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Silicon Whisker and Carbon Nanofiber Composite Anode
Phase II Objectives: Demonstrate production levels of grams per batch; Achieve full cell anode capacity of greater than 1,000 mAh/g at a charge rate of 10 (C/10) and 0 degree C; Establish a full cell cycle life of over 300 cycles; Display an operating temperature of negative 30 degrees C to plus 30 degrees C; Demonstrate a rate capability of C/5 or higher; Deliver to NASA three 2.5 Ah cells (energy density greater than 220 Wh/kg); Exhibit the safety features of the anode and full cells; Design a 1 kWh prismatic battery pack.
Trimethoxymethane: A Fuel For Direct-Oxidation Fuel Cells
Trimethoxymethane (TMM) identified as high-energy fuel for direct-oxidation fuel cells. Synthesized from natural gas (methane) and handled easily because non-toxic, low-vapor-pressure liquid. Data obtained from both half-cell and full-cell tests indicate that TMM oxidized at very high rates. Considered excellent candidate for use in direct-oxidation fuel cells in vehicles and portable power supplies
Advanced on-site power plant development technology program
A 30-cell, full area short stack containing advanced cell features was tested for 2900 hours. A stack acid addition approach was selected and will be evaluated on the stack at 5000 hours test time. A brassboard inverter was designed and fabrication was initiated. Evaluation of this brassboard inverter will take place in 1984. A Teflon coated commercial heat exchanger was selected as the preferred approach for the acid condenser. A reformer catalyst with significantly less pressure drop and equivalent performance relative to the 40-K baseline catalyst was selected for the development reformer. The early 40-kW field power plant history was reviewed and adjustments were made to the On-Site Technology Development Program to address critical component issues.
Improved Li/TiS2 cell cycling in ether-based electrolytes with synergistic additives
Based on an extensive series of normalized full cell Li/TiS2 cycling studies, open-circuit storage tests, microcalorimetry and AC impedance studies, and chemical precedent, we propose an integrated chemical model consistent with experimental observations concerning the behavior of numerous LiAsF6/cyclic ether electrolytes. The particularly striking potency of certain additives such as 2-methylfuran and the hydroxide action resides in their ability to intercept several different adverse catalytic processes concurrently in the bulk electrolyte as well as the Li anode and TiS2 cathode.
Synthesis of adriamycin-coupled polyglutaraldehyde microspheres and evaluation of their cytostatic activity
Adriamycin was coupled to polyglutaraldehyde microspheres having an average diameter of 4500 A. The coupled microspheres remained stable during incubation with cells. Full cytostatic activity was observed when the coupled adriamycin was tested with murine or human leukemia and murine sarcoma cell lines. A 10-fold increase in sensitivity was obtained with drug-resistant human leukemia cell lines. Repeated use of the coupled microspheres in the cytostatic assays did not decrease their activity, indicating that these complexes can be recycled. The results suggest that coupled adriamycin sufficiently perturbs the plasma membrane to lead to cytostatic activity. It is proposed that this mode of drug delivery provides multiple and repetitious sites for drug-cell interactions. In addition, the drug-polymer complexes may overcome those forms of resistance that are the result of decreased drug binding at the cell surface.
Circuit for Full Charging of Series Lithium-Ion Cells
An advanced charger has been proposed for a battery that comprises several lithium-ion cells in series. The proposal is directed toward charging the cells in as nearly an optimum manner as possible despite unit-to-unit differences among the nominally identical cells. The particular aspect of the charging problem that motivated the proposal can be summarized as follows: During bulk charging (charging all the cells in series at the same current), the voltages of individual cells increase at different rates. Once one of the cells reaches full charge, bulk charging must be stopped, leaving other cells less than fully charged. To make it possible to bring all cells up to full charge once bulk charging has been completed, the proposed charger would include a number of top-off chargers one for each cell. The top-off chargers would all be powered from the same DC source, but their outputs would be DC-isolated from each other and AC-coupled to their respective cells by means of transformers, as described below. Each top-off charger would include a flyback transformer, an electronic switch, and an output diode. For suppression of undesired electromagnetic emissions, each top-off charger would also include (1) a resistor and capacitor configured to act as a snubber and (2) an inductor and capacitor configured as a filter. The magnetic characteristics of the flyback transformer and the duration of its output pulses determine the energy delivered to the lithium-ion cell. It would be necessary to equip the cell with a precise voltage monitor to determine when the cell reaches full charge. In response to a full-charge reading by this voltage monitor, the electronic switch would be held in the off state. Other cells would continue to be charged similarly by their top-off chargers until their voltage monitors read full charge.
Considerations for Estimating Electrode Performance in Li-Ion Cells
Advanced electrode materials with increased specific capacity and voltage performance are critical to the development of Li-ion batteries with increased specific energy and energy density. Although performance metrics for individual electrodes are critically important, a fundamental understanding of the interactions of electrodes in a full cell is essential to achieving the desired performance, and for establishing meaningful goals for electrode performance. This paper presents practical design considerations for matching positive and negative electrodes in a viable design. Methods for predicting cell-level discharge voltage, based on laboratory data for individual electrodes, are presented and discussed.
Method for Predicting the Energy Characteristics of Li-Ion Cells Designed for High Specific Energy
Novel electrode materials with increased specific capacity and voltage performance are critical to the NASA goals for developing Li-ion batteries with increased specific energy and energy density. Although performance metrics of the individual electrodes are critically important, a fundamental understanding of the interactions of electrodes in a full cell is essential to achieving the desired performance, and for establishing meaningful goals for electrode performance in the first place. This paper presents design considerations for matching positive and negative electrodes in a viable design. Methods for predicting cell-level performance, based on laboratory data for individual electrodes, are presented and discussed.
Organometallic catalysts for primary phosphoric acid fuel cells
A continuing effort by the U.S. Department of Energy to improve the competitiveness of the phosphoric acid fuel cell by improving cell performance and/or reducing cell cost is discussed. Cathode improvement, both in performance and cost, available through the use of a class of organometallic cathode catalysts, the tetraazaannulenes (TAAs), was investigated. A new mixed catalyst was identified which provides improved cathode performance without the need for the use of a noble metal. This mixed catalyst was tested under load for 1000 hr. in full cell at 160 to 200 C in phosphoric acid H3PO4, and was shown to provide stable performance. The mixed catalyst contains an organometallic to catalyze electroreduction of oxygen to hydrogen peroxide and a metal to catalyze further electroreduction of the hydrogen peroxide to water. Cathodes containing an exemplar mixed catalyst (e.g., Co bisphenyl TAA/Mn) operate at approximately 650 mV vs DHE in 160 C, 85% H3PO4 with oxygen as reactant. In developing this mixed catalyst, a broad spectrum of TAAs were prepared, tested in half-cell and in a rotating ring-disk electrode system. TAAs found to facilitate the production of hydrogen peroxide in electroreduction were shown to be preferred TAAs for use in the mixed catalyst. Manganese (Mn) was identified as a preferred metal because it is capable of catalyzing hydrogen peroxide electroreduction, is lower in cost and is of less strategic importance than platinum, the cathode catalyst normally used in the fuel cell.
Assessment of Lithium-based Battery Electrolytes Developed under the NASA PERS Program
Recently, NASA formally completed the Polymer Energy Rechargeable System (PERS) Program, which was established in 2000 in collaboration with the Air Force Research Laboratory (AFRL) to support the development of polymer-based, lithium-based cell chemistries and battery technologies to address the next generation of aerospace applications and mission needs. The goal of this program was to ultimately develop an advanced, space-qualified battery technology, which embodied a solid polymer electrolyte (SPE) and complementary components, with improved performance characteristics that would address future aerospace battery requirements. Programmatically, the PERS initiative exploited both interagency collaborations to address common technology and engineering issues and the active participation of academia and private industry. The initial program phases focused on R&D activities to address the critical technical issues and challenges at the cell level. A variety of cell and polymeric electrolyte concepts were pursued as part of the development efforts undertaken at numerous governmental, industrial and academic laboratories. Numerous candidate electrolyte materials were developed, synthesized and optimized for evaluation. Utilizing the component screening facility and the "standardized" test procedures developed at the NASA Glenn Research Center, electrochemical screening and performance evaluations of promising candidate materials were completed. This overview summarizes test results for a variety of candidate electrolyte materials that were developed under the PERS Program. Electrolyte properties are contrasted and compared to the original project goals, and the strengths and weaknesses of the electrolyte chemistries are discussed. Limited cycling data for full-cells using lithium metal and vanadium oxide electrodes are also presented. Based on measured electrolyte properties, the projected performance characteristics and temperature limitations of batteries utilizing the advanced electrolytes and components have been estimated. Limitations for the achievement of practical performance levels are also discussed, as well as needs for future research and development.
Gas absorption cell photometer for rocket observations of local interstellar helium
A photometer sensitive in the 584-A line of He I, incorporating a helium-gas absorption cell, has been developed. The helium is confined at a pressure of 0.2 torr between thin-metal-foil broad-band ultraviolet filters. The cell contains sufficient helium to absorb 584-A radiation scattered from atmospheric helium. The ratio of fluxes seen with the cell full and empty provides a valuable datum for fitting models of the local interstellar medium, which is independent of solar 584-A flux, interstellar helium density, and photometer sensitivity.-
Observations of interstellar helium with a gas absorption cell - Limits on the bulk velocity of the interstellar medium
Results are reported for observations of solar 584-A flux resonantly scattered by the 1s(2)-1s2p transition of neutral interstellar helium. A photometer equipped with a helium gas-absorption cell and flown aboard a sounding rocket to a peak altitude of 185 km was employed to observe the sky in Perseus. The data reduction procedure is described, including subtraction of the terrestrial atmospheric background, calculation of the solar flux, and reduction of the number density of scatters to a function of phase-space parameters of the local interstellar medium. The ratio of 584-A fluxes observed with the gas cell full and empty is computed and compared with numerical models of the interstellar-helium flow through the solar system. The results show that the bulk speed of the distant interstellar medium with respect to the sun is unlikely to be less than 10 to 15 km/s, at the 2-sigma level. Since this value is inconsistent with results obtained from Lyman-alpha observations, it is suggested that either the total ionization rate for helium is variable or present models of the behavior of the local interstellar medium need further refinement.
Extreme ultraviolet photometer for observations of helium in interplanetary space
A four-channel photometer sensitive to two solar EUV lines which are resonantly scattered by helium gas was developed for flight on the Apollo-Soyuz Test Project. Two channels observed the 58.4-nm line of He I and used helium gas resonant absorption cells to determine the intensities of the center and wings of that line. The other two channels observed the 30.4-nm line of He II. The instrument surveyed much of the celestial sphere during a series of slow rolling maneuvers by the Apollo spacecraft. The experiment operated properly, and usable data were obtained. Study of the distributions of flux seen, and of the ratio 58.4-nm fluxes seen with gas cells full and empty, will refine current understanding of several poorly known properties of the local interstellar medium. Study of the 30.4-nm flux distribution will refine present knowledge of the structure of the earth's plasmasphere.
Factors Limiting Li+ Charge Transfer Kinetics in Li-ion Batteries
Understanding the factors limiting Li+ charge transfer kinetics in Li-ion batteries is essential in improving the rate performance, especially at lower temperatures. The Li+ charge transfer process involved in the lithium intercalation of graphite anode includes the step of de-solvation of the solvated Li+ in the liquid electrolyte and the step of transport of Li+ in the preformed solid electrolyte interphase (SEI) on electrodes until the Li+ accepts an electron at the electrode and becomes a Li in the electrode. Whether the de-solvation process or the Li+ transport through the SEI is a limiting step depends on the nature of the interphases at the electrode and electrolyte interfaces. Several examples involving the electrode materials such as graphite, lithium titanate (LTO), lithium iron phosphate (LFP), lithium nickel cobalt aluminum oxide (NCA) and solid Li+ conductor such as lithium lanthanum titanate or Li-Al-Ti-phosphate are reviewed and discussed to clarify the conditions at which either the de-solvation or the transport of Li+ in SEI is dominating and how the electrolyte components affect the activation energy of Li+ charge transfer kinetics. How the electrolyte additives impact the Li+ charge transfer kinetics at both the anode and the cathode has been examined at the same time in 3-electrode full cells. The resulting impact on Li+ charge transfer resistance, Rct, and activation energy, Ea, at both electrodes are reported and discussed.
Development of advanced fuel cell system, phase 2
A multiple task research and development program was performed to improve the weight, life, and performance characteristics of hydrogen-oxygen alkaline fuel cells for advanced power systems. Development and characterization of a very stable gold alloy catalyst was continued from Phase I of the program. A polymer material for fabrication of cell structural components was identified and its long term compatibility with the fuel cell environment was demonstrated in cell tests. Full scale partial cell stacks, with advanced design closed cycle evaporative coolers, were tested. The characteristics demonstrated in these tests verified the feasibility of developing the engineering model system concept into an advanced lightweight long life powerplant.
Performance Trade-Offs for MBG Using Different Bandgap Pairs
Present GAInP2/GAAs cell grown on Ge (or GaAs) substrates have demonstrates high efficiency, However, the individual bandgaps (1.85 eV, 1.42 eV respectively) are not the optimum match to convert the AM0 spectrum efficiently, although by reducing the thickness of the GaInP2 cell, good efficiencies have been achieved. Within the III-V alloys, modeling shows that several dual junction cells, comprising different bandgap pairs, could give higher efficiency. This paper outlines the modeling used, the bandgap pairs selected, and projections for the AM0 efficiency assuming that the effects of lattice mismatch associated with the bandgap can be reduced. We also present preliminary data on I-V performance for the selected top and bottom cells and for some full cascade cells. We have included some characterization results to check the bandgaps and lattice strain, to check how closely the fabricated cells conform to the model,
Effects of operating parameters on PAFC stack performance
This work was performed to assess actual relationships of phosphoric acid fuel cell voltage responses obtained from subscale cells with air-cooled and full size cells in stacks as a function of operating parameters. Key relationships were verified and found to be in agreement with the Nerst equation. An empirical equation was developed to predict cell voltages as a function of the measureable parameters.