The Coupling between Voltage Profiles and Mechanical Deformations in LAGP Solid Electrolyte During Li Plating and Stripping
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Aluminum-Lithium (AL-Li) alloys offer significant performance benefits for aerospace structural applications due to their higher specific properties compared with conventional aluminum alloys. For example, the application of an Al-Li alloy to the space shuttle external cryogenic fuel tank contributed to the weight savings that enabled successful deployment of International Space Station components. The composition and heat treatment of this alloy were optimized specifically for strength-toughness considerations for an expendable cryogenic tank. Time dependent properties related to reliability, such as thermal stability, fatigue, and corrosion, will be of significant interest when materials are evaluated for a reusable cryotank structure. As most aerospace structural hardware is weight sensitive, a reusable cryotank will be designed to the limits of the materials mechanical properties. Therefore, this effort was designed to establish the effects of thermal exposure on the mechanical properties and microstructure of one relatively production mature alloy and two developmental alloys C458 and L277. Tensile and fracture toughness behavior was evaluated after exposure to temperatures as high as 3oooF for up to IO00 hrs. Microstructural changes were also evaluated to correlate with the observed data trends. The ambient temperature parent metal data showed an increase in strength and reduction in elongation after exposure at lower temperatures. Strength reached a peak with intermediate temperature exposure followed by a decrease at highest exposure temperature. Characterizing the effect of thermal exposure on the properties of Al-Li alloys is important to defining a service limiting temperature, exposure time, and end-of-life properties.
The objective of this viewgraph representation is to evaluate the effects of thermal exposure on the mechanical properties of both production mature and developmental Al-Li alloys. The researchers find for these alloys, the data clearly shows that there is no deficit in mechanical properties at lower exposure temperatures in some cases, and a signficant deficit in mechanical properties at higher exposure temperatures in all cases. Topics considered include: Al-Li alloys composition, key characteristics of Al-Li alloys and thermal exposure matrix.
Large rocket cryogenic tank domes have typically been fabricated using Al-Cu based alloys like Al-Cu alloy 2219. The use of aluminum-lithium based alloys for rocket fuel tank domes can reduce weight because aluminum-lithium alloys have lower density and higher strength than Al-Cu alloy 2219. However, Al-Li alloys have rarely been used to fabricate rocket fuel tank domes because of the inherent low formability characteristic that make them susceptible to cracking during the forming operations. The ability to form metal by stretch forming or spin forming without excessive thinning or necking depends on the strain hardening exponent "n". The stain hardening exponent is a measure of how rapidly a metal becomes stronger and harder. A high strain hardening exponent is beneficial to a material's ability to uniformly distribute the imposed strain. Marshall Space Flight Center has developed a novel annealing process that can achieve a work hardening exponent on the order of 0.27 to 0.29, which is approximately 50% higher than what is typically obtained for Al-Li alloys using the conventional method. The strain hardening exponent of the Al-Li alloy plates or blanks heat treated using the conventional method is typically on the order of 0.17 to 0.19. The effects of this novel annealing process on the formability of friction stir welded Al-Li alloy blanks are being studied at Marshall Space Flight Center. The formability ratings will be generated using the strain hardening exponent, strain rate sensitivity and forming range. The effects of forming temperature on the formability will also be studied. The objective of this work is to study the deformation behavior of the friction stir welded Al-Li alloy 2195 blank and determine the formability enhancement by the new annealing process.
Aluminum-Lithium alloy 2195 exhibits higher mechanical properties and lower density than aluminum alloy 2219, which is the current baseline material for Space Launch System (SLS) cryogenic tank components. Replacement of Al 2219 with Al-Li 2195 would result in substantial weight savings, as was the case when this replacement was made on the shuttle external tank. A key component of cryogenic tanks are the gores, which are welded together to make the rounded ends of the tanks. The required thicknesses of these gores depend on the specific SLS configuration and may exceed the current experience base in the manufacture of such gores by the stretch forming process. Here we describe the steps taken to enhance the formability of Al-Li 2195 by optimizing the heat treatment and stretch forming processes for gore thicknesses up to 0.75", which envelopes the maximum expected gore thicknesses for SLS tanks. An annealing treatment, developed at Marshall Space Flight Center, increased the forming range and strain hardening exponent of Al-Li 2195 plates. Using this annealing treatment, one 0.525" thick and two 0.75" thick gores were manufactured by the stretch forming process. The annealing treatment enabled the stretch forming of the largest ever cross sectional area (thickness x width) of an Al-Li 2195 plate achieved by the manufacturer. Mechanical testing of the gores showed greater than expected ultimate tensile strength, yield strength, modulus, and elongation values. The gores also exhibited acceptable fracture toughness at room and LN2 temperatures. All of the measured data indicate that the stretch formed gores have sufficient material properties to be used in flight domes.
Aluminum-Lithium alloy 2195 exhibits higher mechanical properties and lower density than aluminum alloy 2219, which is the current baseline material for Space Launch System (SLS) cryogenic tank components. Replacement of Al 2219 with Al-Li 2195 would result in substantial weight savings, as was the case when this replacement was made on the shuttle external tank. A key component of cryogenic tanks are the gores, which are welded together to make the rounded ends of the tanks. The required thicknesses of these gores depend on the specific SLS configuration and may exceed the current experience base in the manufacture of such gores by the stretch forming process. Here we describe the steps taken to enhance the formability of Al-Li 2195 by optimizing the heat treatment and stretch forming processes for gore thicknesses up to 0.75", which envelopes the maximum expected gore thicknesses for SLS tanks. An annealing treatment, developed at Marshall Space Flight Center, increased the forming range and strain hardening exponent of Al-Li 2195 plates. Using this annealing treatment, one 0.525" thick and two 0.75" thick gores were manufactured by the stretch forming process. The annealing treatment enabled the stretch forming of the largest ever cross sectional area (thickness x width) of an Al-Li 2195 plate achieved by the manufacturer. Mechanical testing of the gores showed greater than expected ultimate tensile strength, yield strength, modulus, and elongation values. The gores also exhibited acceptable fracture toughness at room and LN2 temperatures. All of the measured data indicate that the stretch formed gores have sufficient material properties to be used in flight domes.
A procedure is established to determine conditions that result in safe charging of Li-ion batteries under extreme conditions of charge rate and temperature.
In order to improve manufacturing efficiency and reduce structural mass and costs in the production of launch vehicle structures, NASA is pursuing a wide-range of innovative, near-net shape manufacturing technologies. A technology that combines friction stir welding (FSW) and spin-forming has been applied to manufacture a single-piece crew module using Aluminum-Lithium (AL-Li) Alloy 2195. Plate size limitations for Al-Li alloy 2195 require that two plates be FSW together to produce a spin-forming blank of sufficient size to form the crew module. Subsequent forming of the FSW results in abnormal grain growth (AGG) within the weld region upon solution heat treatment (SHT), which detrimentally impacts strength, ductility, and fracture toughness. The current study seeks to identify microstructural factors that contribute to the development of AGG. Electron backscatter diffraction (EBSD) was used to correlate driving forces for AGG, such as stored energy, texture, and grain size distributions, with the propensity for AGG. Additionally, developmental annealing treatments prior to SHT are examined to reduce or eliminate the occurrence of AGG by promoting continuous, or uniform, grain growth
Sputter deposition of LiPON films directly onto high Li+ conductivity solid electrolyte plates has been investigated as a means to minimize the reactivity of the plates to metallic Li. The LiPON films were shown to effectively passivate the plates in contact with metallic Li, in contrast to unpassivated plates that reacted immediately in contact with Li metal.
Friction stir welding process is being evaluated for application on the Al-Cu-Li 2195 Super-Light Weight External Tank of the Space Transportation System. In the present investigation Al-Cu-Li 2195 plates were joined by autogenous friction stir welding (FSW) and hybrid FSW (friction stir welding over existing variable polarity plasma arc weld). Optical microscopy and transmission electron microscopy (TEM) were utilized to characterize microstructures of the weldments processed by both welding methods. TEM observations of autogenous FSW coupons in the center section of the dynamically-recrystallized zone showed an equiaxed recrystallized microstructure with an average grain size of approx. 3.8 microns. No T(sub 1), precipitates were present in the above-mentioned zone. Instead, T(sub B) and alpha precipitates were found in this zone with a lower population. Alternate immersion, anodic polarization, constant load, and slow strain tests were carried out to evaluate the general corrosion and stress-corrosion properties of autogenous and hybrid FSW prepared coupons. The experimental results will be discussed.
Spin forming is a metalworking process used to produce axially-symmetric parts by the application of lateral pressure from a forming tool to a circular blank mounted on a revolving, heated mandrel. This process enables production of cones, domes, or caps that can incorporate features such as flat bulkheads. Friction stir welded (FSW) Al-Li 2195 blanks have been spin formed for single-piece, launch vehicle domes up to 5 m in diameter. Al-Li 2050 plate has the advantage of availability up to 165 mm thick,whereas 2195 plate is traditionally only available up to 57 mm thick. Increased plate thickness enables greater design flexibility for machining of taller structural elements, such as stiffeners. However, 2050 is only available in plate widths up to ~3.9 m. This study demonstrated the capability of making custom 2050 blanks for spin forming large (>7.8 m in diameter), single-piece, light-weight flight articles (e.g., lunar habitats and landers) by FSW two (or more) plates together. Spin forming of welded 2050 blanks has not been attempted before this investigation. The objective was to evaluate the mechanical properties of 2050 parent material and FSW regions after spin forming and subsequent T6 heat treatment. A 3 m diameter x 38 mm thick 2050 blank was fabricated from two 1.5 m wide pieces by FSW and subsequently spin formed into a cone article. Additionally, three 1.2 m diameter x 8.1 mm thick 2050 blanks were produced by FSW and spin formed into subscale cone articles with varying strain input. Mechanical properties are reported for spin formed 2050-T6 parent material and FSW regions on the articles. Abnormal grain growth (AGG) in the FSW during heat treatment was expected based on prior experience with 2195. Implementation of an AGG suppression strategy during heat treatment reduced AGG in the FSW regions and improved ductility.
In the present work, a number of additives have been investigated for their effect on the charge characteristics of cells containing low temperature, high ester content electrolytes (1.0 M LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + methyl propionate (MP) 20:20:60 vol % + X additive). These experimental three-electrode cells are composed of graphite anodes, LiNiCoAlO2 cathodes, and a lithium metal reference electrode. Cells were first subjected to electrochemical characterization at various temperatures, consisting of performing Electrochemical Impedance Spectroscopy (EIS), linear micropolarization and Tafel polarization measurement to determine the kinetic parameters for both the anodes and cathodes. Following electrochemical characterization, the cells were subjected to charging at decreasing temperatures using C/5 rates to 4.10V, with a constant potential C/50 current taper. Analysis of the C/20 discharge following the charge at low temperature revealed either the presence or absence of a high voltage plateau during the initial stages of the discharge. This plateau has been linked to the presence of lithium metal on the anode previously and was used as a measure for the extent of lithium plating in the cell. Differential analysis (dV/dQ) was applied as well to more clearly visualize the position of the high voltage plateau and use the peak position (x-axis) in the dV/dQ plot as a gauge for the amount of plating which took place in the cell on the prior charge. Most additives investigated increased the resistance of the anode and decreased the resistance of the cathode, thereby leading to an overall increase in plating observed at low temperature. One additive, LiFSI, was found to be beneficial during low temperature charging, however studies of electrode kinetics from the cell containing LiFSI did not reveal significant improvements compared to the baseline.
Plates of a solid electrolyte that exhibits high conductivity for positive lithium ions can now be passivated to prevent them from reacting with metallic lithium. Such passivation could enable the construction and operation of high-performance, long-life lithium-based rechargeable electrochemical cells containing metallic lithium anodes. The advantage of this approach, in comparison with a possible alternative approach utilizing lithium-ion graphitic anodes, is that metallic lithium anodes could afford significantly greater energy-storage densities. A major impediment to the development of such cells has been the fact that the available solid electrolytes having the requisite high Li(exp +)-ion conductivity are too highly chemically reactive with metallic lithium to be useful, while those solid electrolytes that do not react excessively with metallic lithium have conductivities too low to be useful. The present passivation method exploits the best features of both extremes of the solid-electrolyte spectrum. The basic idea is to coat a higher-conductivity, higher-reactivity solid electrolyte with a lower-conductivity, lower-reactivity solid electrolyte. One can then safely deposit metallic lithium in contact with the lower-reactivity solid electrolyte without incurring the undesired chemical reactions. The thickness of the lower-reactivity electrolyte must be great enough to afford the desired passivation but not so great as to contribute excessively to the electrical resistance of the cell. The feasibility of this method was demonstrated in experiments on plates of a commercial high-performance solid Li(exp +)- conducting electrolyte. Lithium phosphorous oxynitride (LiPON) was the solid electrolyte used for passivation. LiPON-coated solid-electrolyte plates were found to support electrochemical plating and stripping of Li metal. The electrical resistance contributed by the LiPON layers were found to be small relative to overall cell impedances.
Single-piece, spin-formed domes manufactured from friction stir welded (FSW) plates of Al-Li alloy 2195 have the potential to reduce the cost of fabricating cryogenic propellant tanks. Mechanical properties in the completed domes can be related directly to the final material condition and the microstructures developed. However, these new fabrication techniques have resulted in unexpected material challenges, such as abnormal grain growth in the weld nugget and the propensity for fracture in the adjacent thermo-mechanically affected zone (TMAZ). In this study, the microstructure and texture transformations within the TMAZ are related to fracture location in the vicinity of the weldment. The texture variations in the TMAZ are caused primarily by the varying amounts of shear deformation introduced during the FSW process. Grain morphology and microtexture characteristics are examined as a function of location in the TMAZ via electron backscatter diffraction (EBSD). A strong correlation between fracture location and the presence of texture banding in the TMAZ is observed. The fracture path tends to follow a distinct region of low Taylor Factor (TF) grains.
The antiplane strain problem of an edge cracked elastic plate subjected to a surface displacement load is solved, and the surface line loads are obtained using conformal mapping techniques. Results are presented for the yield, stress, strain and displacement distributions, and stress intensity factors in the plate. A superposition technique and Green's functions are used to determine the strain field on the upper plate surface due to arbitrarily applied tensile stress on the lower plate surface.
The fatigue crack growth rate of aluminum-lithium (Al-Li) alloy 2195 plate and weldments was determined at 200-F, ambient temperature and -320-F. The effects of stress ratio (R), welding process, orientation and thickness were studied. Results are compared with plate data from the Space Shuttle Super Lightweight Tank (SLWT) allowables program. Data from the current series of tests, both plate and weldment, falls within the range of data generated during the SLWT allowables program.
Manufacturing of single-piece end domes for cryogenic tanks employing spin forming of tailored, friction-stir-welded blanks of Al-Li alloy 2195 plate offers cost and reliability benefits. The introduction of plastic deformation into a friction stir weld is a unique feature of the proposed manufacturing route. This investigation addressed abnormal grain growth [AGG] within the friction stir weldments during postfabrication processing of a prototype dome. The phenomenon of AGG was observed during the solution heat treatment [SHT] phase of T8 tempering and is a major concern for meeting specifications. Such abrupt microstructural transitions can be detrimental to notch-sensitive mechanical properties, such as ductility and/or fracture toughness. If the issue of AGG cannot be resolved, then the acceptance of this approach as a viable manufacturing route may be in jeopardy. The innovative approach adopted in this investigation was the insertion of a stand-alone, Intermediate Annealing Treatment [IAT] between the spin forming and T8 processing operations. A simple, recovery annealing step was deemed to be the most readily-scalable solution when fabricating thin-walled, ellipsoidal domes. The research effort culminated in the development of an effective IAT, which resulted in a significant decrease in AGG following SHT. The processing philosophy adopted in designing the IAT is outlined and the microstructural reasons for success are discussed. The analytical results presented are consistent with promoting continuous grain growth during the IAT, thereby suppressing AGG during the SHT.
The effect of crystallographic texture on the mechanical properties of near-net-shape extrusions is of major interest ff these products are to find application in launch vehicle or aircraft structures. The objective of this research was to produce a catalogue containing quantitative texture information for extruded product, sheet and plate. The material characterized was extracted from wide, integrally stiffened panels fabricated from the Al-Cu-Li alloys 1460, 2090, 2096 and 2195. The textural characteristics of sheet and plate products of the same alloys were determined for comparison purposes. The approach involved using X-ray diffraction to generate pole figures in combination with orientation distribution function analysis. The data were compiled as a function of location in the extruded cross-sections and the variation in the major deformation- and recrystallization-related texture components was identified.