Electrolytes with Improved Safety Developed for High Specific Energy Li-Ion Cells with Si-Based Anodes
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A number of electrolyte formulations that have improved safety characteristics have been developed for use with high capacity silicon-based anodes. To improve the compatibility with Si-based anodes, a number of technical approaches have been employed, including: (1) the use of mono-fluoroethylene carbonate (FEC) in conjunction with, or in lieu of, ethylene carbonate (EC), (2) the use of high proportions of fluorinated co-solvents, (3) the use of vinylene carbonate (VC) to stabilize the Si/C electrode, and (4) the use of lithium bis(oxalato)borate (LiBOB) to improve the compatibility of the electrolyte when Si/C electrodes are used in conjunction with high voltage cathodes. Candidate electrolytes were studied in Li/Si-C and Si-C/ Li(MnNiCo)O2 (NMC) coin cells, as well as in larger Si-C/NMC three-electrode cells equipped with lithium reference electrodes. In summary, many electrolytes that contain triphenyl phosphate (TPP), which is used as a flame retardant additive up to concentrations of 15 volume percent, and possess FEC as a co-solvent have been demonstrated to outperform the all-carbonate baseline electrolytes when evaluated in Si-C/ Li(MnNiCo)O2 cells.
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The higher energy content (265 Wh/kg, 725 Wh/L) of the newer cell designs from LG, Panasonic, and Samsung have made them susceptible to side wall ruptures (SWR) during thermal runaway, rather than venting through the intended vent path in the cell header. This is also due to higher reaction kinetics of the electrochemistry, thinner can walls, tight crimp enclosure of the cell header, and inadequate flow rate through the header vent. This effort determined that bottom vents and thicker cell can walls both are necessary for reducing the risk of SWR. Compelling evidence was obtained using novel test methods that included an on-demand internal short circuit device, high speed X-ray videography, and cell thermal runaway calorimetry.
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A method is presented for calculating the three orthogonal components of the velocity perturbations of satellite fragments, with a view to ascertaining the nature and intensity of the satellite breakup. The method employs three simultaneous equations furnished by changes in fragment specific energy, specific angular momentum, and plane orientation. Velocity perturbations are thereby calculated for fragments from 20 major satellite breakup events; these results, in conjunction with a technique for determining fragment masses, yield a description of the breakup process.
The goal of this program is to develop a lightweight nickel electrode for advanced aerospace nickel-hydrogen cells and batteries with improved specific energy and specific volume. The lightweight nickel electrode will improve the specific energy of a nickel-hydrogen cell by >50%. These near-term advanced batteries will reduce power system mass and volume, while decreasing the cost, thus increasing mission capabilities and enabling small spacecraft missions. This development also offers a cost savings over the traditional sinter development methods for fabrication. The technology has been transferred to Eagle-Picher, a major aerospace battery manufacturer, who has scaled up the process developed at NASA GRC and fabricated electrodes for incorporation into flight-weight nickel-hydrogen cells.
Bi-Polar nickel hydrogen design studies indicated a potential improvement in energy density and specific energy if positive electrodes could be manufactured in configurations of twice or more of the present normal thickness. Such electrodes would have to achieve similar active material loading, utilization, and cycle life to conventional 0.8mm I.P.U. nickel hydrogen electrodes. A capability for producing 1.0mm dry sinter and 1.5mm slurry sinter structures on production processes and equipment was demonstrated. The EPI/USAF electrochemical impregnation process proved capable of loading thick electrodes to 1.60 g/cubic centimeters void or higher. Sample electrodes incurred 2000 high rate stress cycles without significant structural or performance degradation. Formation regimes developed for thin plaque are not optimal for thick plaque and further investigation into electrode capacity build-up would seem warranted. Thick electrode technology development is continuing under other programs and shows promise of fulfilling the projected energy density and specific energy improvements.