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Hydrogen production by electrolytic decomposition of water is explained. Power efficiency, efficient energy utilization, and costs were emphasized. Four systems were considered: two were based on current electrolyzer technology using present efficiency values for electrical generation by fossil fired and nuclear thermal stations, and two using projected electrolyzer technology with advanced fossil and nuclear plants.
Future sustainable energy generation technologies such as photovoltaic and wind farms require advanced energy storage systems on a massive scale to make the alternate (green) energy options practical. The daunting requirements of such large-scale energy systems such as long operating and cycle life, safety, and low cost are not adequately met by state-of-the-art energy storage technologies such as vanadium flow cells, lead-acid, and zinc-bromine batteries. Much attention is being paid to redox batteries specifically to the vanadium redox battery (VRB) due to their simplicity, low cost, and good life characteristics compared to other related battery technologies. NASA is currently seeking high-specific- energy and long-cycle-life rechargeable batteries in the 10-to-100-kW range to support future human exploration missions, such as planetary habitats, human rovers, etc. The flow batteries described above are excellent candidates for these applications, as well as other applications that propose to use regenerative fuel cells. A new flow cell technology is proposed based on coupling two novel electrodes in the form of solvated electron systems (SES) between an alkali (or alkaline earth) metal and poly aromatic hydrocarbons (PAH), separated by an ionically conducting separator. The cell reaction involves the formation of such SES with a PAH of high voltage in the cathode, while the alkali (or alkaline earth metal) is reduced from such an MPAH complex in the anode half-cell. During recharge, the reactions are reversed in both electrodes. In other words, the alkali (alkaline earth) metal ion simply shuttles from one M-PAH complex (SES) to another, which are separated by a metal-ion conducting solid or polymer electrolyte separator. As an example, the concept was demonstrated with Li-naphthalene//Li DDQ (DDQ is 2,3-Dichloro-5,6-dicyano- 1,4-benzoquinone) separated by lithium super ion conductor, either ceramic or polymer (solid polymer or gel polymer) electrolytes. The reactants are Li-naphthalene dissolved in tetrahydrofuran (THF) with a lithium salt of 1M LiBF4 (lithium tetra fluoroborate) in the anode compartment, and DDQ again dissolved in THF and also containing 1M LiBF4 salt in the cathode half-cell. The solid electrolyte separator used in the first set of experiments is a ceramic solid electrolyte, available from a commercial source. The open circuit voltage of the cells is close to 3.0 V, as expected from the individual half-cell voltages of Li-naphthalene and Li-DDQ. Upon discharge, the cell shows steady discharge voltage of 2.7 V, which confirms that the electrochemical processes do involve lithium ion shuttling from the anodic compartment to the cathode half-cell. The reversibility or rechargeability is demonstrated by charging the partially discharged cells (i.e., with lithium present in the DDQ half). Once again, a steady voltage close to 3.0 V was observed during charge, indicating that the system is quite reversible. In the subsequent concept-demonstration studies, the ceramic electrolyte has been replaced with a gel polymer electrolyte, e.g., PVDF-HFP (poly vinylene difluoride hexafluoropropene) gel, which has several advantages such as high ionic conductivity (almost comparable to liquid electrolyte and about 2 orders of magnitude better than the ceramic equivalent), lower cost, and possibly higher chemical stability at the anode. In addition, it can be bonded to the electrode by thermal fusion to form membrane electrode assemblies (MEAs), as is done in fuel cells.
Two 25 cell stacks of the 13 inch x 23 inch cell size (about 4kW) remain on test after 4000 hours and 2900 hours, respectively, using simulated reformate fuel. These tests are focusing on the durability of fuel cell stack components developed through the end of 1983. Also, these stacks are serving as forerunners of a 25kW stack that will contain 175 cells of the same size and will employ the same technology base. The stack technology development program has focused on a new, low cost bipolar plate edge seal technique and evaluation of advanced cathode catalysts, an electrolyte replenishment system, and nonmetallic cooling plates in small stacks.
A prototype dual-axis electrolytic tilt sensor package for angular position measurements was built and evaluated in a laboratory environment. The objective was to investigate the use of this package for making wind tunnel wall attitude measurements for the National Transonic Facility (NTF) at NASA Langley Research Center (LaRC). The instrumentation may replace an existing, more costly, and less rugged servo accelerometer package (angle-of-attack package) currently in use. The dual-axis electrolytic tilt sensor package contains two commercial electrolytic tilt sensors thermally insulated with NTF foam, all housed within a stainless steel package. The package is actively heated and maintained at 160 F using foil heating elements. The laboratory evaluation consisted of a series of tests to characterize the linearity, repeatability, cross-axis interaction, lead wire effect, step response, thermal time constant, and rectification errors. Tests revealed that the total RMS errors for the x-axis sensor is 0.084 degree, and 0.182 degree for the y-axis sensor. The RMS errors are greater than the 0.01 degree specification required for NTF wall attitude measurements. It is therefore not a viable replacement for the angle-of-attack package in the NTF application. However, with some physical modifications, it can be used as an inexpensive 5-degree range dual-axis inclinometer with overall accuracy approaching 0.01 degree under less harsh environments. Also, the data obtained from the tests can be valuable for wind tunnel applications of most types of electrolytic tilt sensors.
An advanced nuclear-electrolytic hydrogen-production facility concept was synthesized at a conceptual level with the objective of minimizing estimated hydrogen-production costs. The concept is a closely-integrated, fully-dedicated (only hydrogen energy is produced) system whose components and subsystems are predicted on ''1985 technology.'' The principal components are: (1) a high-temperature gas-cooled reactor (HTGR) operating a helium-Brayton/ammonia-Rankine binary cycle with a helium reactor-core exit temperature of 980 C, (2) acyclic d-c generators, (3) high-pressure, high-current-density electrolyzers based on solid-polymer electrolyte technology. Based on an assumed 3,000 MWt HTGR the facility is capable of producing 8.7 million std cu m/day of hydrogen at pipeline conditions, 6,900 kPa. Coproduct oxygen is also available at pipeline conditions at one-half this volume. It has further been shown that the incorporation of advanced technology provides an overall efficiency of about 43 percent, as compared with 25 percent for a contemporary nuclear-electric plant powering close-coupled contemporary industrial electrolyzers.
A review of the current phosphoric acid fuel cell system technology development efforts is presented both for multimegawatt systems for electric utility applications and for multikilowatt systems for on-site integrated energy system applications. Improving fuel cell performance, reducing cost, and increasing durability are the technology drivers at this time. Electrodes, matrices, intercell cooling, bipolar/separator plates, electrolyte management, and fuel selection are discussed.
Solid-electrolyte-based amperometric sensors for measuring concentrations of CO2 in air are being developed for use in detection of fires, environmental monitoring, and other applications where liquid-based electrochemical cells are problematic. These sensors are small (sizes of the order of a millimeter), are robust, are amenable to batch fabrication at relatively low cost, and exhibit short response times (seconds) and wide detection ranges. A sensor of this type at a previous stage of development included a solid electrolyte of Na3Zr2Si2PO12 deposited mainly between interdigitated Pt electrodes on an alumina substrate, all overcoated with an auxiliary solid electrolyte of (Na2CO3:BaCO3 in a molar ratio of 1:1.7). It was necessary to heat this device to a temperature as high as 600 C to obtain the desired sensitivity and rapid response. Heating sensors increases the power consumption of the sensor system and complicates the use of the sensor in some applications. Thus, decreasing a sensor s power consumption while maintaining its performance is a technical goal of ongoing development.
A characterization of the physical parameters and life cycle data on nickel composite electrodes was conducted. Attempts to improve the nickel composite electrodes with respect to longevity, light weight, and low cost were made. The physical characteristics of a group of electrodes were examined with emphasis on the porosity of the plaques, the thickness of the electrodes, and the potential presence of electrolytes contamination. It was concluded that the nickel composite electrodes exhibit good life cycle characteristics and that their fabrication seems to present real possibilities for the future as a method of making electrodes that are durable, lightweight, and low cost.
Dual-membrane hollow-fiber electrode increases reliability and lowers costs. Leakage of fuel or oxidizer through fiber does not result in failure; excess product water migrates into electrolyte where it is removed by evaporation or distillation; constant exposure of fiber to electrolyte eliminates problems of drying and consequent failure; reference electrode monitors current collectors and overall cell performance.
Report is made of the cost analysis of four leading oxygen recovery subsystems which include two carbon dioxide reduction subsystems and two water electrolysis subsystems, namely, the solid polymer electrolyte and the circulating KOH electrolyte. The four oxygen recovery systems were quantitatively evaluated. System characteristics, including process flows, performance, and physical characteristics were also analyzed. Additionally, the status of development of each of the systems considered and the required advance technology efforts required to bring conceptual and/or pre-prototype hardware to an operational prototype status were defined. Intimate knowledge of the operations, development status, and capabilities of the systems to meet space mission requirements were found to be essential in establishing the cost estimating relationships for advanced life support systems.
Modules designed for long life, light weight, reliability, and low cost. Stack of alkaline fuel cells based on modules, consisting of three fuel cells and cooler. Each cell includes following components: ribbed carbon fine-pore anode electrolyte-reservoir plate; platinum-on-carbon catalyst anode; potassium titanate matrix bonded with butyl rubber; gold-plated nickel-foil electrode substrates; and silver plated, gold-flashed molded polyphenylene sulfide cell holder. Each cell has active area of 1ft to the 2nd power (0.09 m to the 2nd power). Materials and configurations of parts chosen to extend life expectancy, reduce weight and manufacturing cost, and increase reliability.
An advanced technology, fully dedicated nuclear-electrolytic hydrogen production facility is presented. This plant will produce hydrogen and oxygen only and no electrical power will be generated for off-plant use. The conceptual design was based on hydrogen production to fill a pipeline at 1000 psi and a 3000 MW nuclear base, and the base-line facility nuclear-to-shaftpower and shaftpower-to-electricity subsystems, the water treatment subsystem, electricity-to-hydrogen subsystem, hydrogen compression, efficiency, and hydrogen production cost are discussed. The final conceptual design integrates a 3000 MWth high-temperature gas-cooled reactor operating at 980 C helium reactor-out temperature, direct dc electricity generation via acyclic generators, and high-current density, high-pressure electrolyzers based on the solid polymer electrolyte approach. All subsystems are close-coupled and optimally interfaced and pipeline hydrogen is produced at 1000 psi. Hydrogen costs were about half of the conventional nuclear electrolysis process.
The plating sequences Pd-Cr-Cu and Pd-Ni-Cu are demonstrated. The surface was sensitized with a 50 A-thick Pd layer obtained from an immersion bath. After 15 min heating at 400 C in N2, a thin barrier layer of either Cr or Ni was deposited from electroless baths operated at temperatures around 90 C. The sintering process was repeated, and a thin copper layer of 500 A was deposited by electroless means. An electrolytic copper bath was used to build the copper layer to 3-4 micron thicknesses. Cells with good I-V curves were obtained, and the all-plated contacts had good adhesion. Preliminary cost estimates show that the process costs approximately 12 cents per watt excluding the cost of the masking procedure.
A novel method for electroplating ultra-high-strength glassy metals, nickel-phosphorous and nickel-cobalt-phosphorous, has been developed at NASA Marshall Space Flight Center, cooperatively with the University of Alabama in Huntsville. Traditionally, thin coatings of these metals are achieved via electroless deposition. Benefits of the new electrolytic process include thick, low-stress deposits, free standing shapes, lower plating temperature, low maintenance, and safer operation with substantially lower cost.
The construction of the 50 MT Si/year experimental process system development unit was deferred until FY 1980, and the fluidized bed, zinc vaporizer, by-product condenser, and electrolytic cell were combined with auxiliary units, capable of supporting 8-hour batchwise operation, to form the process development unit (PDU), which is scheduled to be in operation by October 1, 1979. The design of the PDU and objectives of its operation are discussed. Experimental program support activities described relate to: (1) a wetted-wall condensor; (2) fluidized-bed modeling; (3) zinc chloride electrolysis; and (4) zinc vaporizer.
The purpose of the solid polymer electrolyte (SPE) fuel cell program is to advance the SPE fuel cell technology in four target areas. These areas are: (1) reduced fuel cell costs; (2) reduced fuel cell weight; (3) improved fuel cell efficiency; and (4) increased systems compatibility.
A solid polymer electrolyte fuel cell was studied for the purpose of improving the characteristics of the technology. Several facets were evaluated, namely: (1) reduced fuel cell costs; (2) reduced fuel cell weight; (3) improved fuel cell efficiency; and (4) increased systems compatibility. Demonstrated advances were incorporated into a full scale hardware design. A single cell unit was fabricated. A substantial degree of success was demonstrated.
A fully dedicated nuclear-electrolytic hydrogen-production facility, based on advanced (1985) technology, has been synthesized and assessed at the conceptual level. The facility integrates an HTGR operating a binary shaftpower-extraction cycle at 980 C top temperature, direct dc electricity generation via acyclic generators, and high-current density high-pressure electrolyzers based on the solid polymer electrolyte approach. All subsystems are close-coupled and optimally interfaced. Pipeline-pressure hydrogen and coproduct oxygen are produced at 6900 kPa. On consistent costing bases, the advanced facility concept was found to provide hydrogen costs that were approximately half those associated with conventional, contemporary-technology nuclear electrolysis. The nuclear heat-to-hydrogen energy conversion efficiency for the advanced system was estimated as 43%, against 25% for the baseline present-day approach.