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Ambient temperature secondary lithium cells have a number of intrinsic advantages over aqueous secondary systems such as higher specific energy and energy density as well as long active shelf life.
NASA requires lightweight rechargeable batteries for future missions to Mars and the outer planets that are capable of operating over a wide range of temperatures, with high specific energy and energy densities. Due to their attractive performance characteristics, lithium-ion batteries have been identified as the battery chemistry of choice for a number of future applications, including planetary orbiters, rovers and landers. For example, under the Mars Surveyor Program MSP 01 lithium-ion batteries were developed by Lithion (each being 28 V, 25 Ah, 8-cells. and 9 kg) and fully qualified prior to mission cancellation. In addition to the requirement of being able to supply at least 90 cycles on the surface of Mars, the battery demonstrated operational capability (both charge and discharge) over a large temperature range (-2O'C to +4OoC), with tolerance to non-operational excursions to -30nd 50Currently, JPL is implementing lithium-ion technology on the 2003 Mars Exploration Rover (MER), which will be coupled with a solar array. This mission has similar performance requirements to that of the 2001 Lander in that high energy density and a wide operating temperature range are necessitated. In addition to planetary rover and lander applications, we are also engaged in determining the viability of using lithium-ion technology for orbiter applications that require exceptionally long life (>20,000 cydes at partial depth of discharge). To assess the viabili of lithium-ion cells for these applications, a number of performance characterization tests have been performed (at the cell and battery level) on state-of-art prototype lihium- ion cells, induding: assessing the cycle life performance (at varying DODs), life characteristics at extreme temperatures (< -10nd >+4OoC), rate capability as a function of temperature (-30' to 4OoC), pulse capability, self-discharge and storage characteristics, as well as, mission profile capability. This paper will describe the current and future NASA missions that are considering lithium ion batteries and will contain results of the cell testing conducted to-date to validate the technology for these missions.
NASA's 2003 Mars Exploration Rover (MER) missions, Spirit and Opportunity, have been performing exciting surface exploration studies for the past six months. These two robotic missions were aimed at examining the presence of water and, thus, any evidence of life, and at understanding the geological conditions of Mars, These rovers have been successfully assisted by primary lithium-sulfur dioxide batteries during the critical entry, descent, and landing (EDL) maneuvers. These batteries were located on the petals of the lander, which, unlike in the Mars Pathfinder mission, was designed only to carry the rover. The selection of the lithium-sulfur dioxide battery system for this application was based on its high specific energy and high rate discharge capability, combined with low heat evolution, as dictated by this application. Lithium-sulfur dioxide batteries exhibit voltage delay, which tends to increase at low discharge temperatures, especially after extended storage at warm temperatures, In the absence of a depassivation circuit, as provided on earlier missions, e.g., Galileo, we were required to depassivate the lander primary batteries in a unique manner. The batteries were brought onto a shunt-regulated bus set at pre-selected discharge voltages, thus affecting depassivation during constant discharge voltages. Several ground tests were preformed, on cells, cell strings and battery assembly with five parallel strings, to identify optimum shunt voltages and durations of depassivation. We also examined the repassivation of lithium anodes, subsequent to depassivation. In this paper, we will describe these studies, in detail, as well as the depassivation of the lander flight batteries on both Spirit and Opportunity rover prior to the EDL sequence and their performance during landing on Mars.
SAFT prismatic wound 5 Ahr MP series cells were evaluated for potential application in a lithium ion battery designed for Tactical Mobile Robots (TMR). In order to satisfy battery design requirements, a 10 Ahr battery containing two parallel 8-cell strings was proposed. The proposed battery has a weight and volume of approximately 3.2kg and 1.6 liters, respectively. Cell qualification procedures include initial characterization, followed by charge/discharge cycling at 100% DOD with intermittent EIS measurements at various state of charge. Certain cells were also subjected to extreme operational temperatures for worst-case analysis. Excellent specific energy (>130 Whr/kg) was obtained with initial characterization cycles. Even at abusive thermal conditions, the cell capacity fade was less than Ahr after 300 cycles. Rate characterization showed good cell discharge behavior with minimal decrease in capacity. At various state of charge, impedance measurements suggest that the cathode play a more significant role in capacity. At various state of charge impedance measurements suggest that the cathode play a more significant role in capacity fade than the anode.
Due to its high specific energy content, liquid hydrogen (LH2) is emerging as an alternative fuel for future aircraft. As a result, there is a need for hydrogen tank storage systems, for these aircraft applications, that are expected to provide sufficient capacity for flight durations ranging from a few minutes to several days. It is understood that the development of a large, lightweight, reusable cryogenic liquid storage tank is crucial to meet the goals of and supply power to hydrogen-fueled aircraft, especially for long flight durations. This report provides an annotated review (including the results of an extensive literature review) of the current state of the art of cryogenic tank materials, structural designs, and insulation systems along with the identification of key challenges with the intent of developing a lightweight and long-term storage system for LH2. The broad classes of insulation systems reviewed include foams (including advanced aerogels) and multilayer insulation (MLI) systems with vacuum. The MLI systems show promise for long-term applications. Structural configurations evaluated include single- and double-wall constructions, including sandwich construction. Potential wall material candidates are monolithic metals as well as polymer matrix composites and discontinuously reinforced metal matrix composites. For short-duration flight applications, simple tank designs may suffice. Alternatively, for longer duration flight applications, a double-wall construction with a vacuum-based insulation system appears to be the most optimum design. The current trends in liner material development are reviewed in the case that a liner is required to minimize or eliminate the loss of hydrogen fuel through permeation.
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.
This guideline discusses a standard approach for defining, determining, and addressing safety, handling, and qualification standards for lithium-ion (Li-Ion) batteries to help the implementation of the technology in aerospace applications. Information from a variety of other sources relating to Li-ion batteries and their aerospace uses has been collected and included in this document. The sources used are listed in the reference section at the end of this document. The Li-Ion chemistry is highly energetic due to its inherent high specific energy and its flammable electrolyte. Due to the extreme importance of appropriate design, test, and hazard control of Li-ion batteries, it is recommended that all Government and industry users and vendors of this technology for space applications, especially involving humans, use this document for appropriate guidance prior to implementing the technology.
This viewgraph presentation reviews NASA Space Missions that are enabled by Space Nuclear Systems. The topics include: 1) Space Nuclear System Applications; 2) Trade Space for Electric Power Systems; 3) Power Generation Specific Energy Trade Space; 4) Radioisotope Power Generation; 5) Radioisotope Missions; 6) Fission Power Generation; 7) Solar Powered Lunar Outpost; 8) Fission Powered Lunar Outpost; 9) Fission Electric Power Generation; and 10) Fission Nuclear Thermal Propulsion.
In 2009, the Cascade Distillation Subsystem (CDS) wastewater processor (Honeywell International, Torrance, CA) was assessed in the National Aeronautics and Space Administration (NASA) Exploration Life Support (ELS) distillation comparison test. The purpose of the test was to collect data to support down-selection and development of a primary distillation technology for application in a lunar outpost water recovery system. The CDS portion of the comparison test was conducted between May 6 and August 19, 2009. The system was challenged with two pretreated test solutions, each intended to represent a feasible wastewater generated in a surface habitat. The 30-day equivalent wastewater loading volume for a crew of four was processed for each wastewater solution. Test Solution 1 consisted of a mixed stream containing human-generated urine and humidity condensate. Test Solution 2 contained the addition of human-generated hygiene wastewater to the solution 1 waste stream components. Approximately 1500 kg of total wastewater was processed through the CDS during testing. Respective recoveries per solution were 93.4 +/- 0.7 and 90.3 +/- 0.5%. The average specific energy of the system was calculated to be less than 130 W-hr/kg. The following paper provides detailed information and data on the performance of the CDS as challenged per the ELS distillation comparison test.
Lithium dinitramide, LiN(NO2)2 has shown promise as an additive to nonaqueous electrolytes in rechargeable and non-rechargeable lithium-ion-based electrochemical power cells. Such non-aqueous electrolytes consist of lithium salts dissolved in mixtures of organic ethers, esters, carbonates, or acetals. The benefits of adding lithium dinitramide (which is also a lithium salt) include lower irreversible loss of capacity on the first charge/discharge cycle, higher cycle life, lower self-discharge, greater flexibility in selection of electrolyte solvents, and greater charge capacity. The need for a suitable electrolyte additive arises as follows: The metallic lithium in the anode of a lithium-ion-based power cell is so highly reactive that in addition to the desired main electrochemical reaction, it engages in side reactions that cause formation of resistive films and dendrites, which degrade performance as quantified in terms of charge capacity, cycle life, shelf life, first-cycle irreversible capacity loss, specific power, and specific energy. The incidence of side reactions can be reduced through the formation of a solid-electrolyte interface (SEI) a thin film that prevents direct contact between the lithium anode material and the electrolyte. Ideally, an SEI should chemically protect the anode and the electrolyte from each other while exhibiting high conductivity for lithium ions and little or no conductivity for electrons. A suitable additive can act as an SEI promoter. Heretofore, most SEI promotion was thought to derive from organic molecules in electrolyte solutions. In contrast, lithium dinitramide is inorganic. Dinitramide compounds are known as oxidizers in rocket-fuel chemistry and until now, were not known as SEI promoters in battery chemistry. Although the exact reason for the improvement afforded by the addition of lithium dinitramide is not clear, it has been hypothesized that lithium dinitramide competes with other electrolyte constituents to react with lithium on the surface of the anode to form a beneficial SEI. Apparently, nitrides and oxides that result from reduction of lithium dinitramide on the anode produce a thin, robust SEI different from the SEIs formed from organic SEI promoters. The SEI formed from lithium dinitramide is more electronically insulating than is the film formed in the presence of an otherwise identical electrolyte that does not include lithium dinitramide. SEI promotion with lithium dinitramide is useful in batteries with metallic lithium and lithium alloy anodes.
An object has a taggant placed in a first portion thereof and has a visible symbol placed on a second portion thereof. When the object is to be identified and authenticated, the taggant is made to radiate with a specific energy signature. The energy signature and at least one image of the symbol are recorded along with a relative location that identifies the first portion of the object. The combination of the energy signature, symbol image and relative location are used to repeatedly identify and authenticate the object.
In 2009, the Cascade Distillation Subsystem (CDS) wastewater processor (Honeywell International, Torrance, California) was assessed in the National Aeronautics and Space Administration (NASA) Exploration Life Support (ELS) distillation comparison test. The purpose of the test was to collect data to support down-selection and development of a primary distillation technology for application in a lunar outpost water recovery system. The CDS portion of the comparison test was conducted between May 6 and August 19, 2009. The system was challenged with two pretreated test solutions, each intended to represent a feasible wastewater generated in a surface habitat. The 30-day equivalent wastewater loading volume for a crew of four was intended to be processed for each wastewater solution. Test Solution 1 consisted of a mixed stream containing human-generated urine and humidity condensate. Test Solution 2 contained the addition of human-generated hygiene wastewater to the solution 1 waste stream components. Approximately 1500 kg of total wastewater was processed through the CDS during testing. Respective recoveries per solution were 93.4 +/- 0.7 and 90.3 +/- 0.5 percent. The average specific energy of the system during testing was calculated to be less than 120 W-hr/kg. The following paper provides detailed information and data on the performance of the CDS as challenged per the ELS distillation comparison test.
Testing of the Wiped-film Rotating-disk (WFRD) evaporator was conducted in support of the Exploration Life Support Distillation Down-Select Test. The WFRD was constructed at NASA Ames Research Center (ARC) and tested at NASA Marshall Space Flight Center (MSFC). The WFRD was delivered to MSFC in September 2009, and testing of solution #1 and solution #2 immediately following. Solution #1 was composed of humidity condensate and urine, including flush water and pretreatment chemicals. Solution #2 was composed of hygiene water, humidity condensate, and urine, including flush water and pretreatment chemicals. During the testing, the operational parameters of the WFRD were recorded and samples of the feed, brine, and product were collected and analyzed. The steady-state results of processing 414L of feed solution #1 and 1283L of feed solution #2 demonstrated that running the WFRD at a brine temperature of 50 C gave an average production rate of 16.7 L/hr. The specific energy consumption was 80.5W-hr/L. Data Analysis shows that the water recovery rates were 94% and 91%, respectively. The total mass of the WFRD as delivered to MSFC was 300 Kg. The volume of the tests stand rack was 1m width x 0.7m depth x 1.9m height or 1.5 cu m of which about half of the total volume is occupied by equipment. Chemical analysis of the distillate showed an average TOC of 20ppm, a pH of 3.5, and a conductivity of 98 mho/cm. The conductivity of the distillate, compared to the feed, decreased by 98.9%., the total ion concentration decreased by 99.6%, the total organics decreased 98.6%, and the metals were at or below detection limits
The NASA Glenn Research Center (GRC) Electrochemistry Branch designed and built five lithium-ion battery packs for demonstration in spacesuit simulators as a part of the 2007 Desert Research and Technology Studies (D-RATS) activity at Cinder Lake, Arizona. The experimental batteries incorporated advanced, NASA-developed electrolytes and included internal protection against over-current, overdischarge and over-temperature. The 500-g experimental batteries were designed to deliver a constant power of 22 W for 2.5 hr with a minimum voltage of 13 V. When discharged at the maximum expected power output of 38.5 W, the batteries operated for 103 min of discharge time, achieving a specific energy of 130 Wh/kg. This report summarizes design details and safety considerations. Results for field trials and laboratory testing are summarized.
In support of launch vehicle base heating and pressure prediction efforts using the Loci-CHEM Navier-Stokes computational fluid dynamics solver, 35 numerical simulations of the NASA TND-1093 wind tunnel test have been modeled and analyzed. This test article is composed of four JP-4/LOX 500 lbf rocket motors exhausting into a Mach 2 - 3.5 wind tunnel at various ambient pressure conditions. These water-cooled motors are attached to a base plate of a standard missile forebody. We explore the base heating profiles for fully coupled finite-rate chemistry simulations, one-way coupled RAMP (Reacting And Multiphase Program using Method of Characteristics)-BLIMPJ (Boundary Layer Integral Matrix Program - Jet Version) derived solutions and variable and constant specific heat ratio frozen flow simulations. Variations in turbulence models, temperature boundary conditions and thermodynamic properties of the plume have been investigated at two ambient pressure conditions: 255 lb/sq ft (simulated low altitude) and 35 lb/sq ft (simulated high altitude). It is observed that the convective base heat flux and base temperature are most sensitive to the nozzle inner wall thermal boundary layer profile which is dependent on the wall temperature, boundary layer s specific energy and chemical reactions. Recovery shock dynamics and afterburning significantly influences convective base heating. Turbulence models and external nozzle wall thermal boundary layer profiles show less sensitivity to base heating characteristics. Base heating rates are validated for the highest fidelity solutions which show an agreement within +/-10% with respect to test data.
A number of future NASA missions involving the exploration of the Moon and Mars will be human-rated and thus require high-specific-energy rechargeable batteries that possess enhanced safety characteristics. Given that Li-ion technology is the most viable rechargeable energy storage device for near-term applications, effort has been devoted to improving the safety characteristics of this system. There is also a strong desire to develop Li-ion batteries with improved safety characteristics for terrestrial applications, most notably for hybrid electric vehicle (HEV) and plug-in hybrid electric vehicle (PHEV) automotive applications. Therefore, extensive effort has been devoted recently to developing non-flammable electrolytes to reduce the flammability of the cells/battery. A number of electrolyte formulations have been developed, including systems that (1) incorporate greater concentrations of the flame-retardant additive (FRA); (2) use di-2,2,2-trifluoroethyl carbonate (DTFEC) as a co-solvent; (3) use 2,2,2- trifluoroethyl methyl carbonate (TFEMC); (4) use mono-fluoroethylene carbonate (FEC) as a co-solvent and/or a replacement for ethylene carbonate in the electrolyte mixture; and (5) utilize vinylene carbonate as a "SEI promoting" electrolyte additive, to build on the favorable results previously obtained. To extend the family of electrolytes developed under previous work, a number of additional electrolyte formulations containing FRAs, most notably triphenyl phosphate (TPP), were investigated and demonstrated in experimental MCMB (mesocarbon micro beads) carbon- LiNi(0.8)Co(0.2)O2 cells. The use of higher concentrations of the FRA is known to reduce the flammability of the electrolyte solution, thus, a concentration range was investigated (i.e., 5 to 20 percent by volume). The desired concentration of the FRA is the highest amount tolerable without adversely affecting the performance in terms of reversibility, ability to operate over a wide temperature range, and the discharge rate capability. The use of fluorinated carbonates, much in the same manner as the incorporation of fluorinated ester-based solvents, was employed to reduce the inherent flammability of mixtures. Thus, electrolyte formulations that embody both approaches are anticipated to have much lower flammability, resulting in enhanced safety.
Lithium primary and lithium ion secondary batteries provide high specific energy and energy density. The use of these batteries also helps to reduce launch weight. Both primary and secondary cells can be packaged as high-rate cells, which can present a threat to crew and equipment in the event of external or internal short circuits. Overheating of the cell interior from high current flows induced by short circuits can result in exothermic reactions in lithium primary cells and fully charged lithium ion secondary cells. Venting of the cell case, ejection of cell components, and fire have been reported in both types of cells, resulting from abuse, cell imperfections, or faulty electronic control design. A switch has been developed that consists of a thin layer of composite material made from nanoscale particles of nickel and Teflon that conducts electrons at room temperature and switches to an insulator at an elevated temperature, thus interrupting current flow to prevent thermal runaway caused by internal short circuits. The material is placed within the cell, as a thin layer incorporated within the anode and/or the cathode, to control excess currents from metal-to-metal or metal-to-carbon shorts that might result from cell crush or a manufacturing defect. The safety of high-rate cells is thus improved, preventing serious injury to personnel and sensitive equipment located near the battery. The use of recently available nanoscale particles of nickel and Teflon permits an improved, homogeneous material with the potential to be fine-tuned to a unique switch temperature, sufficiently below the onset of a catastrophic chemical reaction. The smaller particles also permit the formation of a thinner control film layer (<50 m), which can be incorporated into commercial high-rate lithium primary and secondary cells. The innovation permits incorporation in current lithium and lithium-ion cell designs with a minimal impact on cell weight and volume. The composite thermal switch (CTS(TradeMark)) coating can be incorporated in either the anode or cathode or both. The coating can be applied in a variety of different processes that permits incorporation in the cell and electrode manufacturing processes. The CTS responds quickly and halts current flow in the hottest parts of the cell first. The coating can be applied to metal foil and supplied as a cell component onto which the active electrode materials are coated.
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.