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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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At least 19 records

High-Capacity, High-Voltage Composite Oxide Cathode Materials

This SBIR project integrates theoretical and experimental work to enable a new generation of high-capacity, high-voltage cathode materials that will lead to high-performance, robust energy storage systems. At low operating temperatures, commercially available electrode materials for lithium-ion (Li-ion) batteries do not meet energy and power requirements for NASA's planned exploration activities. NEI Corporation, in partnership with the University of California, San Diego, has developed layered composite cathode materials that increase power and energy densities at temperatures as low as 0 degC and considerably reduce the overall volume and weight of battery packs. In Phase I of the project, through innovations in the structure and morphology of composite electrode particles, the partners successfully demonstrated an energy density exceeding 1,000 Wh/kg at 4 V at room temperature. In Phase II, the team enhanced the kinetics of Li-ion transport and electronic conductivity at 0 degC. An important feature of the composite cathode is that it has at least two components that are structurally integrated. The layered material is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated and deliver a large amount of energy with stable cycling.

Hagh, Nader M.↗

Oxide Fiber Cathode Materials for Rechargeable Lithium Cells

LiCoO2 and LiNiO2 fibers have been investigated as alternatives to LiCoO2 and LiNiO2 powders used as lithium-intercalation compounds in cathodes of rechargeable lithium-ion electrochemical cells. In making such a cathode, LiCoO2 or LiNiO2 powder is mixed with a binder [e.g., poly(vinylidene fluoride)] and an electrically conductive additive (usually carbon) and the mixture is pressed to form a disk. The binder and conductive additive contribute weight and volume, reducing the specific energy and energy density, respectively. In contrast, LiCoO2 or LiNiO2 fibers can be pressed and sintered to form a cathode, without need for a binder or a conductive additive. The inter-grain contacts of the fibers are stronger and have fewer defects than do those of powder particles. These characteristics translate to increased flexibility and greater resilience on cycling and, consequently, to reduced loss of capacity from cycle to cycle. Moreover, in comparison with a powder-based cathode, a fiber-based cathode is expected to exhibit significantly greater ionic and electronic conduction along the axes of the fibers. Results of preliminary charge/discharge-cycling tests suggest that energy densities of LiCoO2- and LiNiO2-fiber cathodes are approximately double those of the corresponding powder-based cathodes.

Rice, Catherine E.↗

Studies on niobium triselenide cathode material for lithium rechargeable cells

NbSe3 exhibits superior characteristics such as high capacity, high volumetric and gravimetric energy densities, and high discharge rate capability, as compared to other intercalating cathodes. This paper reports the preparation, characterization, and performance of NbSe3. Several electrochemical techniques, such as cyclic voltammetry, constant-current/constant-potential discharges, dc potentiodynamic scans, ac impedance, and ac voltammetry, have been used to give insight to the mechanisms of intercalation of three lithiums with NbSe3 and also into the rate determining process in the reduction of NbSe3.

Ratnakumar, B. V.↗

Mixed-Domain Charge Transport in S-Se Alloys as a Li-S Battery Cathode Material

Lithium-sulfur batteries are emerging candidate systems for the next-generation long-range electric aircraft application owing to their potential to deliver high energy density per weight. Their cathodes are to be made primarily with sulfur, but sulfur by itself has much too low electron conductivity to serve as a useful cathode. An idea that has been suggested to overcome this bottleneck is to alloy sulfur with selenium in the hope that electron mobility, which is thought to improve charge transport at some expense of increased weight and reduced energy density. However, understanding of these alloy structures and their transport mechanism is insufficient, and electron mobility at varying degrees of selenium content is not well charted, which are critical for determining the optimum selenium content and testing whether this strategy is generally feasible. The difficulty of computationally characterizing these alloy systems is rooted in the structure. The structures of both sulfur and selenium exhibit eight-atom rings that pack together in various orientations to form their respective crystals. For one, because these crystals (and presumably their alloys as well) feature multiple polymorphs such that their structural coherence is rather unclear. Secondly, these are also relatively large systems (32 atoms per cell) with low-symmetry, which complicate computation both in terms of accuracy and efficiency. Thirdly, such semi-molecular, semi-crystalline structures lead to a combination of band-transport characteristics and hopping-transport characteristics, each of which is a domain with its own physics and set of computational, theoretical challenges. In addition, there is a general dearth of experimental transport data for sulfur-selenium alloys. In this study, we make a comprehensive attempt to tackle this problem using a wide array of first-principles methods. We generate special quasirandom structures to simulate alloy structures, and compute their first-principles Raman spectra for comparison with experimental data to ensure their structural soundness. We then proceed to use recently developed, state-of-the-art tool (AMSET) in order to efficiently compute electronic mobilities under band transport of pure sulfur, pure selenium, as well as their alloys of various compositions at a reasonable accuracy. We then sample numerous dimer configurations of nearest-neighbor eight-atom-ring-pairs and compute electronic hopping rates between them, which yields hopping mobility. A combination of these efforts lead to a general mapping of electron transport behaviors throughout the alloy range. Preliminary results show that introduction of selenium into sulfur initially damages electron mobility due to disorder but eventually improves it beyond that of pure sulfur with additional selenium content, ultimately peaking at the pure-selenium limit. Band transport dominates for holes in sulfur and electrons in selenium, but in all other cases, hopping transport is dominant. Ongoing efforts include determination of charge concentration and conductivity, as well as performing multiphysics modeling to determine the optimum selenium content for best tradeoff between conductivity and energy density for aircraft range.

Junsoo Park↗

Aerospace applications of sodium batteries using novel cathode materials

Preliminary fundamental investigations aimed at evaluating sodium metal chloride systems for future aerospace applications are described. Since the sodium metal chloride systems are relatively new, the approach has been to characterize their fundamental properties in order to understand their limitations. To this end, a series of fundamental electrochemical investigations have been carried out, the results of which are reported here. The metal chloride cathodes show high exchange current densities which corroborate their good reversibility in a battery application. The reduction mechanisms appear to be complex and involve multielectron transfer steps and intermediates. Such intermediates in the reaction mechanism have already been identified in the case of FeCl2. Similar mechanisms may be operative in the case of NiCl2. CuCl2, however, exhibits a second relaxation loop in the impedance plot at low frequencies and also a sloping discharge curve, unlike FeCl2 and NiCl2, which may indicate the existence of monovalent copper in the reduction mechanism.

Ratnakumar, B. V.↗

Filed emission cathodes for electrodynamic tethers: identifying compatible cathode materials

Several material combinations were considered as candidates for the electrodynamic tether application in the investigation discussed in this paper. Critical characteristics like work function, resistance, sputter yield and sensitivity to oxidizing environments were considered. The material investigation included, ZrC/Mo, Mo, MgPt, Pt, NbC/Nb, NbNi/Nb, Nb, RuTa/Ta, Ru/Ta and Ta. The results of the measurements suggest that NbC/Nb, NbNi/Nb, and MgPt are the most promising candidates.

electrodynamics tethers cathodes oxidation↗

Electrochemical studies on niobium triselenide cathode material for lithium rechargeable cells

The electrochemical behavior of NbSe3 in the battery electrolyte 1.5M LiAsF6/2Me-THF is reported. A detailed study has been carried out using various ac and dc electrochemical techniques to establish the mechanism of intercalation of three equivalents of Li with NbSe3 as well as the rate governing processes in the reduction of NbSe3. An equivalent circuit has been formulated to represent the NbSe3-solution interface. The kinetic parameters for the reduction of NbSe3 were evaluated from the ac and dc measurements. The structural change in NbSe3 on lithiation during initial discharge which results in higher cell voltages and different electrochemical response as compared to virgin NbSe3 was identified to be a loss of crystallographic order.

Ratnakumar, B. V.↗

Life test results for an ensemble of CO2 lasers

The effects of cathode material, cathode operating temperature, anode configuration, window materials, and hydrogen additives on laser lifetime are determined. Internally oxidized copper and silber-copper alloy cathodes were tested. The cathode operating temperature was raised in some tubes through the use of thermal insulation. Lasers incorporating thermally insulated silver copper oxide cathodes clearly yielded the longest lifetimes-typically in excess of 22,000 hours. The use of platinum sheet versus platinum pin anodes had no observable effect on laser lifetime. Similarly, the choice of germanium, cadmium telluride, or zinc selenide as the optical window material appears to have no impact on lifetime.

Peruso, C. J.↗

Oxygen and iron production by electrolytic smelting of lunar soil

Work during the past year involved two aspects: (1) electrolysis experiments on a larger scale than done before, and (2) collaboration with Carbotek Inc. on design for a lunar magma electrolysis cell. It was demonstrated previously that oxygen can be produced by direct electrolysis of silicate melts. Previous experiments using 50-100 mg of melt have succeeded in measuring melt resistivities, oxygen production efficiencies, and have identified the character of metal products. A series of experiments using 1-8 grams of silicate melt, done in alumina and spinel containers sufficiently large that surface tension effects between the melt and the wall are expected to have minor effect on the behavior of the melt in the region of the electrodes were completed. The purpose of these experiments was to demonstrate the durability of the electrode and container materials, demonstrate the energy efficiency of the electrolysis process, further characterize the nature of the expected metal and spinel products, measure the efficiency of oxygen production and compare to that predicted on the basis of the smaller-scale experiments, and identify any unexpected benefits or problems of the process. Four experimental designs were employed. Detailed results of these experiments are given in the appendix ('Summary of scaling-up experiments'); a general report of the results is given in terms of implications of the experiments on container materials, cathode materials, anode materials, bubble formation and frothing of the melt, cell potential, anode-cathode distance, oxygen efficiency, and energy efficiency.

Colson, R. O.↗

The loss of material from the cathode of metal arcs

A study was made of the effect of arc length, cathode thickness, current strength, gas pressure and the chemical nature of the cathode material and filling gases upon the material loss from Cu, Fe, and Ag cathodes in arcs. The results show that the analysis of the phenomenon is complex and the energy balance is difficult to formulate.

Seeliger, R.↗

Composite Cathodes for Dual-Rate Li-Ion Batteries

Composite-material cathodes that enable Li-ion electrochemical cells and batteries to function at both high energy densities and high discharge rates are undergoing development. Until now, using commercially available cathode materials, it has been possible to construct cells that have either capability for high-rate discharge or capability to store energy at average or high density, but not both capabilities. However, both capabilities are needed in robotic, standby-power, and other applications that involve duty cycles that include long-duration, low-power portions and short-duration, high-power portions. The electrochemically active ingredients of the present developmental composite cathode materials are: carbon-coated LiFePO4, which has a specific charge capacity of about 160 mA h/g and has been used as a high-discharge-rate cathode material and Li[Li(0.17)Mn(0.58)Ni(0.25)]O2, which has a specific charge capacity of about 240 mA h/g and has been used as a high-energy-density cathode material. In preparation for fabricating the composite material cathode described, these electrochemically active ingredients are incorporated into two sub-composites: a mixture comprising 10 weight percent of poly(vinylidine fluoride); 10 weight percent of carbon and 80 weight percent of carbon coated LiFePO4; and, a mixture comprising 10 weight percent of PVDF, and 80 weight percent of Li[Li(0.17)Mn(0.58)Ni(0.25)]O2. In the fabrication process, these mixtures are spray-deposited onto an aluminum current collector. Electrochemical tests performed thus far have shown that better charge/discharge performance is obtained when either 1) each mixture is sprayed on a separate area of the current collector or (2) the mixtures are deposited sequentially (in contradistinction to simultaneously) on the same current-collector area so that the resulting composite cathode material consists of two different sub-composite layers.

Whitacre, Jay↗

Nanostructured MnO2-Based Cathodes for Li-Ion/Polymer Cells

Nanostructured MnO2-based cathodes for Li-ion/polymer electrochemical cells have been investigated in a continuing effort to develop safe, high-energy-density, reliable, low-toxicity, rechargeable batteries for a variety of applications in NASA programs and in mass-produced commercial electronic equipment. Whereas the energy densities of state-of-the-art lithium-ion/polymer batteries range from 150 to 175 W h/kg, the goal of this effort is to increase the typical energy density to about 250 W h/kg. It is also expected that an incidental benefit of this effort will be increases in power densities because the distances over which Li ions must diffuse through nanostructured cathode materials are smaller than those through solid bulk cathode materials.

Skandan, Ganesh↗

Electrochemistry of lunar rocks

Electrolysis of silicate melts has been shown to be an effective means of producing metals from common silicate materials. No fluxing agents need be added to the melts. From solution in melts of diopside (CaMgSi2O6) composition, the elements Si, Ti, Ni, and Fe have been reduced to their metallic states. Platinum is a satisfactory anode material, but other cathode materials are needed. Electrolysis of compositional analogs of lunar rocks initially produces iron metal at the cathode and oxygen gas at the anode. Utilizing mainly heat and electricity which are readily available from sunlight, direct electrolysis is capable of producing useful metals from common feedstocks without the need for expendable chemicals. This simple process and the products obtained from it deserve further study for use in materials processing in space.

Lindstrom, D. 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↗

NbSe3 Cathodes For Li Rechargeable Cells

Report describes experimental studies involving preparation, characterization, and measurements of performance of NbSe3, intended for use as cathode material in lithium rechargeable electrochemical cells. Characteristics superior to those of other intercalating cathode materials, including high volumetric and gravimetric energy densities and ability to sustain discharges at high rates.

Bugga, Ratnakumar V.↗

Cold cathodes for sealed off CO2 lasers

Experimental results of a group of theoretically selected cold cathode materials are presented. These tests indicate Ag-CuO, Cu and Pt-Cu as three new cold cathode materials for sealed off CO2 lasers. The power output of a test with an Ag-CuO cathode and a gas volume of only 50 cubic centimeters varied from 0.72 W to 1.1 W at 3000 hours and yields still 0.88 W after 8000 hours. Gas discharge tubes with Cu cathodes and a volume of 25 cubic centimeters yield life times in excess of 10,000 hours. Gas analysis results, obtained from a similar tube over a period of 3000 hours, look most promising. A Pt-Cu alloy cathode shows an extremely promising V-I characteristic over a period of 2800 hours.

Hochuli, U.↗