nondispersive infrared absorption (NDIR) is the most appropriate high Technology Readiness Level (TRL) technology for the CO2 sensor for the Cx space suit. The maturity of the technology is high, as it is the basis for the CO2 sensor in the Extravehicular Mobility Unit (EMU). The study further determined that while there is a range of commercial sensors available, the Cx CO2 sensor should be a new design. Specifically, there are light sources (e.g., infrared light emitting diodes) and detectors (e.g., cooled detectors) that are not in typical commercial sensors due to cost. These advanced technology components offer significant advantages in performance (weight, volume, power, accuracy) to be implemented in the new sensor. The exact sensor design (light source, transmitting optics, path length, receiving optics and detector) will be specific for the Cx space suit and will be determined by the performance requirements of the Cx space suit. The paper further identifies specifications for some of the critical performance parameters as well as discussing the engineering aspects of implementing the sensor into the Portable Life Support System (PLSS). The paper then presents testing results from three CO2 sensors with respect to issues important to Extravehicular Activity (EVA) applications; stability, humidity dependence and low pressure compatibility. The three sensors include two NDIR sensors, one commercial and one custom-developed by NASA (for a different purpose), and one commercial electrochemical sensor. The results show that both NDIR sensors have excellent stability, no dependence on ambient humidity (when the ambient temperature is above the dew point) and operate in low pressure conditions and after being exposed to a full vacuum. The commercial electrochemical sensor was not suitable for the Cx space suit for surface exploration. Finally, the paper identifies a number of techniques currently under development that offer significant advantages for EVA applications. These include miniaturized, room temperature, solid electrolyte systems and advanced optical detectors.
Dietrich, Daniel L.↗
Development of high energy density primary batteries Fourth quarterly report, 22 Mar. - 21 Jun. 1966
High energy density primary batteries for space flight applications - electrolyte systems, cell systems, and positive electrode construction
SPACE FLIGHT↗
Development of high energy density primary batteries Topical report
Development of high energy density primary batteries - construction and performance tests of experimental copper fluoride-lithium cells using methyl formate electrolyte system
Abens, S. G.↗