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An Experimental Study of Upward Burning Over Long Solid Fuels: Facility Development and Comparison

As NASA's mission evolves, new spacecraft and habitat environments necessitate expanded study of materials flammability. Most of the upward burning tests to date, including the NASA standard material screening method NASA-STD-6001, have been conducted in small chambers where the flame often terminates before a steady state flame is established. In real environments, the same limitations may not be present. The use of long fuel samples would allow the flames to proceed in an unhindered manner. In order to explore sample size and chamber size effects, two large chambers were developed at NASA GRC under the Flame Prevention, Detection and Suppression (FPDS) project. The first was an existing vacuum facility, VF-13, located at NASA John Glenn Research Center. This 6350 liter chamber could accommodate fuels sample lengths up to 2 m. However, operational costs and restricted accessibility limited the test program, so a second laboratory scale facility was developed in parallel. By stacking additional two chambers on top of an existing combustion chamber facility, this 81 liter Stacked-chamber facility could accommodate a 1.5 m sample length. The larger volume, more ideal environment of VF-13 was used to obtain baseline data for comparison with the stacked chamber facility. In this way, the stacked chamber facility was intended for long term testing, with VF-13 as the proving ground. Four different solid fuels (adding machine paper, poster paper, PMMA plates, and Nomex fabric) were tested with fuel sample lengths up to 2 m. For thin samples (papers) with widths up to 5 cm, the flame reached a steady state length, which demonstrates that flame length may be stabilized even when the edge effects are reduced. For the thick PMMA plates, flames reached lengths up to 70 cm but were highly energetic and restricted by oxygen depletion. Tests with the Nomex fabric confirmed that the cyclic flame phenomena, observed in small facility tests, continued over longer sample. New features were also observed at the higher oxygen/pressure conditions available in the large chamber. Comparison of flame behavior between the two facilities under identical conditions revealed disparities, both qualitative and quantitative. This suggests that, in certain ranges of controlling parameters, chamber size and shape could be one of the parameters that affect the material flammability. If this proves to be true, it may limit the applicability of existing flammability data.

Kleinhenz, Julie↗

Gasdynamics of relativistically expanding gamma-ray burst sources - Kinematics, energetics, magnetic fields, and efficiency

We calculate both analytically and numerically the evolution of highly relativistic fireballs through the stages of free expansion and coasting, and determine the dependence of the thermodynamic and radiation variables in the comoving and laboratory flames. The dynamics and the comoving geometry change at the (lab) expansion factors r/r(0) greater than eta and r/r(0) greater than eta-squared, respectively, where eta = E(0)/M(0)c-squared is the initial Lorentz factor. In the lab, the gas appears concentrated in a thin shell of width r(0) until r/r(0) of less than about eta-squared, and increases linearly after that. Magnetic fields may have been important in the original impulsive event. We discuss their effect on the fireball dynamics and also consider their effects on the radiation emitted when the fireball runs into an external medium and is decelerated. The inverse synchro-Compton mechanism can then yield high radiative efficiency in the reverse shock (and through turbulent instabilities and mixing also in the forward blast wave), producing a burst of nonthermal radiation mainly in the MeV to GeV range. The energy and duration depend on eta, the magnetic field strength, and the external density, and can match the range of properties observed in cosmic gamma-ray bursts.

Meszaros, P.↗

Expanded Benefits for Humanity from the International Space Station

In 2012, the International Space Station (ISS) partnership published the updated International Space Station Benefits for Humanity, 2nd edition, a compilation of stories about the many benefits being realized in the areas of human health, Earth observations and disaster response, and global education. This compilation has recently been revised to include updated statistics on the impacts of the benefits, and new benefits that have developed since the first publication. Two new sections have also been added to the book, economic development of space and innovative technology. This paper will summarize the updates on behalf of the ISS Program Science Forum, made up of senior science representatives across the international partnership. The new section on "Economic Development of Space" highlights case studies from public-private partnerships that are leading to a new economy in low earth orbit (LEO). Businesses provide both transportation to the ISS as well as some research facilities and services. These relationships promote a paradigm shift of government-funded, contractor-provided goods and services to commercially-provided goods purchased by government agencies. Other examples include commercial firms spending research and development dollars to conduct investigations on ISS and commercial service providers selling services directly to ISS users. This section provides examples of ISS as a test bed for new business relationships, and illustrates successful partnerships. The second new section, Innovative Technology, merges technology demonstration and physical science findings that promise to return Earth benefits through continued research. Robotic refueling concepts for life extensions of costly satellites in geo-synchronous orbit have applications to robotics in industry on Earth. Flame behavior experiments reveal insight into how fuel burns in microgravity leading to the possibility of improving engine efficiency on Earth. Nanostructures and smart fluids are examples of materials improvements that are being developed using data from ISS. The publication also expands the benefits of research results in human health, environmental change and disaster response and in education activities developed to capture student imaginations in support of science, technology, engineering and mathematics, or STEM, education internationally. Applications to human health of the knowledge gained on ISS continues to grow and improve healthcare technologies and our understanding of human physiology. Distinct benefits return to Earth from the only orbiting multi-disciplinary laboratory of its kind. The ISS is a stepping stone for future space exploration by providing findings that develop LEO and improve life on our planet.

Rai, Amelia↗

SRB combustion dynamics analysis computer program (CDA-1)

A two-dimensional numerical model is developed for the unsteady oscillatory combustion of the solid propellant flame zone. Variations of pressure with low and high frequency responses across the long flame, such as in the double-base propellants, are accommodated. The formulation is based on a premixed, laminar flame with a one-step overall chemical reaction and the Arrhenius law of decomposition for the gaseous phase with no condensed phase reaction. Numerical calculations are carried out using the Galerkin finite elements, with perturbations expanded to the zeroth, first, and second orders. The numerical results indicate that amplification of oscillatory motions does indeed prevail in high frequency regions. For the second order system, the trend is similar to the first order system for low frequencies, but instabilities may appear at frequencies lower than those of the first order system. The most significant effect of the second order system is that the admittance is extremely oscillatory between moderately high frequency ranges.

Chung, T. J.↗

Flame Retardant Fibers for Human Space Exploration - Past, Present, and Future

The National Aeronautics and Space Administration (NASA) has led the development of unique flame retardant fibers for the specific requirements of different space programs. Three of these fibers have greatly contributed to the safety of all the space missions since the Apollo program. Beta alumina-silica microfiber developed for the outer layer of the space suit after the Apollo 1 fire is no longer used and has been replaced by other glass fibers. Expanded polytetrafluoroethylene (e-PTFE) fiber used in the current spacesuit is mostly known today through its trade mark Gore-Tex®. Polybenzimidazole (PBI) filament fiber used in many applications from the Apollo to the Space Shuttle program is no longer available. More recently, TOR"TM" copolymer of polyimide fiber developed during the space shuttle program to resist the atomic oxygen present in Low Earth Orbit has been barely used. The high cost and narrow range of aeronautical and aerospace applications have, however, led to a limited production of these fibers. Only fibers that found niche markets survived. Yet, deep space exploration will require more of these inherently flame retardant fibers than what is available today. There is a need for new flame retardant fabrics inside the space vehicles as well as a need for logistics reduction for long term space missions. Materials like modacrylic and polyimide are good candidates for future flame retardant aerospace fabrics. New fabrics must be developed for astronauts' clothing, as well as crew quarters and habitat. Therefore, both staple and filament fibers of various linear densities are needed for a three years mission to Mars.

Orndoff, Evelyne↗

Microgravity Combustion Science: 1995 Program Update

Microgravity greatly benefits the study of fundamental combustion processes. In this environment, buoyancy-induced flow is nearly eliminated, weak or normally obscured forces and flows can be isolated, gravitational settling or sedimentation is nearly eliminated, and temporal and spatial scales can be expanded. This document reviews the state of knowledge in microgravity combustion science with the emphasis on NASA-sponsored developments in the current period of 1992 to early 1995. The subjects cover basic research in gaseous premixed and diffusion-flame systems, flame structure and sooting, liquid droplets and pools, and solid-surface ignition and flame spread. They also cover applied research in combustion synthesis of ceramic-metal composites, advanced diagnostic instrumentation, and on-orbit fire safety. The review promotes continuing research by describing the opportunities for Principal Investigator participation through the NASA Research Announcement program and the available NASA Lewis Research Center ground-based facilities and spaceflight accommodations. This review is compiled by the members and associates of the NASA Lewis Microgravity Combustion Branch, and it serves as an update of two previous overview reports.

Ross, Howard D.↗

Combustion chemistry of solid propellants

Several studies are described of the chemistry of solid propellant combustion which employed a fast-scanning optical spectrometer. Expanded abstracts are presented for four of the studies which were previously reported. One study of the ignition of composite propellants yielded data which suggested early ammonium perchlorate decomposition and reaction. The results of a study of the spatial distribution of molecular species in flames from uncatalyzed and copper or lead catalyzed double-based propellants support previously published conclusions concerning the site of action of these metal catalysts. A study of the ammonium-perchlorate-polymeric-fuel-binder reaction in thin films, made by use of infrared absorption spectrometry, yielded a characterization of a rapid condensed-phase reaction which is likely important during the ignition transient and the burning process.

Baer, A. D.↗

Interaction of Burning Metal Particles

Physical characteristics of the combustion of metal particle groups have been addressed in this research. The combustion behavior and interaction effects of multiple metal particles has been studied using a microgravity environment, which presents a unique opportunity to create an "aerosol" consisting of relatively large particles, i.e., 50-300 micrometer diameter. Combustion behavior of such an aerosol could be examined using methods adopted from well-developed single particle combustion research. The experiment included fluidizing relatively large (order of 100 micrometer diameter) uniform metal particles under microgravity and igniting such an "aerosol" using a hot wire igniter. The flame propagation and details of individual particle combustion and particle interaction have been studied using a high speed movie and video-imaging with cameras coupled with microscope lenses to resolve individual particles. Interference filters were used to separate characteristic metal and metal oxide radiation bands form the thermal black body radiation. Recorded flame images were digitized and employed to understand the processes occurring in the burning aerosol. The development of individual particle flames, merging or separation, and extinguishing as well as induced particle motion have been analyzed to identify the mechanisms governing these processes. Size distribution, morphology, and elemental compositions of combustion products were characterized and used to link the observed in this project aerosol combustion phenomena with the recently expanded mechanism of single metal particle combustion.

Dreizin, Edward L.↗

Interaction of Burning Metal Particles

Physical characteristics of the combustion of metal particle groups have been addressed in this research. The combustion behavior and interaction effects of multiple metal particles has been studied using a microgravity environment, which presents a unique opportunity to create an "aerosol" consisting of relatively large particles, i.e., 50-300 m diameter. Combustion behavior of such an aerosol could be examined using methods adopted from well-developed single particle combustion research. The experiment included fluidizing relatively large (order of 100 m diameter) uniform metal particles under microgravity and igniting such an "aerosol" using a hot wire igniter. The flame propagation and details of individual particle combustion and particle interaction have been studied using a high speed movie and video-imaging with cameras coupled with microscope lenses to resolve individual particles. Interference filters were used to separate characteristic metal and metal oxide radiation bands from the thermal black body radiation. Recorded flame images were digitized and various image processing techniques including flame position tracking, color separation, and pixel by pixel image comparison were employed to understand the processes occurring in the burning aerosol. The development of individual particle flames, merging or separation, and extinguishment as well as induced particle motion have been analyzed to identify the mechanisms governing these processes. Size distribution, morphology, and elemental compositions of combustion products were characterized and used to link the observed in this project aerosol combustion phenomena with the recently expanded mechanism of single metal particle combustion.

Dreizin, Edward L.↗

An Unusual Precursor Burst with Oscillations from SAX J1808.4-3658

We report the finding of an unusual, weak precursor to a thermonuclear X-ray burst from the accreting millisecond pulsar SAX 51808.4-3658. The burst in question was observed on Oct. 19, 2002 with the Rossi X-Ray Timing Explorer (RXTE) proportional counter array (PCA). The precursor began approx. equal to 1 s prior to the onset of a strong radius expansion burst, lasted for about 0.4 s, and exhibited strong oscillations at the 401 Hz spin frequency. Oscillations are not detected in the approx. equal to 0.5 s interval between the precursor and the main burst. The estimated peak photon flux and energy fluence of the precursor are about 1/25, and 1/500 that of the main burst, respectively. From joint spectral and temporal modeling, we find that an expanding burning region with a relatively low temperature on the spinning neutron star surface can explain the oscillations, as well as the faintness of the precursor with respect to the main part of the burst. We discuss some of the implications of our findings for the ignition and spreading of thermonuclear flames on neutron stars.

Bhattacharyya, Sudip↗

Spontaneous emission from ScF in a supersonic mixing flame

An investigation was conducted of the two reactions: Sc + F2 yields ScF(asterisk) + F and Y + Cl2 yields YCl(asterisk) + Cl. Experiments were designed for studying the reactions under the relatively high pressure conditions (5-20 torr) appropriate for chemical laser operation. A shock tube was used to provide a short duration flow through a supersonic nozzle array. Shock wave heating is used to dissociate the ScCl3 or YCl3 at temperatures of about 6000 K, before the gases are accelerated and expanded through the supersonic nozzle array. The expanded primary flow is then mixed with a secondary flow of F2 introduced through slots at the trailing edge of each nozzle blade. Graphs show the temporal behavior of the visible spontaneous emission over the range from 3000 to 9000 A for a typical test condition, a microdensitometer tracing of the visible emission over the range from 4000 to 7000 A, and the spontaneous emission from ScF(asterisk) obtained by computer image processing of intensity data.

Fischell, D. R.↗

The conductive propagation of nuclear flames. I - Degenerate C + O and O + Ne + Mg white dwarfs

The paper determines the physical properties - speed, width, and density structure - of conductive burning fronts in degenerate carbon-oxygen (C + O) and oxygen-neon-magnesium (O + Ne + Mg) compositions for a grid of initial densities and compositions. The dependence of the physical properties of the flame on the assumed values of nuclear reaction rates, the nuclear reaction network employed, the thermal conductivity, and the choice of coordinate system are investigated. The occurrence of accretion-induced collapse of a white dwarf is found to be critically dependent on the velocity of the nuclear conductive burning front and the growth rate of hydrodynamic instabilities. Treating the expanding area of the turbulent burning region as a fractal whose tile size is identical to the minimum unstable Rayleigh-Taylor wavelength, it is found, for all reasonable values of the fractal dimension, that for initial C + O or O + Ne + Mg densities above about 9 x 10 exp 9 g/cu cm the white dwarf should collapse to a neutron star.

Timmes, F. X.↗

Internal Heterogeneous Processes in Aluminum Combustion

This paper discusses the aluminum particle combustion mechanism which has been expanded by inclusion of gas dissolution processes and ensuing internal phase transformations. This mechanism is proposed based on recent normal and microgravity experiments with particles formed and ignited in a pulsed micro-arc. Recent experimental findings on the three stages observed in Al particle combustion in air and shows the burning particle radiation, trajectory (streak), smoke cloud shapes, and quenched particle interiors are summarized. During stage I, the radiation trace is smooth and the particle flame is spherically symmetric. The temperature measured using a three-color pyrometer is close to 3000 K. Because it exceeds the aluminum boiling point (2730 K), this temperature most likely characterizes the vapor phase flame zone rather than the aluminum surface. The dissolved oxygen content within particles quenched during stage I was below the detection sensitivity (about 1 atomic %) for Wavelength Dispersive Spectroscopy (WDS). After an increase in the radiation intensity (and simultaneous decrease in the measured color temperature from about 3000 to 2800 K) indicative of the transition to stage II combustion, the internal compositions of the quenched particles change. Both oxygen-rich (approx. 10 atomic %) and oxygen-lean (< 1 %) regions are identified within the particles using back-scattered electron imaging and WDS. During stage II, oscillations are observed in particle radiation and the flame and smoke cloud are distorted from their original spherically-symmetric shape. In stage III, particle radiation continues to exhibit oscillations, but its radiation intensity drops and remains at a nearly constant level. The measured temperature decreases to about 2300 K. Also, larger changes in particle velocities are observed, and oxide caps are found on quenched particle surfaces. While these results showed the correlation between the aluminum particle combustion behavior and the evolution of its internal composition, the change from the spherically symmetric to asymmetric flame shape occurring upon the transition from stage I to stage II combustion could not be understood based only on the fact that dissolved oxygen is detected in the particles. The connection between the two phenomena appeared even less significant because in earlier aluminum combustion studies carried in O2/Ar mixtures, flame asymmetry was not observed as opposed to experiments in air or O2/CO mixtures. It has been proposed that the presence of other gases, i.e., hydrogen, or nitrogen causes the change in the combustion regime.

Dreizin, E. L.↗

Toxicity of Carbon Nanotubes and Its Implications for Occupational and Environmental Health

Carbon nanotubes (CNTs), which possess desirable electrical and mechanical properties, potentially have wide industrial applications. CNTs exist in two forms, single-wall (SW) and multi-wall (MW). There has been great concern that if CNTs enter the work environment as suspended respirable particulate matter (PM), they could pose an inhalation hazard. The results of recent rodent studies have collectively shown that CNTs can produce inflammation, epithelioid granulomas, fibrosis, and biochemical changes in the lungs. Studies in mice given equal amounts of test dusts showed that CNTs were more toxic than quartz and produced lesions that became progressively more pronounced. These results have led us to recommend that respirable CNT dust be considered a serious occupational health hazard, and that exposure limits be established in the expectation of expanded industrial applications. CNTs, which are totally insoluble and fibrous, would be expected to be more biopersistent than mineral fibers. Biopersistence is the key factor determining the long-term toxicity of mineral fibers and certainly of CNTs too. We have postulated that the electrical and fibrous properties of CNTs also play important roles in the toxicity of CNTs in the lungs. Recently, MWCNTs have been found in ultrafine PM aggregates in combustion streams of methane, propane, and natural-gas flames of typical stoves; indoor and outdoor fine (< 2.5 micron) PM samples were reported to contain significant fractions of MWCNTs. Environmental fine PM is mainly formed from combustion of fuels, and fine PM has been reported to be a major contributor to the induction of cardiopulmonary diseases by pollutants. Given that manufactured SWCNTs and/or MWCNTs have elicited pathological changes in the lungs and heart, we have postulated that exposure to combustion-generated MWCNTs in fine PM in the air may play a significant role in air pollution-related cardiopulmonary diseases. Therefore, CNTs from manufacturing and combustion sources in the environment could have adverse effects on human health.

Lam, Chiu-wing↗

Preliminary Results of the Third Test Series of Nonmetal Material Flammability Evaluation In SKOROST Apparatus on the Space Station Mir

The work has been done according to the US/Russian Joint Project "Experimental Evaluation of the Material Flammability in Microgravity" a continued combustion study in the SKOROST test apparatus on the OS Mir. The objective of the project was to evaluate the flammability and flame-spread rate for the selected polymer materials in low velocity flow in microgravity. Lately, the issue of nonmetal material combustion in microgravity has become of great importance, based on the necessity to develop the fire safety system for the new International Space Station (ISS). Lack of buoyant flow in microgravity reduces oxygen transfer into the combustion zone, which leads to flame extinction when the flow velocity is less than the limiting flow velocity V(sub lim) for the material. The ISS FGB fire-safety system was developed based on this phenomenon. The existence of minimum flow velocity V(sub lim) to sustain fire for the selected materials was determined both theoretically and experimentally. In the latter, it is shown that, even for thermally thin nonmetal materials with a very low oxygen index C(sub lim) of 12.5% (paper sheets with the thickness of 0.1 mm), a limiting flow velocity V(sub lim) exists at oxygen concentration Co(sub OX) = 17-21%, and is about 1.0 - 0.1 cm/sec. This might be explained by the relative increase in thermal losses due to radiation from the surface and from the gaseous phase. In the second series of experiments in Skorost apparatus on Orbital Station Mir the existence of the limiting flow velocity V(sub lim) for combustion was confirmed for PMMA and glass-epoxy composite strip samples 2 mm thick at oxygen concentration C(sub OX) = 21.5%. It was concluded that V(sub lim) depends on C(sub OX) for the PMMA sample with a low oxygen index of 15.5%, the limiting flow velocity V(sub lim) was less than 0.5 cm/sec, and for the glass-epoxy composite sample with a high oxygen index of 19%, the limiting flow velocity V(sub lim) was higher than 15 cm/sec. As of now only those materials that maintain their integrity during combustion were investigated. The materials that disintegrate when burning present more danger for fire safety because the flame can spread farther with the parts of the structure, ejected melt drops, et cetera. Materials such as polyethylene are of great interest since they form a lengthy melt zone during the combustion in normal gravity. This melt zone generates drops of liquids that promote faster flame spread compared to usual combustion. The preliminary results of polyethylene insulation flammability evaluation in microgravity are shown in the NASA Wire Insulation Flammability (WIF) experiment during Space Shuttle flight STS-50. A lot of interesting data was collected during the WIF test program. However, one of the most important results was that, in microgravity, the extinction of the polyethylene occurred almost immediately when the flow of relatively low oxygen concentration (C(sub OX)=21%) was stopped. The purpose of the work reported here is to expand the existing data base on material flammability in microgravity and to conduct the third series of the space experiment using Skorost apparatus on Orbiatl Station Mir with melting polymers, which might increase the probability of fire and its propagation in ventilated microgravity environment of orbiting spacecraft.

Ivanov, A. V.↗

Large Scale Experiments on Spacecraft Fire Safety

Full scale fire testing complemented by computer modelling has provided significant know how about the risk, prevention and suppression of fire in terrestrial systems (cars, ships, planes, buildings, mines, and tunnels). In comparison, no such testing has been carried out for manned spacecraft due to the complexity, cost and risk associated with operating a long duration fire safety experiment of a relevant size in microgravity. Therefore, there is currently a gap in knowledge of fire behaviour in spacecraft. The entire body of low-gravity fire research has either been conducted in short duration ground-based microgravity facilities or has been limited to very small fuel samples. Still, the work conducted to date has shown that fire behaviour in low-gravity is very different from that in normal-gravity, with differences observed for flammability limits, ignition delay, flame spread behaviour, flame colour and flame structure. As a result, the prediction of the behaviour of fires in reduced gravity is at present not validated. To address this gap in knowledge, a collaborative international project, Spacecraft Fire Safety, has been established with its cornerstone being the development of an experiment (Fire Safety 1) to be conducted on an ISS resupply vehicle, such as the Automated Transfer Vehicle (ATV) or Orbital Cygnus after it leaves the ISS and before it enters the atmosphere. A computer modelling effort will complement the experimental effort. Although the experiment will need to meet rigorous safety requirements to ensure the carrier vehicle does not sustain damage, the absence of a crew removes the need for strict containment of combustion products. This will facilitate the possibility of examining fire behaviour on a scale that is relevant to spacecraft fire safety and will provide unique data for fire model validation. This unprecedented opportunity will expand the understanding of the fundamentals of fire behaviour in spacecraft. The experiment is being developed by an international topical team that is collaboratively defining the experiment requirements and performing supporting analysis, experimentation and technology development. This paper presents the objectives, status and concept of this project.

Urban, David L.↗

Large Scale Experiments on Spacecraft Fire Safety

Full scale fire testing complemented by computer modelling has provided significant knowhow about the risk, prevention and suppression of fire in terrestrial systems (cars, ships, planes, buildings, mines, and tunnels). In comparison, no such testing has been carried out for manned spacecraft due to the complexity, cost and risk associated with operating a long duration fire safety experiment of a relevant size in microgravity. Therefore, there is currently a gap in knowledge of fire behaviour in spacecraft. The entire body of low-gravity fire research has either been conducted in short duration ground-based microgravity facilities or has been limited to very small fuel samples. Still, the work conducted to date has shown that fire behaviour in low-gravity is very different from that in normal gravity, with differences observed for flammability limits, ignition delay, flame spread behaviour, flame colour and flame structure. As a result, the prediction of the behaviour of fires in reduced gravity is at present not validated. To address this gap in knowledge, a collaborative international project, Spacecraft Fire Safety, has been established with its cornerstone being the development of an experiment (Fire Safety 1) to be conducted on an ISS resupply vehicle, such as the Automated Transfer Vehicle (ATV) or Orbital Cygnus after it leaves the ISS and before it enters the atmosphere. A computer modelling effort will complement the experimental effort. Although the experiment will need to meet rigorous safety requirements to ensure the carrier vehicle does not sustain damage, the absence of a crew removes the need for strict containment of combustion products. This will facilitate the possibility of examining fire behaviour on a scale that is relevant to spacecraft fire safety and will provide unique data for fire model validation. This unprecedented opportunity will expand the understanding of the fundamentals of fire behaviour in spacecraft. The experiment is being developed by an international topical team that is collaboratively defining the experiment requirements and performing supporting analysis, experimentation and technology development. This paper presents the objectives, status and concept of this project.

Urban, David↗

Optimized Li-Ion Electrolytes Containing Fluorinated Ester Co-Solvents

A number of experimental lithium-ion cells, consisting of MCMB (meso-carbon microbeads) carbon anodes and LiNi(0.8)Co(0.2)O2 cathodes, have been fabricated with increased safety and expanded capability. These cells serve to verify and demonstrate the reversibility, low-temperature performance, and electrochemical aspects of each electrode as determined from a number of electrochemical characterization techniques. A number of Li-ion electrolytes possessing fluorinated ester co-solvents, namely trifluoroethyl butyrate (TFEB) and trifluoroethyl propionate (TFEP), were demonstrated to deliver good performance over a wide temperature range in experimental lithium-ion cells. The general approach taken in the development of these electrolyte formulations is to optimize the type and composition of the co-solvents in ternary and quaternary solutions, focusing upon adequate stability [i.e., EC (ethylene carbonate) content needed for anode passivation, and EMC (ethyl methyl carbonate) content needed for lowering the viscosity and widening the temperature range, while still providing good stability], enhancing the inherent safety characteristics (incorporation of fluorinated esters), and widening the temperature range of operation (the use of both fluorinated and non-fluorinated esters). Further - more, the use of electrolyte additives, such as VC (vinylene carbonate) [solid electrolyte interface (SEI) promoter] and DMAc (thermal stabilizing additive), provide enhanced high-temperature life characteristics. Multi-component electrolyte formulations enhance performance over a temperature range of -60 to +60 C. With the need for more safety with the use of these batteries, flammability was a consideration. One of the solvents investigated, TFEB, had the best performance with improved low-temperature capability and high-temperature resilience. This work optimized the use of TFEB as a co-solvent by developing the multi-component electrolytes, which also contain non-halogenated esters, film forming additives, thermal stabilizing additives, and flame retardant additives. Further optimization of these electrolyte formulations is anticipated to yield improved performance. It is also anticipated that much improved performance will be demonstrated once these electrolyte solutions are incorporated into hermetically sealed, large capacity prototype cells, especially if effort is devoted to ensure that all electrolyte components are highly pure.

Prakash, G. K. Surya↗