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Coating electrodes of silver-cadmium cells with thermostable electrodeposits of calcium hydroxide or magnesium hydroxide reduces silver migration and increases cell life. Absence of organic matter enables assembled cells to be sterilized without oxidation of the material of the separators.
The rechargeability of electrochemical cells is often limited by negative electrode problems. These may include loss of capacity, increased impedance, macroscopic shape change, dendrite growth, or a tendency for filamentary or whisker growth. In principle, these problems can be reduced or eliminated by the use of alloys that undergo either displacement or insertion reactions at reactant species activities less than unity, rather than pure elements. The fundamental reasons for some of these problems with elemental electrodes, as well as the basic principles involved in the different behavior of alloys, are briefly discussed. More information is now available concerning the thermodynamic and kinetic properties of a number of alloys of potential interest for use as electrodes in elevated temperature lithium battery systems. Recent results have extended these results down to ambient temperatures, indicating that some such materials may be of interest for use with new low temperature molten salt electrolytes, or with organic solvent electrolytes. The all solid mixed conductor matrix concept is also reviewed.
A flexible, porous battery separator includes a coating applied to a porous, flexible substrate. The coating comprises: (1) a thermoplastic rubber-based resin which is insoluble and unreactive in the alkaline electrolyte, (2) a polar organic plasticizer which is reactive with the alkaline electrolyte to produce a reaction product which contains a hydroxyl group and/or a carboxylic acid group, and (3) a mixture of polar particulate filler materials which are unreactive with the electrode. The mixture comprises at least one first filler material having a surface area of greater than 25 sq meters/gram, at last one second filler material having a surface area of 10 to 25 sq meters/gram. The volume of the mixture of filler materials is less than 45% of the total volume of the fillers and the binder. The filler surface area per gram of binder is about 20 to 60 sq meters/gram, and the amount of plasticizer is sufficient to coat each filler particle.
Theoretical and experimental studies on high pressure electrolysis producing hydrogen and oxygen for energy storage and reconversion are reported. Moderate temperature, high pressure hydrogen/oxygen fuel cells with nickel electrodes are investigated for effects of pressure, temperature, and membrane porosity. Test results from an aphodid burner turbine generator combination obtained 40 percent kilowatt hours out of the fuel cell divided by kilowatt hours into the electrolyzer. It is concluded that high pressure hydrogenation of organic materials can be used to synthesize hydrozenes and methanes for making synthetic vehicular fuels.
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
Many primitive meteorites contain an insoluble organic material, much like terrestrial kerogen, whose mode of origin is currently unknown. When sujbected to stepwise decomposition, this material, unlike its terrestrial counterpart, reveals characteristic release patterns for the stable isotopes of carbon, hydrogen and nitrogen as a function of fractional release of each element. The purpose of this study is to try to match those release patterns using organic matter synthesised in the laboratory under controlled conditions. If successful, such a study would shed light on the origin of kerogen-like organic matter in the early solar system and, by extension, on prebiotic organic synthesis in general. The range of possible syntheses, starting materials and reaction conditions to be investigated is considerable. Samples analysed to date include: a heavy oil produced by Fischer-Tropsch-type catalysis of CO + H2; a solid residue generated by a plasma discharge in CO + H2 + N2; a solid deposited on the electrodes of a Miller-Urey synthesis operating on CH4 + H2O + N2; and a solid residue formed by polymerization of light hydrocarbons procured by a Miller-Urey discharge acting on CH4. Significant structure is observed in the release patterns for the carbon and hydrogen isotopes from the synthetic samples, though there is little evidence for isotopic fractionation during the analysis itself.
Contamination of surface and ground waters with nitrate usually involves leaching through soil of nitrate produced by mineralization of soil organic matter, decomposition of animal wastes or plant residues, or derived from fertilizers. Nitrate concentrations in the soil solution may be measured by several chemical procedures or by the nitrate electrode. since nitrate is produced throughout the soil mass it is difficult to identify a source of nitrate contamination by conventional means. This problem can be solved by use of N-15-enriched or N-15-depleted materials as tracers. The latter is particularly attractive because of the negligible possibility of the tracer hazardous to health.
The chemical sensor market has been projected to grow to better than $40 billion dollars worldwide within the next 10 years. Some of the primary motivations to develop nanostructured chemical sensors are monitoring and control of environmental pollution; improved diagnostics for consumption; improvement in measurement precision and accuracy; and improved detection limits for Homeland security, battlefield environments, and process and quality control of industrial applications. In each of these applications, there is demand for sensitivity, selectivity and stability of environmental and biohazard detection and capture beyond what is currently commercially available. Nanotechnology offers the ability to work at the molecular level, atom by atom, to create large structures with fundamentally new molecular organization. It is essentially concerned with materials, devices, and systems whose structures and components exhibit novel and significantly improved physical, chemical and biological properties, phenomena, and process control due to their nanoscale size. One such nanotechnology-enabled chemical sensor has been developed at NASA Ames leveraging nanostructures, such as single walled carbon nanotubes (SWNTs) and metal oxide nanobelts or nanowires, as a sensing medium bridging a pair of interdigitated electrodes (IDE) realized through a silicon-based microfabrication and micromachining technique. The DE fingers are fabricated on a silicon substrate using standard photolithography and thin film metallization techniques. It is noteworthy that the fabrication techniques employed are not confined to the silicon substrate. Through spin casting and careful substrate selection (i.e. clothing, glass, polymer, etc.), additional degrees of freedom can be exploited to enhance sensitivity or to conform to unique applications. Both in-situ growth of nanostructured materials and casting of nanostructured dispersions were used to produce analogous chemical sensing devices.
For future electric aviation, advanced battery cell chemistry beyond lithium ion batteries are required to meet mission requirements. High energy density battery concepts such as lithium-sulfur (Li-S) and lithiumoxygen (Li-O2) chemistries are being intensively investigated to realize their extraordinary theoretical promise in terms of energy density. Most fabrication methods of cathodes for these novel battery chemistries followed a conventional approach. In this approach, the active material is mixed with a polymer binder and a conductive carbon in a high-boiling organic solvent to form a slurry, followed by casting onto a current collector and solvent evaporation. The process is usually lengthy and poses environmental hazards due to the use of organic solvents.
An ambient temperature oxygen microsensor, based on a Nafion polymer electrolyte, has been developed and was microfabricated using thin-film technologies. A challenge in the operation of Nafion-based sensor systems is that the conductivity of Nafion film depends on the humidity in the film. Nafion film loses conductivity when the moisture content in the film is too low, which can affect sensor operation. The advancement here is the identification of a method to retain the operation of the Nafion films in lower humidity environments. Certain salts can hold water molecules in the Nafion film structure at room temperature. By mixing salts with the Nafion solution, water molecules can be homogeneously distributed in the Nafion film increasing the film s hydration to prevent Nafion film from being dried out in low-humidity environment. The presence of organics provides extra sites in the Nafion film to promote proton (H+) mobility and thus improving Nafion film conductivity and sensor performance. The fabrication of ambient temperature oxygen microsensors includes depositing basic electrodes using noble metals, and metal oxides layer on one of the electrode as a reference electrode. The use of noble metals for electrodes is due to their strong catalytic properties for oxygen reduction. A conducting polymer Nafion, doped with water-retaining components and extra sites facilitating proton movement, was used as the electrolyte material, making the design adequate for low humidity environment applications. The Nafion solution was coated on the electrodes and air-dried. The sensor operates at room temperature in potentiometric mode, which measures voltage differences between working and reference electrodes in different gases. Repeat able responses to 21-percent oxygen in nitrogen were achieved using nitrogen as a baseline gas. Detection of oxygen from 7 to 21 percent has also been demonstrated. The room-temperature oxygen micro sensor developed has extremely low power consumption (no heating for operation, no voltage applied to the sensor, only a voltmeter is needed to measure the output), is small in size, is simple to batch-fabricate, and is high in sensor yield. It is applicable in a wide humidity range, with improved operation in low humidity after the additives were added to the Nafion film. Through further improvement and development, the sensor can be used for aerospace applications such as fuel leak detection, fire detection, and environmental monitoring.
There are many different kinds of conjugated polymers that may be useful in photovoltaic devices. So far, the most popular and successful conjugated polymers used in photovoltaic devices include poly(1,4-)phenylenevinylenes (PPV), C60 and their derivatives. The discovery of electro-luminescence in PPV has stimulated a great deal of interest in developing "plastic" solid-state semiconductor devices. The overall synthetic methodology for the preparation of PPV can be divided into three main categories: (1) side chain derivatization, (2) precursor approach, and (3) in-situ polymerization. In this project, the first method was adopted. As discussed in project proposal and literatures, the overall efficiency of photovoltaic devices containing conjugated polymers is determined by the materials ability to generate excitons from incoming radiation, and then to separate the charges at donor/acceptor interfaces, and then to transport charges to respective electrodes. Given that effective exciton diffusion range are typical less then 30 nm, unique morphological structures are needed. This need led to several research groups to the idea that interpenetrating or bi-continuous networks of donor (electron donating) and acceptor (electron withdrawing) polymers should give better results. One approach involved the use of functionalized PPV. The attachment of electron withdrawing cyano groups to a PPV forms the CN-PPV, making it a strong electron acceptor. Underivatized PPV is a generally considered a hole-transporting material. Using blends of MEH-PPV, a soluble donor PPV derivative, as a hole transporter and CN-PPV as an electron transporter, a quantum efficiencies of up to 6% was achieved.
Advanced secondary batteries operating at intermediate temperatures (100 to 200 C) have attracted considerable interest due to their inherent advantages (reduced corrosion and safety risks) over higher temperature systems. Current work in this laboratory has involved research on a class of intermediate temperature Na/beta double prime- alumina/RSSR batteries conceptually similar to Na/S cells, but operating within a temperature range of 100 to 150 C, and having an organosulfur rather than inorganic sulfur positive electrode. The organosulfur electrodes are based on the reversible, two electron eduction of organodisulfides to the corresponding thiolate anions, RSSR + 2 electrons yield 2RS(-), where R is an organic moiety. Among the advantages of such a generic redox couple for battery research is the ability to tailor the physical, chemical, and electrochemical properties of the RSSR molecule through choice of the organic moiety. The viscosity, liquidus range, dielectric constant, equivalent weight, and redox potential can in fact be verified in a largely predictable manner. The current work concerns the use of multiple nitrogen organosulfur molecules, chosen for application in Na/RSSR cells for their expected oxidizing character. In fact, a Na/RSSR cell containing one of these materials, the sodium salt of 5-mercapto 1-methyltetrazole, yielded the highest open circuit voltage obtained yet in the laboratory; 3.0 volts in the charged state and 2.6 volts at 100 percent discharge. Accordingly, the cycling behavior of a series of multiple nitrogen organodisulfides as well as polymeric organodisulfides are presented in this manuscript.
All-electric vertical take-off and landing vehicles (eVTOL) for urban air mobility (UAM) concepts face numerous challenging technical barriers before their introduction into the consumer marketplace. The primary barrier to overcome is developing an energy storage system that meets rigorous aerospace safety and performance criteria. The performance metrics for eVTOL vehicles are at least two times greater than those of electric ground vehicles. Furthermore, inherently non-flammable batteries are essential for the safe operation of commercial electric aero vehicles. The SABERS concept proposes a battery that meets the critical performance criteria by developing a solid-state architecture battery utilizing a high-capacity sulfur-selenium cathode and lithium metal anode. The combination of sulfur and selenium offers a balanced energy-to-power density ratio, which can be tailored to the specific application by altering the stoichiometric ratios of sulfur to selenium. This hybrid cathode will be developed using NASA-patented holey graphene technology as a highly conductive, ultra-lightweight electrode scaffold. A solid-state electrolyte will be used as a safe, non-flammable replacement for the highly flammable liquid organic electrolytes currently in SOA lithium-ion batteries. This solid-state lithium-sulfur/selenium cell will be designed in a serial stacking configuration to enable the dense packaging of the battery cells. The serial stacking configuration is termed a bipolar stack, which has the advantages of reducing overall cell weight, simplifying the interfaced connections for the cell, and minimizing the cooling requirements. Lastly, the optimization of battery components will occur through a robust and rigorous combination of various computational modeling techniques covering multiple length scales. The expected result will be a fully solid-state battery with operational temperatures up to 150°C, providing the required energy density, discharge rates, and inherent safety to meet the strict aerospace mission performance criteria. The SABERS team employed novel materials development, computational modeling, and design-of-experiments (DOE) optimization studies in their research. This presentation will show the results of these studies and demonstrate a feasible path for solid-state cells with a specific energy greater than 400 Wh/kg to enable electric aircraft.
A bio-nanobattery is an electrical energy storage device that utilizes organic materials and processes on an atomic, or nanometer-scale. The bio-nanobattery under development at NASA s Langley Research Center provides new capabilities for electrical power generation, storage, and distribution as compared to conventional power storage systems. Most currently available electronic systems and devices rely on a single, centralized power source to supply electrical power to a specified location in the circuit. As electronic devices and associated components continue to shrink in size towards the nanometer-scale, a single centralized power source becomes impractical. Small systems, such as these, will require distributed power elements to reduce Joule heating, to minimize wiring quantities, and to allow autonomous operation of the various functions performed by the circuit. Our research involves the development and characterization of a bio-nanobattery using ferritins reconstituted with both an iron core (Fe-ferritin) and a cobalt core (Co-ferritin). Synthesis and characterization of the Co-ferritin and Fe-ferritin electrodes were performed, including reducing capability and the half-cell electrical potentials. Electrical output of nearly 0.5 V for the battery cell was measured. Ferritin utilizing other metallic cores were also considered to increase the overall electrical output. Two dimensional ferritin arrays were produced on various substrates to demonstrate the feasibility of a thin-film nano-scaled power storage system for distributed power storage applications. The bio-nanobattery will be ideal for nanometerscaled electronic applications, due to the small size, high energy density, and flexible thin-film structure. A five-cell demonstration article was produced for concept verification and bio-nanobattery characterization. Challenges to be addressed include the development of a multi-layered thin-film, increasing the energy density, dry-cell bionanobattery development, and selection of ferritin core materials to allow the broadest range of applications. The potential applications for the distributed power system include autonomously-operating intelligent chips, flexible thin-film electronic circuits, nanoelectromechanical systems (NEMS), ultra-high density data storage devices, nanoelectromagnetics, quantum electronic devices, biochips, nanorobots for medical applications and mechanical nano-fabrication, etc.
All-electric and hybrid electric aerovehicle concepts face numerous technical barriers prior to their introduction into the consumer marketplace in order to meet sustainable aviation goals. One of the primary barriers to overcome is developing an energy dense storage system capable of meeting the rigorous aerospace safety and performance criteria. Additionally, the electric aviation market requires that the batteries be fabricated in a sustainable manner with materials that are readily available and abundant within the U.S. to ensure there are no supply chain issues during manufacturing. The performance metrics to enable electric aviation are at least two times greater than those of electric ground vehicles. Furthermore, inherently non-flammable batteries are essential for safe operation of commercial electric aerovehicles. The SABERS concept proposes a battery that meets the key performance criteria through development of a solid-state architecture battery utilizing high-capacity sulfur-selenium cathode and lithium metal anode. The combination of sulfur and selenium offers a balanced energy-to-power density ratio, which can be tailored to the specific application by altering the stoichiometric ratios of sulfur to selenium. The hybrid cathode has been developed by implementing NASA patented holey graphene technology as a highly conductive, ultra-lightweight electrode scaffold. A solid-state electrolyte has been used as a safe, non-flammable replacement to the highly flammable liquid organic electrolytes currently used in SOA lithium-ion batteries. This solid-state lithium-sulfur/selenium cell will be designed into a serial stacking configuration to enable dense packaging of the battery cells. The serial stacking configuration is termed a bipolar stack, which has the advantages of reducing overall cell weight, simplifying the interfaced connections for the cell, and minimizing the cooling requirements. Lastly, optimization of battery components will occur through a robust and rigorous combination of various computational modeling techniques covering multiple length scales. The expected result will be a fully solid-state battery with operational temperatures up to 150 °C which provides the required energy density, discharge rates, and inherent safety to meet the strict aerospace mission performance criteria. This poster summarizes recent results from battery component optimization to scale-up production of full SABERS pouch cells.
All-electric vertical take-off and landing vehicles (eVTOL) for urban air mobility (UAM) concepts face numerous challenging technical barriers before their introduction into the consumer marketplace. The primary barrier to overcome is developing an energy storage system capable of meeting the rigorous aerospace safety and performance criteria. The performance metrics for eVTOL vehicles are at least two times greater than those of electric ground vehicles. Furthermore, inherently non-flammable batteries are essential for safe operation of commercial electric aerovehicles. The SABERS concept proposes a battery that meets the key performance criteria through development of a solid-state architecture battery utilizing high-capacity sulfur-selenium cathode and lithium metal anode. The combination of sulfur and selenium offers a balanced energy-to-power density ratio, which can be tailored to the specific application by altering the stoichiometric ratios of sulfur to selenium. This hybrid cathode will be developed by implementing NASA patented holey graphene technology as a highly conductive, ultra-lightweight electrode scaffold. A solid-state electrolyte will be used as a safe, non-flammable replacement to the highly flammable liquid organic electrolytes currently used in SOA lithium-ion batteries. This solid-state lithium-sulfur/selenium cell will be designed into a serial stacking configuration to enable dense packaging of the battery cells. The serial stacking configuration is termed a bipolar stack, which has the advantages of reducing overall cell weight, simplifying the interfaced connections for the cell, and minimizing the cooling requirements. Lastly, optimization of battery components will occur through a robust and rigorous combination of various computational modeling techniques covering multiple length scales. The expected result will be a fully solid-state battery with operational temperatures up to 150 °C which provides the required energy density, discharge rates, and inherent safety to meet the strict aerospace mission performance criteria. This presentation will demonstrate a feasible path for solid-state cells that possess a specific energy of greater than 400 Wh/kg to enable electric aircraft. The presentation will also explore novel materials and computational models used to achieve all solid-state cells that operate safely at very high temperatures and specific energies. The cells can withstand damage while operating without an increase in temperature or spontaneous ignition.
Single wall carbon nanotubes have attracted considerable attention because of their remarkable mechanical properties and electrical and thermal conductivities. Use of these materials as primary or secondary reinforcements in polymers or ceramics could lead to new materials with significantly enhanced mechanical strength and electrical and thermal conductivity. Use of carbon-nanotube-reinforced materials in aerospace components will enable substantial reductions in component weight and improvements in durability and safety. Potential applications for single wall carbon nanotubes include lightweight components for vehicle structures and propulsion systems, fuel cell components (bipolar plates and electrodes) and battery electrodes, and ultra-lightweight materials for use in solar sails. A major barrier to the successful use of carbon nanotubes in these components is the need for methods to economically produce pure carbon nanotubes in large enough quantities to not only evaluate their suitability for certain applications but also produce actual components. Most carbon nanotube synthesis methods, including the HiPCO (high pressure carbon monoxide) method developed by Smalley and others, employ metal catalysts that remain trapped in the final product. These catalyst impurities can affect nanotube properties and accelerate their decomposition. The development of techniques to remove most, if not all, of these impurities is essential to their successful use in practical applications. A new method has been developed at the NASA Glenn Research Center to purify gram-scale quantities of single wall carbon nanotubes. This method, a modification of a gas phase purification technique previously reported by Smalley and others, uses a combination of high-temperature oxidations and repeated extractions with nitric and hydrochloric acid. This improved procedure significantly reduces the amount of impurities (catalyst and nonnanotube forms of carbon) within the nanotubes, increasing their stability significantly. The onset of decomposition of the purified nanotubes (determined by thermal gravimetric analysis in air) is more than 300 C higher than that of the crude nanotubes. Transmission electron microscopy analysis of nanotubes purified by this method reveals near complete removal of iron catalyst particles. Analysis of the nanotubes using inductively coupled plasma spectroscopy revealed that the iron content of the nanotubes was reduced from 22.7 wt% in the crude nanotubes to less than 0.02 wt%. X-ray photoelectron spectroscopy revealed a decrease in iron content after purification as well as an increase in oxygen content due to the formation of carboxylic acid groups on the surface of the nanotubes. Nanotubes purified by this improved method can be readily dispersed in common organic solvents, in particular N,N-dimethylformamide, using prolonged ultrasonic treatment. These dispersions can then be used to incorporate single wall carbon nanotubes into polymer films.