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Simplified configuration and procedure developed for assembly of stacks of solid-electrolyte cells separating oxygen from air electrochemically. Reduces number of components and thus reduces probability of such failures as gas leaks, breakdown of sensitive parts, and electrical open or short circuits. Previous, more complicated version of cell described in "Improved Zirconia Oxygen-Separation Cell" (NPO-16161).
More than a metric ton of water is transported to the International Space Station (ISS) each year to provide breathing oxygen for the astronauts. Water is a safe and compact form of stored oxygen. The water is electrolyzed on ISS and ambient pressure oxygen is delivered to the cabin. A much smaller amount of oxygen is used each year in spacesuits to conduct Extra Vehicular Activities (EVAs). Space suits need high pressure (>1000 psia) high purity oxygen (must meet Aviator Breathing Oxygen "ABO" specifications, >99.5% O2). The water / water electrolysis system cannot directly provide high pressure, high purity oxygen, so oxygen for EVAs is transported to ISS in high pressure gas tanks. The tanks are relatively large and heavy, and the majority of the system launch weight is for the tanks and not the oxygen. Extracting high purity oxygen from cabin air and mechanically compressing the oxygen might enable on-board production of EVA grade oxygen using the existing water / water electrolysis system. This capability might also benefit human spaceflight missions, where oxygen for EVAs could be stored in the form of water, and converted into high pressure oxygen on-demand. Cerium oxide solid electrolyte-based ion transport membranes have been shown to separate oxygen from air, and a supported monolithic wafer form of the CeO2 electrolyte membrane has been shown to deliver oxygen at pressures greater than 300 psia. These supported monolithic wafers can withstand high pressure differentials even though the membrane is very thin, because the ion transport membrane is supported on both sides (Fig 1). The monolithic supported wafers have six distinct layers, each with matched coefficients of thermal expansion. The wafers are assembled into a cell stack which allows easy air flow across the wafers, uniform current distribution, and uniform current density (Fig 2). The oxygen separation is reported to be "infinitely selective" to oxygen [1] with reported purity of 99.99% [2]. Combined with a mechanical compressor, a Solid Electrolyte Oxygen Separator (SEOS) should be capable of producing ABO grade oxygen at pressures >2400 psia, on the space station. Feasibility tests using a SEOS integrated with a mechanical compressor identified an unexpected contaminant in the oxygen: water vapour was found in the oxygen product, sometimes at concentrations higher than 40 ppm (the ABO limit for water vapour is 7 ppm). If solid electrolyte membranes are really "infinitely selective" to oxygen as they are reported to be, where did the water come from? If water is getting into the oxygen, what other contaminants might get into the oxygen? Microscopic analyses of wafers, welds, and oxygen delivery tubes were performed in an attempt to find the source of the water vapour contamination. Hot and cold pressure decay tests were performed. Measurements of water vapour as a function of O2 delivery rate, O2 delivery pressure, and process air humidity levels were the most instructive in finding the source of water contamination (Fig 3). Water contamination was directly affected by oxygen delivery rate (doubling the oxygen production rate cut the water level in half). Water was affected by process air humidity levels and delivery pressure in a way that indicates the water was diffusing into the oxygen delivery system.
Air separation using a zirconia solid electrolyte membrane is a possible alternative source of oxygen. The process of zirconia oxygen separation is reviewed, and an oxygen plant concept using such separation is described. Potential cell designs, stack designs, and testing procedures are examined. Fabrication of the materials used in a zirconia module as well as distribution plate design and fabrication are examined.
Better gas-distribution plates fabricated more easily. Oxygen-separation cell redesigned to make it more efficient, smaller, lighter, and easier to manufacture. Potential applications include use as gas separators, filters, and fuel cells.
Extravehicular activities (EVAs) require high-pressure, high-purity oxygen. Shuttle EVAs use oxygen that is stored and transported as a cryogenic fluid. EVAs on the International Space Station (ISS) presently use the Shuttle cryo O2, which is transported to the ISS using a transfer hose. The fluid is compressed to elevated pressures and stored as a high-pressure gas. With the retirement of the shuttle, NASA has been searching for ways to deliver oxygen to fill the highpressure oxygen tanks on the ISS. A method was developed using low-pressure oxygen generated onboard the ISS and released into ISS cabin air, filtering the oxygen from ISS cabin air using a pressure swing absorber to generate a low-pressure (high-purity) oxygen stream, compressing the oxygen with a mechanical compressor, and transferring the high-pressure, high-purity oxygen to ISS storage tanks. The pressure swing absorber (PSA) can be either a two-stage device, or a single-stage device, depending on the type of sorbent used. The key is to produce a stream with oxygen purity greater than 99.5 percent. The separator can be a PSA device, or a VPSA device (that uses both vacuum and pressure for the gas separation). The compressor is a multi-stage mechanical compressor. If the gas flow rates are on the order of 5 to 10 lb (.2.3 to 4.6 kg) per day, the compressor can be relatively small [3 ~16 ~16 in. (.8 ~41 ~41 cm)]. Any spacecraft system, or other remote location that has a supply of lowpressure oxygen, a method of separating oxygen from cabin air, and a method of compressing the enriched oxygen stream, has the possibility of having a regenerable supply of highpressure, high-purity oxygen that is compact, simple, and safe. If cabin air is modified so there is very little argon, the separator can be smaller, simpler, and use less power.
Cell structure distributes feed gas more evenly for more efficent oxygen production. Multilayer cell structure containing passages, channels, tubes, and pores help distribute pressure evenly over zirconia electrolytic membrane. Resulting more uniform pressure distribution expected to improve efficiency of oxygen production.
Oxygen can be extracted from carbon dioxide via thermal dissociation at elevated temperatures. However, temperatures in excess of 1000 K are needed to effect significant levels of dissociation. The experiments reported here have examined the feasibility of using a glow-discharge in low-pressure carbon dioxide to produce increased atomic oxygen yields at lower temperatures (on the order of 800 K). The experiments have shown that when silver membranes are used simultaneously as anodes for the glow discharge and as permeable membranes for oxygen separation, oxygen yields which are comparable to the permeation rates for pure oxygen, can be produced. Since the silver membrane can be employed as the electrode interface between Mars atmosphere and a stabilized-zirconia electrochemical pump, glow-discharge enhancement can be considered as a complementary technology which can be used with the zirconia-based oxygen extraction systems described previously by others. Not only can glow-discharge be used to increase oxygen yields at lowered temperatures, but it can also be considered as a possible way to avoid filtration and compression of Mars atmosphere, since the glow-discharge can be sustained in Mars ambient pressures.
NASA has been developing and testing two different types of oxygen separation systems. One type of oxygen separation system uses pressure swing technology, the other type uses a solid electrolyte electrochemical oxygen separation cell. Both development systems have been subjected to long term testing, and performance testing under a variety of environmental and operational conditions. Testing these two systems revealed that measuring the product purity of oxygen, and determining if an oxygen separation device meets Aviator's Breathing Oxygen (ABO) specifications is a subtle and sometimes difficult analytical chemistry job. Verifying product purity of cryogenically produced oxygen presents a different set of analytical chemistry challenges. This presentation will describe some of the sample acquisition and analytical chemistry challenges presented by verifying oxygen produced by an oxygen separator - and verifying oxygen produced by cryogenic separation processes. The primary contaminant that causes gas samples to fail to meet ABO requirements is water. The maximum amount of water vapor allowed is 7 ppmv. The principal challenge of verifying oxygen produced by an oxygen separator is that it is produced relatively slowly, and at comparatively low temperatures. A short term failure that occurs for just a few minutes in the course of a 1 week run could cause an entire tank to be rejected. Continuous monitoring of oxygen purity and water vapor could identify problems as soon as they occur. Long term oxygen separator tests were instrumented with an oxygen analyzer and with an hygrometer: a GE Moisture Monitor Series 35. This hygrometer uses an aluminum oxide sensor. The user's manual does not report this, but long term exposure to pure oxygen causes the aluminum oxide sensor head to bias dry. Oxygen product that exceeded the 7 ppm specification was improperly accepted, because the sensor had biased. The bias is permanent - exposure to air does not cause the sensor to return to its original response - but the bias can be accounted for by recalibrating the sensor. After this issue was found, continuous measurements of water vapor in the oxygen product were made using an FTIR. The FTIR cell is relatively large, so response time is slow - but moisture measurements were repeatable and accurate. Verifying ABO compliance for oxygen produced by commercial cryogenic processes has a different set of sample acquisition and analytical chemistry challenges. Customers want analytical chemists to conserve as much as possible. Hygrometers are not exposed to hours of continuous flow of oxygen, so they don't bias, but small amounts of contamination in valves can cause a "fail". K bottles are periodically cleaned and recertified - after cleaning residual moisture can cause a "fail". Operators let bottle pressure drop to room pressure, introduce outside air into the bottle, and the subsequent fill will "fail". Outside storage of K‐bottles has allowed enough in‐leakage, so contents will "fail".
The overall purpose of the Electrolysis Performance Improvement Concept Study flight experiment is to demonstrate and validate in a microgravity environment the Static Feed Electrolyzer concept as well as investigate the effect of microgravity on water electrolysis performance. The scope of the experiment includes variations in microstructural characteristics of electrodes and current densities in a static feed electrolysis cell configuration. The results of the flight experiment will be used to improve efficiency of the static feed electrolysis process and other electrochemical regenerative life support processes by reducing power and expanding the operational range. Specific technologies that will benefit include water electrolysis for propulsion, energy storage, life support, extravehicular activity, in-space manufacturing and in-space science in addition to other electrochemical regenerative life support technologies such as electrochemical carbon dioxide and oxygen separation, electrochemical oxygen compression and water vapor electrolysis. The Electrolysis Performance Improvement Concept Study flight experiment design incorporates two primary hardware assemblies: the Mechanical/Electrochemical Assembly and the Control/Monitor Instrumentation. The Mechanical/Electrochemical Assembly contains three separate integrated electrolysis cells along with supporting pressure and temperature control components. The Control/Monitor Instrumentation controls the operation of the experiment via the Mechanical/Electrochemical Assembly components and provides for monitoring and control of critical parameters and storage of experimental data.
An apparatus in the form of a disk for the separation of oxygen from gases, or for the pumping of oxygen, uses a substantially circular disk geometry for the solid electrolyte with radial flow of gas from the outside edge of the disk to the center of the disk. The reduction in available surface area as the gas flows toward the center of the disk reduces the oxygen removal area proportionally to provide for a more uniform removal of oxygen.
There is considerable interest in in-situ propellant manufacturing on the moon and Mars. One of the concepts of oxygen production that is being actively pursued is the processing of atmospheric carbon dioxide on Mars to produce oxygen by means of thermal decomposition and electrochemical separation. The key component of such a production facility is the electrochemical separation cell that filters out the oxygen from the gas mixture of carbon dioxide, carbon monoxide, and oxygen. Efficient design of the separation cell and the selection of electrolyte and electrode materials of superior performance for the cell would translate to significant reduction in the power requirement and the mass of the production facility. The objective is to develop the technology required to produce the cells in-house and test various electrolyte and electrode materials systematically until the optimal combination is found. An effective technique was developed for the fabrication of disk shaped cells. Zirconia and Ceria cells were made in-house. Complete modules of the electrochemical cell and housings were designed, fabricated, and tested.
Research conducted to extract oxygen from air or water with possible applications to oxygen production on Mars, the moon, or the Space Station is discussed. The technology under development involves an electrochemical process which is energy-efficient, regenerative and, in combination with a fuel cell, will provide net positive power, and generate oxygen for life support systems. The history of chemical oxygen separation and details of the oxygen separation technology are presented.
The way in which a chemical processor that uses the Martian atmosphere as its only feedstock, thereby reducing the mass that must be launched from earth, can help to return a surface sample from Mars from a single Space Shuttle launch is described. Richter's (1981) study on both the theoretical and experimental aspects of oxygen separation using yttria-stabilized zirconia membranes is cited. Here, separation is accomplished by applying a voltage across the membrane which results in the selective conduction of oxygen ions from one side to the other. It is noted that by using thermal dissociation of the carbon dioxide in the Martian atmosphere to produce oxygen (and carbon monoxide), these zirconia electrolytic cells can be employed to separate oxygen from the atmospheric stream. Descriptions are also given of atmospheric filtration, atmospheric compression, and waste heat recovery, and of the oxygen precooler and oxygen compressor.
For manned missions to Mars to become a reality, an efficient and reliable means of obtaining oxygen from the carbon dioxide-rich atmosphere will be required. Otherwise, the high cost of transporting the oxygen needed to sustain the astronauts will severely restrict the expedition to the martian surface. Recently, the use of electrochemical devices has been explored as a means of obtaining oxygen from the carbon dioxide-rich atmosphere. In these devices, oxygen ions diffuse through solid oxide membranes, thus, separating oxygen from the other gases presented. This phenomenon has only recently been explored as a means of obtaining large quantities of oxygen from toxic atmospheres, although first observed by Walter nernst in 1899. Nernst observed that stabilized zirconia will conduct oxygen ions when an electrical potential is applied across metallic electrodes applied to the ceramic membrane. Diatomic oxygen molecules are dissociated at the positive electrode/electrolyte interface. The oxygen ions enter the ceramic body due to the ion density gradient which is produced by the electrical potential across the electrolytic membrane. Once the ions have diffused through the membrane, they reform diatomic oxygen molecules at the anode. The separation of oxygen from carbon dioxide is achieved by the combination of thermal and electrochemical processes. The thermal decomposition of carbon dioxide (at 1000 C) results in the production of carbon monoxide and oxygen by the reaction.
High purity oxygen is required for a number of scientific, medical, and industrial applications. Traditionally, these needs have been met by cryogenic distillation or pressure swing adsorption systems designed to separate oxygen from air. Oxygen separation from air via solid-state zirconia electrolyte technology offers an alternative to these methods. The technology has several advantages over the traditional methods, including reliability, compactness, quiet operation, high purity output, and low power consumption.
Presently, the Extra-Vehicular Activities (EVAs) conducted from the Quest Joint Airlock on the International Space Station use high pressure, high purity oxygen that is delivered to the Space Station by the Space Shuttle. When the Space Shuttle retires, a new method of delivering high pressure, high purity oxygen to the High Pressure Gas Tanks (HPGTs) is needed. One method is to use a cabin air separator to sweep oxygen from the cabin air, generate a low pressure/high purity oxygen stream, and compress the oxygen with a multistage mechanical compressor. A main advantage to this type of system is that the existing low pressure oxygen supply infrastructure can be used as the source of cabin oxygen. ISS has two water electrolysis systems that deliver low pressure oxygen to the cabin, as well as chlorate candles and compressed gas tanks on cargo vehicles. Each of these systems can feed low pressure oxygen into the cabin, and any low pressure oxygen source can be used as an on-board source of oxygen. Three different oxygen separator systems were evaluated, and a two stage Pressure Swing Adsorption system was selected for reasons of technical maturity. Two different compressor designs were subjected to long term testing, and the compressor with better life performance and more favorable oxygen safety characteristics was selected. These technologies have been used as the basis of a design for a flight system located in Equipment Lock, and taken to Preliminary Design Review level of maturity. This paper describes the Cabin Air Separator for EVA Oxygen (CASEO) concept, describes the separator and compressor technology trades, highlights key technology risks, and describes the flight hardware concept as presented at Preliminary Design Review (PDR)
One of the concepts for oxygen production from Martian atmospheric carbon dioxide involves the use of tubular electrochemical membranes for oxygen separation. The tubular configuration offers the advantage of being able to separate the oxygen at pressures of up to 500 psi, thereby eliminating the need for a pre-liquefaction oxygen compressor. A key technology that has to be developed in order for the electrochemical separator to combine as a compressor is a high temperature static seal between the ceramic separation cell and the nickel-based super-alloy tube. Equipment was designed and fabricated to test the seals. Efforts are under way to develop a finite element model to study the thermal stresses at the joints and on the seal, and the optimal shape of the seal. The choice of seal materials and the technique to be used to fabricate the seals are also being investigated.
Permeation membrane of a magnesium-nickel alloy of silver has the ability to permeate oxygen at high temperatures for an extended period of operation without failure. The measured rates of oxygen permeation in a tubular configuration of this alloy are higher than any previous rates published.