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At least 127 records · Page 7

Development of High Conductivity Lithium-Ion Electrolytes for Low Temperature Cell Applications

NASA has continued interest in developing power sources which are capable of operating at low temperatures (-20 C and below) to enable future missions, such as the Mars Rover and Lander. Thus, under a program sponsored by the Mars Exploration Program, we have been involved in developing Li-ion batteries with improved low temperature performance. To accomplish this task, the focus of the research has been upon the development of advanced electrolyte systems with improved low temperature properties. This had led to the identification of a carbonate-based electrolyte, consisting of 1.0 M LiPF6 in EC + DEC + DMC (33:33:34), which has been shown to have excellent performance at -20 C in Li-ion AA-size prototype cells. Other groups are also actively engaged in developing electrolytes which can result in improved low temperature performance of Li-ion cells, including Polystor, Yardney, and Covalent. In addition to developing cells capable of operation at -20 C, there is continued interest in systems which can successfully operate at even lower temperatures (less than -30 C) and at high discharge rates (greater than C/2). Thus, we are currently focusing upon developing advanced electrolytes which are highly conductive at low temperatures and will result in cells capable of operation at -40 C. One approach to improve the low temperature conductivity of ethylene carbonate-based electrolytes involves adding co-solvents which will decrease the viscosity and extend the liquid range. Candidate solvent additives include formates, acetates, cyclic and aliphatic ethers, lactones, as well as other carbonates. Using this approach, we have prepared a number of electrolytes which contain methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), ethyl proprionate (EP), and 1,2-dimethoxyethane (DME), some of which have been characterized and reported. Other groups have also reported electrolytes based on mixtures of carbonates and acetates. In the present study, electrolytes which have been identified to have good low temperature conductivity and stability were incorporated into lithium-graphite cells for evaluation. Using various electrochemical methods, including ac impedence and DC micropolarization techniques, the film formation characteristics of graphite electrodes in contact with various lectrolyte formulations was investigated.

Smart, M. C.↗

Performance of LI-1542 reusable surface insulation system in a hypersonic stream

The thermal and structural performance LI-1542 reusable surface insulation (RSI) tiles was investigated. The test panel was designed to represent part of the surface structure on a space shuttle orbiter fuselage along a 1250 K isotherm. Aerothermal tests were conducted at a free-stream Mach number of 6.6, a total temperature of 1820 K, Reynolds numbers of 2 millon and 5 million per meter, and dynamic pressures of 26 and 65 kPa. The RSI tiles demonstrated good thermal protection and structural integrity. High temperatures were caused by misalinement in tile height, offset the tile longitudinal alinement, and leakage around thermal seals when differential pressure existed across the panel. The damage tolerance of LI-1542 RSI appeared high. The tile coating crazed early in the test program, but this did not effect the tile integrity. Erosion of the tile edges occurred at forward-facing steps and at the ends of longitudinal gaps because of particle impacts and flow shear.

Hunt, L. R.↗

Performance of LI-1542 reusable surface insulation system in a hypersonic stream

The thermal and structural performance of a large panel of LI-1542 reusable surface insulation tiles was determined by a series of cyclic heating tests using radiant lamps and aerothemal tests in the Langley 8-foot high-temperature structures tunnel. Aerothermal tests were conducted at a free-stream Mach number of 6.6, a total temperature of 1830 K, Reynolds numbers of 2.0 and 4,900,000 per meter, and dynamic pressures of 29 and 65 kPa. The results suggest that pressure gradients in gaps and flow impingement on the header walls at the end of longitudinal gaps are sources for increased gap heating. Temperatures higher than surface radiation equilibrium temperature were measured deep in gaps and at the header walls. Also, the damage tolerance of the LI-1542 tiles appears to be very high. Tile edge erosion rate was slow; could not be tolerated in a shuttle application. Tiles soaked with water and subjected to rapid depressurization and aerodynamic heating showed no visible evidence of damage.

Hunt, L. R.↗

Notch sensitivity of space shuttle tile materials

Tests were conducted at room temperature to determine the notch sensitivity of the thermal protection tile for the space shuttle. Two types of RSI tile were studied: LI-900 and LI-2200. Three point bend specimens were cut from discarded tiles in the in-plane (ip) and through-the-thickness (ttt) directions. They were tested with or without a sharp notch. The LI-900 (ip and ttt) specimens were not very notch sensitive, but the LI-2200 (ip and ttt) specimens were. The LI-2200 material showed about a 35 percent reduction in strength due to the presence of the notch. This reduction in strength should be considered in the design of mechanically fastened tile concepts.

Newman, J. C., Jr.↗

A lithium oxygen secondary battery

Some recent work on a lithium-oxygen secondary battery is reported in which stabilized zirconia oxygen vacancy conducting solid electrolytes were used for the effective separation of respective half-cell reactions. The electroactive material consisted of alloys possessing the general composition Li(x)FeSi2 immersed in a ternary molten salt comprising LiF, LiCl, and Li2O. The manufacture of the cell is described, and discharge-current voltage curves for partially charged cells are shown and discussed. A galvanostatic IR free-changing curve and an IR-free charge-discharge curve are also shown.

Semkow, Krystyna W.↗

Potential applications of MMC and aluminum-lithium alloys in cameras for CRAF spacecraft

In undertaking the design of a 2000-mm focal length camera for the Mariner Mark II series of spacecraft, JPL sought novel materials with the requisite dimensional and thermal stability, outgassing and corrosion resistance, low mass, high stiffness, and moderate cost. Metal-matrix composites and Al-Li alloys have, in addition to excellent mechanical properties and low density, a suitably low coefficient of thermal expansion, high specific stiffness, and good electrical conductivity. The greatest single obstacle to application of these materials to camera structure design is noted to have been the lack of information regarding long-term dimensional stability.

Lane, Marc↗

Performance Testing of Yardney MCMB-LiNiCoAlO2 Lithium-ion Cells Possessing Electrolytes with Improved Safety Characteristics

Many future NASA missions aimed at exploring the Moon and Mars require high specific energy rechargeable batteries that possess enhanced safety characteristics. There is also a strong desire to develop Li-ion batteries with improved safety characteristics for terrestrial applications, most notably for HEV and PHEV automotive applications. In previous work focused upon evaluating various potential flame retardant additives1, triphenyl phosphate (TPP)2 was observed to have the most desirable attributes, including good life characteristics and resilience to high voltage operation. We have employed a number of approaches in the design of promising TPP-based electrolytes with improved safety, including: (a) varying the flame retardant additive (FRA) content (from 5 to 15%), (b) the use of fluorinated co-solvents, (c) the use of additives to improve compatibility, and (c) the use of ester co-solvents to decrease the viscosity and increase the conductivity. In recent work, we have demonstrated a number of these electrolyte formulations to be compatible with a number of chemistries, including: MCMB carbon-LiNi0.8Co0.2O2, graphite-LiNi0.8Co0.15Al0.05O2, Li-Li(Li0.17Ni 0.25 Mn 0.58 )O2, Li-LiNiCoMnO2 and graphite- LiNiCoMnO2.3,4 In the current study, we have demonstrated the performance of a number of TPP-containing electrolytes in 7 Ah prototype MCMB-LiNiCoO2 cells. We will describe the results of a number of performance tests, including: a) 100% DOD cycle life testing at various temperatures, b) discharge rate characterization as a function of temperature, c) charge rate characterization as a function of temperature, and d) impedance as a function of temperature. In addition to displaying good life characteristics, being comparable to baseline chemistries, a number of cells were observed to provide good performance over a wide temperature range.

Li-ion batteries↗

Functional and Multifunctional Polymers: Materials for Smart Structures

The ultimate goal of the research in smart structures and smart materials is the development of a new generation of products/devices which will perform better than products/devices built from passive materials. There are a few examples of multilayer polymer systems which function as smart structures, e.g. a synthetic muscle which is a multilayer assembly of a poly(ethylene) layer, a gold layer, and a poly(pyrrole) layer immersed in a liquid electrolyte. Oxidation and reductions of the active pyrrole layer causes the assembly to reversibly deflect and mimic biological muscles. The drawback of such a setup is slow response times and the use of a liquid electrolyte. We have developed multifunctional polymers which will eliminate the use of a liquid electrolyte, and also because the functionalities of the polymers are within a few hundred angstroms, an improved response time to changes in the external field should be possible. Such multifunctional polymers may be classified as the futuristic 'smart materials.' These materials are composed of a number of different functionalities which work in a synergistic fashion to function as a device. The device performs on the application of an external field and such multifunctional polymers may be scientifically labeled as 'field responsive polymers.' Our group has undertaken a systematic approach to develop functional and multifunctional polymers capable of functioning as field responsive polymers. Our approach utilizes multicomponent polymer systems (block copolymers and graft copolymers), the strategy involves the preparation of block or graft copolymers where the functionalities are limited to different phases in a microphase separated system. Depending on the weight (or volume) fractions of each of the components, different microstructures are possible. And, because of the intimate contact between the functional components, an increase in the synergism between the functionalities may be observed. In this presentation, three examples of multifunctional polymers developed in our labs will be reported. The first class of multifunctional polymers are the microphase separated mixed (ionic and electronic) conducting or MIEC block copolymers. The second class being developed in our labs are the biocompatible conductive materials and the conductive fluids. The final class may be considered microwave active smart polymers.

Arnold, S.↗

Analysis of Regen Cooling in Rocket Combustors

The use of detailed CFD modeling for the description of cooling in rocket chambers is discussed. The overall analysis includes a complete three-dimensional analysis of the flow in the regenerative cooling passages, conjugate heat transfer in the combustor walls, and the effects of film cooling on the inside chamber. The results in the present paper omit the effects of film cooling and include only regen cooling and the companion conjugate heat transfer. The hot combustion gases are replaced by a constant temperature wall boundary condition. Load balancing for parallel cluster computations is ensured by using single-block unstructured grids for both fluids and solids, and by using a 'multiple physical zones' to account for differences in the number of equations. Validation of the method is achieved by comparing simple two-dimensional solutions with analytical results. Representative results for cooling passages are presents showing the effects of heat conduction in the copper walls with tube aspect ratios of 1.5:l.

Harper, Brent↗

Effect of strain isolator pad modulus on inplane strain in Shuttle Orbiter thermal protection system tiles

The thermal protection system used on the Space Shuttle orbiter to determine strains in the reusable surface insulation tiles under simulated flight loads was investigated. The effects of changes in the strain isolator pad (SIP) moduli on the strains in the tile were evaluated. To analyze the SIP/tile system, it was necessary to conduct tests to determine inplane tension and compression modulus and inplane failure strain for the densified layer of the tiles. It is shown that densification of the LI-900 tile material increases the modulus by a factor of 6 to 10 and reduces the failure strain by about 50%. It is indicated that the inplane strain levels in the Shuttle tiles in the highly loaded regions are approximately 2 orders of magnitude lower than the failure strain of the material. It is concluded that most of the LI-900 tiles on the Shuttle could be mounted on a SIP with tensile and shear stiffnesses 10 times those of the present SIP without inplane strain failure in the tile.

Sawyer, J. W.↗

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

The objective of this research was to identify promising electrocatalyst/support systems for the oxygen cathode in alkaline fuel cells operating at relatively high temperatures, O2 pressures and current densities. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, and lithiated NiO. Several of these were prepared using techniques that had not been previously used to prepare them. Particularly interesting is the use of the alkaline solution technique to prepare the Pt-doped Pb-Ru pyrochlore in high area form. Well-crystallized Pb(2)Ru(2)O(7-y) was used to fabricate high performance O2 cathodes with relatively good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approximately 140 C in concentrated KOH. Other pyrochlores were found to be either unstable (amorphous samples) or the fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. High area platinum supported on conductive metal oxide supports produced mixed results: small improvements in O2 reduction performance for Pb(2)Ru(2)O(7-y) but a large improvement for Li-doped NiO at room temperature. Nearly reversible behavior was observed for the O2/OH couple for Li-doped NiO at approximately 200 C.

Tryk, D.↗

Effect of iron content on the electrical conductivity of perovskite and magnesiowuestite assemblages at lower mantle conditions

The electrical conductivity of (Mg/0.76/Fe/0.24/)SiO3 perovskite and of an assemblage of (Mg/0.89/Fe/0.11/)SiO3 perovskite + (Mg/0.70/Fe/0.30/)O magnesiowiestite was measured at pressures of 45-80 GPa and temperatures from 295 to 3600 K. The apparent activation energy for electrical conduction is 0.24 (+ or - 0.10) eV for the perovskite and 0.20 (+ or - 0.08) eV for the perovskite + magnesiowuestite assemblage. Comparing present results with those derived previously for Fe-poor samples, it is found that the electrical conductivities of both the silicate perovskite and the perovskite + magnesiowuestite assemblage depend strongly on iron content. Thus, the electrical conductivity distribution inside the earth could provide an important constraint in modeling the composition of the lower mantle.

Li, Xiaoyuan↗

A Search for Star Formation in the Translucent Cloud MBM 40

The star formation status of the translucent high-latitude molecular cloud, MBM 40, is explored through analysis of radio, infrared, optical, and X-ray data. With a peak visual extinction of 1 to 2 mag, MBM 40 is an example of a high-latitude cloud near the diffuse/translucent demarcation. However, unlike most translucent clouds, MBM 40 exhibits a compact morphology and a kinetic energy-to gravitational potential energy ratio near unity. Our radio data, encompassing the CO (J = 1-0), CS (J = 2-1), and H2CO 1(sub 11-1(sub 10), spectral line transitions, reveal that the cloud contains a ridge of molecular gas with n greater than or equal to 10(exp 3)/ cc. In addition, the molecular data, together with IRAS data, indicate that the mass of MBM 40 is approx. 40 solar mass. In light of the ever-increasing number of recently formed stars far from any dense molecular clouds or cores, we searched the environs of MBM 40 for any trace of recent star formation. We used the ROSAT All-Sky Survey X-ray data and a ROSAT PSPC pointed observation toward MBM 40 to identify 33 stellar candidates with properties consistent with pre-main-sequence (PMS) stars. Follow-up optical spectroscopy of the candidates with V less than 15.5 was conducted with the 1.5 m Fred Lawrence Whipple Observatory telescope in order to identify signatures of T Tauri or pre-main- sequence stars (such as the Li 6708 A resonance line). Since none of our optically observed candidates display standard PMS signatures, we conclude that MBM 40 displays no evidence of recent or ongoing star formation. The absence of high-density molecular cores in the cloud and the relatively low column density compared to star-forming interstellar clouds may be the principal reasons that MBM 40 is devoid of star formation. More detailed comparison between this cloud and other, higher extinction translucent and dark clouds may elucidate the necessary initial conditions for the onset of low-mass star formation.

Magnani, Loris↗

Technique for Determining the Viscosity and Electrical Conductivity of Semiconducting Liquids

A novel apparatus for determining the viscosity and electrical conductivity of semiconducting liquids has been developed at NASA/MSFC. The apparatus is based on the transient torque technique and utilizes a 125 micrometer diameter quartz fiber as a torsion wire and a sensitive angular detector to measure the deflection angle of the crucible containing the liquid. A rotating flow is induced in the semiconducting melt by the application of a rotating magnetic field and measurement of the magnitude and transient behavior of the induced deflection angle allows the simultaneous determination of the viscosity and electrical conductivity of the melt. Measurements at room temperature and up to 900 C were made on high purity melts.

Li, C.↗

The Dielectric Constant at P-Band for Salinity from 0 to 150 pss

Measurements have been made at P-band (0.707 GHz) to construct a model for the dielectric constant of sea water and extend the model for the dielectric constant to high salinity (50-150 pss). The measurements are part of research to develop a model for the dielectric constant suitable for future wide-bandwidth remote sensing of salinity and for application to water bodies such as the Great Salt Lake with salinity significantly above that found in the open ocean. Measurements have been made at temperatures from 2 to 30 °C and salinity from 0 to 138 pss. The data have been fit to a Debye model for the dielectric constant with a single resonance as has been employed at L-band (1.413 GHz) where remote sensing of salinity is currently done. Comparison with contemporary models developed from data at L-band indicates that the L-band model and new P-band model do well at both frequencies for salinity less than 50 pss but at higher values of salinity the L-band models diverge from the data. The data has also been used to test at high salinity the mathematical relationship between salinity and conductivity which is the basis for the practical salinity scale (pss).

Dielectric Constant↗

Characterization of PVT Grown ZnSe by Low Temperature Photoluminescence

ZnSe, a II-VI semiconductor with a large direct band gap of 2.7 eV at room temperature and 2.82 eV at 10 K, is considered a promising material for optoelectric applications in the blue-green region of the spectrum. Photoemitting devices and diode laser action has been demonstrated as a result of decades of research. A key issue in the development of II-VI semiconductors is the control of the concentration of the various impurities. The II-VI semiconductors seem to defy the effort of high level doping due to the well known self compensation of the donors and the acceptors. A good understanding of roles of the impurities and the behavior of the various intrinsic defects such as vacancies, interstitials and their complexes with impurities is necessary in the development and application of these materials. Persistent impurities such as Li and Cu have long played a central role in the photoelectronic properties of many II-VI compounds, particularly ZnSe. The shallow centers which may promote useful electrical conductivity are of particular interest. They contribute the richly structured near gap edge luminescence, containing weak to moderate phonon coupling and therefore very accessible information about the energy states of the different centers. Significance of those residual impurities which may contribute such centers in II-VI semiconductors must be fully appreciated before improved control of their electrical properties may be possible. Low temperature photoluminescence spectroscopy is an important source of information and a useful tool of characterization of II-VI semiconductors such as ZnSe. The low temperature photoluminescence spectrum of a ZnSe single crystal typically consists of a broad band emission peaking at 2.34 eV, known as the Cu-green band, and some very sharp lines near the band gap. These bands and lines are used to identify the impurity ingredients and the defects. The assessment of the quality of the crystal based on the photoluminescence analysis is then possible. In this report we present the characterization of a ZnSe single crystal as grown by the physical vapor transport method, with special intention paid to the possible effects of the gravitational field to the growth of the crystal.

Wang, Ling Jun↗

Development of Solid State Electrolytes for Li-Metal Based High Capacity Battery

NASA future missions demand safe, high specific energy (>400 Wh/kg) batteries. Current state-of-the-art (SOA) lithium-ion batteries (LIBs) can only provide ~150-200 Wh/kg in energy capacity, which is unable to meet NASA's future energy goals, and also pose safety issues due to the use of liquid flammable electrolyte. There are intense on-going development activities to increase battery energy density. The use of Li metal as an anode material has emerged as one highly attractive option for achieving high-energy, next generation batteries. This is because Li has many advantages. It is the lightest metal, but also has the highest theoretical capacity. It also has the lowest potential, which boosts whole cell voltage, and Li metal is 100% active material and requires no binder. Thus, Li metal is an ideal anode material for high energy battery chemistries. Lithium metal based advanced battery chemistries are envisioned to be mission enhancing and, in many cases, mission enabling for future space and aeronautic applications. However, the reliable use of this exceptionally high capacity anode in a commercial rechargeable battery has not been achieved due to safety and reliability concerns resulting from thermal runaway and short-circuit issues due to dendritic growth on the Li metal anode from lithium plating during charge-discharge cycles. A solid state electrolyte, such as garnet/ceramic or solid polymer nanocomposite electrolyte, is a promising approach to make Li metal safely cycling. The solid state electrolyte is non-flammable and eliminates leakage and fire hazard by replacing the liquid flammable electrolyte. However, the low-ionic conductivity and high interfacial impedance are the key issues to be overcome. In this presentation, the research activities on solid state electrolyte development funded by the NASA Advanced Energy Storage System program and by the NASA Center Innovative Fund will be presented, and the progress and results will be also discussed.

Wu, James J.↗