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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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Aluminum-oxygen batteries for space applications

An aluminum oxygen fuel cell is under development. Several highly efficient cell designs were constructed and tested. Air cathodes catalyzed with cobalt tetramethoxy porphorin have demonstrated more than 2000 cycles in intermittant use conditions. Aluminum alloys have operated at 4.2 kWH/kg at 200 mA/sq cm. A novel separator device, an impeller fluidizer was coupled with the battery to remove the solid hydrargillite discharge product. A 60 kW, 720 kWH battery system is projected to weigh about 2200 lbs., for an energy density of 327 WH lb.

Niksa, Marilyn J.↗

A Study on Advanced Lithium-Based Battery Cell Chemistries to Enhance Lunar Exploration Missions

NASA's Exploration Technology Development Program (ETDP) Energy Storage Project conducted an advanced lithium-based battery chemistry feasibility study to determine the best advanced chemistry to develop for the Altair lunar lander and the Extravehicular Activities (EVA) advanced lunar surface spacesuit. These customers require safe, reliable energy storage systems with extremely high specific energy as compared to today's state-of-the-art batteries. Based on customer requirements, the specific energy goals for the development project are 220 watt-hours per kilogram (Wh/kg) delivered at the battery level at 0 degrees Celsius (degrees Celcius) at a C/10 discharge rate. Continuous discharge rates between C/5 and C/2, operation over 0 to 30 degrees C, and 200 cycles are targeted. The team, consisting of members from NASA Glenn Research Center, Johnson Space Center, and Jet Propulsion laboratory, surveyed the literature, compiled information on recent materials developments, and consulted with other battery experts in the community to identify advanced battery materials that might be capable of achieving the desired results with further development. A variety of electrode materials were considered, including layered metal oxides, spinel oxides, and olivine-type cathode materials, and lithium metal, lithium alloy, and silicon-based composite anode materials. lithium-sulfur systems were also considered. Hypothetical cell constructs that combined compatible anode and cathode materials with suitable electrolytes, separators, current collectors, headers, and cell enclosures were modeled. While some of these advanced materials are projected to obtain the desired electrical performance, there are risks that also factored into the decision making process. The risks include uncertainties due to issues such as safety of a system containing some of these materials, ease of scaling-up of large batches of raw materials, adaptability of the materials to processing using established or reasonable cost manufacturing techniques, manufacturability of the materials in dimensions required for integration into battery cells of practical capacities, low Technology Readiness levels (TRl), and the ability to achieve the desired performance by the customer need dates. The advanced cell chemistry options were evaluated with respect to multiple quantitative and qualitative attributes while considering their projected performance at the end of the available development timeframe. Following a rigorous ranking process, a chemistry that combines a lithiated nickel manganese cobalt oxide (lithium NMC) cathode with a silicon-based composite anode was selected as the technology that can offer the best combination of safety, specific energy, energy density, and likelihood of success. Tasks over the next three years will focus on development of electrode materials, compatible electrolytes, and separator materials, and integration of promising components to assess their combined performance in working cells. Cells of the chosen chemistry will be developed to TRl 6 by 2014 and will then be transferred to the customers for infusion into their mission paths.

Reid, Concha↗

Development of Large-Format Lithium-Ion Cells with Silicon Anode and Low Flammable Electrolyte

NASA is developing safe, high energy and high capacity lithium-ion cell designs and batteries for future missions under NASAs Advanced Space Power System (ASPS) project. Advanced cell components, such as high specific capacity silicon anodes and low-flammable electrolytes have been developed for improving the cell specific energy and enhancing safety. To advance the technology readiness level, we have developed large-format flight-type hermetically sealed battery cells by incorporating high capacity silicon anodes, commercially available lithium nickel, cobalt, aluminum oxide (NCA) cathodes, and low-flammable electrolytes. In this report, we will present the performance results of these various battery cells. In addition, we will also discuss the post-test cell analysis results as well.

lithium-ion cell↗

A Study on Advanced Lithium-Based Battery Cell Chemistries to Enhance Lunar Exploration Missions

NASAs Exploration Technology Development Program (ETDP) Energy Storage Project conducted an advanced lithium-based battery chemistry feasibility study to determine the best advanced chemistry to develop for the Altair Lunar Lander and the Extravehicular Activities (EVA) advanced Lunar surface spacesuit. These customers require safe, reliable batteries with extremely high specific energy as compared to state-of-the-art. The specific energy goals for the development project are 220 watt-hours per kilogram (Wh/kg) delivered at the battery-level at 0 degrees Celsius ( C) at a C/10 discharge rate. Continuous discharge rates between C/5 and C/2, operation between 0 and 30 C and 200 cycles are targeted. Electrode materials that were considered include layered metal oxides, spinel oxides, and olivine-type cathode materials, and lithium metal, lithium alloy, and silicon-based composite anode materials. Advanced cell chemistry options were evaluated with respect to multiple quantitative and qualitative attributes while considering their projected performance at the end of the available development timeframe. Following a rigorous ranking process, a chemistry that combines a lithiated nickel manganese cobalt oxide Li(LiNMC)O2 cathode with a silicon-based composite anode was selected as the technology that can potentially offer the best combination of safety, specific energy, energy density, and likelihood of success.

Reid, Concha M.↗

High contrast cathode ray tube

A layer of material is described, which contains fine grains of phosphor material stimulated by electrons to produce visible radiation. The layer, which also contains fine grains of cobalt oxide, is deposited on the glass screen of a cathode ray tube to provide high contrast, by absorbing most of the visible radiation which is directed to the layer through the screen, while not materially affecting the visible light which the phosphor material produces in response to the electron stimulation.

Lisovicz, E. J.↗

An Integrated, Layered-Spinel Composite Cathode for Energy Storage Applications

At low operating temperatures, commercially available electrode materials for lithium-ion batteries do not fully meet the energy and power requirements for NASA fs exploration activities. The composite cathode under development is projected to provide the required energy and power densities at low temperatures and its usage will considerably reduce the overall volume and weight of the battery pack. The newly developed composite electrode material can provide superior electrochemical performance relative to a commercially available lithium cobalt system. One advantage of using a composite cathode is its higher energy density, which can lead to smaller and lighter battery packs. In the current program, different series of layered-spinel composite materials with at least two different systems in an integrated structure were synthesized, and the volumetric and gravimetric energy densities were evaluated. In an integrated network of a composite electrode, the effect of the combined structures is to enhance the capacity and power capabilities of the material to levels greater than what is possible in current state-of-the-art cathode systems. The main objective of the current program is to implement a novel cathode material that meets NASA fs low temperature energy density requirements. An important feature of the composite cathode is that it has at least two components (e.g., layered and spinel) that are structurally integrated. The layered material by itself is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated, thereby delivering a large amount of energy with stable cycling. A key aspect of the innovation has been the development of a scalable process to produce submicronand micron-scale particles of these composite materials. An additional advantage of using such a composite electrode material is its low irreversible loss (.5%), which is primarily due to the unique activation of the composite. High columbic efficiency (greater than 99%) upon cycling may indicate the formation of a stable SEI (solid-electrolyte interface) layer, which can contribute to long cycle life. The innovation in the current program, when further developed, will enable the system to maintain high energy and power densities at low temperatures, improve efficiency, and further stabilize and enhance the safety of the cell.

Hagh, Nader↗

Characterization of physio-chemical properties of polymeric and electrochemical materials for aerospace flight

Sealed nickel cadmium cells having undergone a large number of cycles were discharged using the Hg/HgO reference electrode. The negative electrode exhibited the second plateau. SEM of negative plates of such cells show clusters of large crystals of cadmium hydroxide. These large crystals on the negative plates disappear after continuous overcharging in flooded cells. Atomic Absorption Spectroscopy and standard wet chemical methods are being used to determine the cell materials viz: nickel, cadmium, cobalt, potassum and carbonate. The anodes and cathodes are analyzed after careful examination and the condition of the separator material is evaluated.

Rock, M.↗

Performance of (CoPC)n catalyst in active lithium-thionyl chloride cells

An experimental study was conducted with anode limited D size cells to characterize the performance of an active lithium-thionyl chloride (Li/SOCl2) system using the polymeric cobalt phthalocyanine, (CoPC)n, catalyst in carbon cathodes. The author describes the results of this experiment with respect to initial voltage delays, operating voltages, and capacities. The effectiveness of the preconditioning methods evolved to alleviate passivation effects on storage are also discussed. The results clearly demonstrated the superior high rate capability of cells with the catalyst. The catalyst did not adversely impact the performance of cells after active storage for up to 6 months, while retaining its beneficial influences.

Shah, Pinakin M.↗

Sintered Cathodes for All-Solid-State Structural Lithium-Ion Batteries

All-solid-state structural lithium ion batteries serve as both structural load-bearing components and as electrical energy storage devices to achieve system level weight savings in aerospace and other transportation applications. This multifunctional design goal is critical for the realization of next generation hybrid or all-electric propulsion systems. Additionally, transitioning to solid state technology improves upon battery safety from previous volatile architectures. This research established baseline solid state processing conditions and performance benchmarks for intercalation-type layered oxide materials for multifunctional application. Under consideration were lithium cobalt oxide and lithium nickel manganese cobalt oxide. Pertinent characteristics such as electrical conductivity, strength, chemical stability, and microstructure were characterized for future application in all-solid-state structural battery cathodes. The study includes characterization by XRD, ICP, SEM, ring-on-ring mechanical testing, and electrical impedance spectroscopy to elucidate optimal processing parameters, material characteristics, and multifunctional performance benchmarks. These findings provide initial conditions for implementing existing cathode materials in load bearing applications.

Ceramics↗

Cathode catalysts for primary phosphoric acid fuel cells

Alkylation or carbon Vulcan XC-72, the support carbon, was shown to provide the most stable bond type for linking cobalt dehydrodibenzo tetraazannulene (CoTAA) to the surface of the carbon; this result is based on data obtained by cyclic voltammetry, pulse voltammetry and by release of 14C from bonded CoTAA. Half-cell tests at 100 C in 85% phosphoric acid showed that CoTAA bonded to the surface of carbon (Vulcan XC-72) via an alkylation procedure is a more active catalyst than is platinum based on a factor of two improvement in Tafel slope; dimeric CoTAA had catalytic activity equal to platinum. Half-cell tests also showed that bonded CoTAA catalysts do not suffer a loss in potential when air is used as a fuel rather than oxygen. Commercially available polytetrafluroethylene (PTFE) was shown to be unstable in the fuel cell environment with degradation occurring in 2000 hours or less. The PTFE was stressed at 200 C in concentrated phosphoric acid as well as electrochemically stressed in 150 C concentrated phosphoric acid; the surface chemistry of PTFE was observed to change significantly. Radiolabeled PTFE was prepared and used to verify that such chemical changes also occur in the primary fuel cell environment.

Source record↗

Electrodeposition in microgravity: Ground-based experiments

Electrodeposition was studied at one-hundreth g and compared with bench studies at 1 g. The low gravity was achieved during KC-135 aircraft parobolic flights. Flow in a simple cobalt cell (1 M CoSO4) operating under typical commercial conditions (10 to 20 mA/sq cm and 1 V) was monitored with a Schlieren optical system. Natural convection was absent at one-hundreth g. Quantitative comparisons on a cobalt cell with shielded electrodes using interferometry were carried out. Fringe shift differences indicate greater semi-infinite linear diffusion at 1 g than at one-hundreth g for cobalt. Since a shielded electrode operates under diffusion controlled conditions, no differences between 1 g and one-hundreth g would be expected. Similar comparisons on a shielded electrode copper cell were inconclusive. Bench codeposition experiments using polystyrene neutral buoyancy particles coupled with a shielded electrode cobalt cell were begun. Tracking of 12 micron particles showed no measurable difference between thermal/Brownian motion when the cell was operational or nonoperational. Initial experiments on codeposition quality showed a strong dependence upon cathode surface preparation in a shielded electrode configuration.

Riley, C.↗

Oxygen reduction of several gold alloys in 1-molar potassium hydroxide

With rotated disk-and-ring equipment, polarograms and other electrochemical measurements were made of oxygen reduction in 1-molar potassium hydroxide on an equiatomic gold-copper (Au-Cu) alloy and a Au-Cu alloy doped with either indium (In) or cobalt (Co) and on Au doped with either nickel (Ni) or platinum (Pt). The results were compared with those for pure Au and pure Pt. The two-electron reaction dominated on all Au alloys as it did on Au. The polarographic results at lower polarization potentials were compared, assuming exclusively a two-step reduction. A qualified ranking of cathodic electrocatalytic activity on the freshly polished reduced disks was indicated: anodized Au Au-Cu-In Au-Cu Au-Cu-Co is equivalent or equal to Au-Pt Au-Ni. Aging in distilled water improved the electrocatalytic efficiency of Au-Cu-Co, Au-Cu, and (to a lesser extent) Au-Cu-In.

Miller, R. O.↗

Electrocatalytic reduction of oxygen on modified oxide surfaces

A first step which frequently occurs in the reduction of dioxygen, e.g., at the cathode of the alkaline fuel cell, is the two-electron reduction to the peroxyl ion, HO bar 2. For the efficiency of the fuel cell, this ion must be further reduced, or decomposed, to OH(-). Rate constants for HO bar 2 decomposition have been determined in 31 percent KOH at 25 C for the following catalysts in the form of suspended powders and Teflon-bonded electrodes: Pt, Au, cobalt tetrametoxyl phenyl porphyrin (CoTMPP), and La sub 0.5Pb sub 0.5MnO3. Rates were normalized to unit surface area measured by several methods as suitable. Where possible, four methods were used to measure rate constants: gasometric, oxygen probe, rotating disk electrode, and open-circuit potential decay. Steady-state polarization was also tried but was not as satisfactory. Comparisons are given for the methods in regard to reliability, applicability to the material, and convenience.

Chaffins, Scott A.↗

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.

Delp, Samuel A.↗

Sodium-metal chloride battery research at JPL

Sodium - metal chloride batteries have certain distinct advantages over sodium - sulfur batteries such as increased safety, inherent overcharge capability and lower operating temperatures. Two systems, i.e., Na/FeCl2 and Na/NiCl2 were developed extensively elsewhere and evaluated for various applications including electric vehicles and space. Their performance has been very encouraging and prompted a detailed fundamental study on these cathodes here at the Jet Propulsion Laboratory. A brief review of our studies on these new cathode materials is presented here. The initial efforts focused on the methods of fabrication of the electrodes and their electrochemical characterization." Subsequent studies were aimed at establishing the reaction mechanism, determining the kinetics and identifying the rate-limiting processes in the reduction of metal chloride cathodes. Nickel chloride emerged from these studies as the most promising candidate material and was taken up for further detailed study on its passivation - a rate limiting process - under different experimental conditions. Also, the feasibility of using copper chloride, which is expected to have higher energy density, has been assessed. Based on the criteria established from the voltametric response of FeCl2, NiCl2 and CuCI2, several other transition metal chlorides were screened. Of these, molybdenum and cobalt chlorides appear promising.

B V Ratnakumar↗

A Review of Sodium-Metal Chloride Battery Activity At JPL

Following the disclosures by Coetzer et al. on the use of transition metal chlorides in chloroaluminates as alternate cathodes to sulfur in rechargeable sodium batteries, several laboratories, including the Jet Propulsion Laboratory, focused their attention on these systems. These systems have certain distinct advantages over sodium-sulfur batteries such as increased safety, inherent overcharge capability, and lower operating temperatures. Two systems, i.e., Na/FeCl2 and NaNiCl2, were developed extensively and evaluated in various applications including electric vehicles and space. Their performance has been very encouraging and warrants a detailed fundamental study on these cathodes. At the Jet Propulsion Laboratory a program was initiated two years back to understand the electrochemical behavior of FeCl2 and NiCl2, and to identify and evaluate other transition metal chlorides of promise. The initial efforts focused on the methods of fabrication of the electrodes and their electrochemical characterization. Subsequent studies were aimed at establishing the reaction mechanism, determining the kinetics, and identifying the rate-limiting processes in te reduction of metal chloride cathodes. Nickel chloride emerged form these studies as the most promising candidate material and was taken up for further detailed study on its passivation- a rate limiting process-under different experimental conditions. Also, the feasibility of using copper chloride, which is expected to have a higher energy density, has been assessed. On the basis of the criteria established from the voltammetric response of FeCl2, NiCl2, and CuCl2, several other transition metal chlorides were screened. Of these, molybdenum and cobalt appear promising.

Ratnakumar, B. V.↗