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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Filled Nd(sub z) Fe(sub x) Co(sub 4-x) Sb(sub 12-y) Ge(sub y) Skutterudites: Processing and Thermoelectric Properties
Skutterudites have proven to be a useful thermoelectric system as a result of their enhanced figure of merit (ZT1), cheap material cost, favorable mechanical properties, and good thermal stability. The majority of skutterudite interest in recent years has been focused on binary skutterudites like CoSb3. Binary skutterudites are often double and triple filled, with a range of elements from the lanthanide series, in order to reduce the lattice component of thermal conductivity. Ternary and quaternary skutterudites, such as Co4Ge6Se6 or Ni4Sb8Sn4, provide additional paths to tune the electronic structure. The thermal conductivity can further be improved in these complex skutterudites by the introduction of fillers. The Nd (sub z) Fe (sub x) Co (sub 4-x) Sb (sub 12-y)Ge (sub y) system has been investigated as a p-type thermoelectric material, and is stable up to 600 degrees Centigrade. The influence of Fe and Ge content, along with filler Nd, was investigated on thermoelectric transport properties. In addition to the chemical influence on properties, some processing details of the system will also be addressed.
Filled Nd(z)Fe(x)Co(4-x)Sb(12-y)Ge(y) Skutterudites: Processing and Thermoelectric Properties
Skutterudites have proven to be a useful thermoelectric system as a result of their enhanced figure of merit (ZT1), cheap material cost, favorable mechanical properties, and good thermal stability. The majority of skutterudite interest in recent years has been focused on binary skutterudites like CoSb3. Binary skutterudites are often double and triple filled, with a range of elements from the lanthanide series, in order to reduce the lattice component of thermal conductivity. Ternary and quaternary skutterudites, such as Co4Ge6Se6 or Ni4Sb8Sn4, provide additional paths to tune the electronic structure. The thermal conductivity can further be improved in these complex skutterudites by the introduction of fillers. The Nd(z)Fe(x)Co(4-x)Sb(12-y)Ge(y) system has been investigated as a p-type thermoelectric material, and is stable up to 600 C. The influence of Fe and Ge content, along with filler Nd, was investigated on thermoelectric transport properties. In addition to the chemical influence on properties, some processing details of the system will also be addressed.
Sintered Cathodes for All-Solid-State Structural Lithium-Ion Batteries
All-solid-state structural lithium ion batteries serve as both structural load-bearing components and as electrical energy storage devices to achieve system level weight savings in aerospace and other transportation applications. This multifunctional design goal is critical for the realization of next generation hybrid or all-electric propulsion systems. Additionally, transitioning to solid state technology improves upon battery safety from previous volatile architectures. This research established baseline solid state processing conditions and performance benchmarks for intercalation-type layered oxide materials for multifunctional application. Under consideration were lithium cobalt oxide and lithium nickel manganese cobalt oxide. Pertinent characteristics such as electrical conductivity, strength, chemical stability, and microstructure were characterized for future application in all-solid-state structural battery cathodes. The study includes characterization by XRD, ICP, SEM, ring-on-ring mechanical testing, and electrical impedance spectroscopy to elucidate optimal processing parameters, material characteristics, and multifunctional performance benchmarks. These findings provide initial conditions for implementing existing cathode materials in load bearing applications.
Freeze Casting of LAGP for 3D Textured Solid-State Structural Electrolytes
In this study, all-solid-state structural lithium-ion batteries, a type of load bearing electrochemical energy storage that provides systems-level weight savings is being pursued for the realization of inherently safe next generation hybrid-electric and all-electric green aerospace propulsion systems. Currently investigated all-solid-state batteries do not meet the requirements for specific power and mechanical stability. To address these issues, freeze casting of lithium aluminum germanium phosphate (LAGP) electrolyte material has been explored for the creation of a textured 3D electrolyte scaffold with large interfacial surface area for high power discharge and hierarchical porosity for accommodation of active material volume changes during electrochemical cycling. We report the effects of freeze casting processing parameters on the microstructural development and mechanical performance of the scaffolds, characterized through scanning electron microscopy and ring-on-ring mechanical testing. Slurry composition and casting parameters such as solids loading, casting speed, tape angle, and temperature gradients have been modified to determine the impact on density, lamellar morphology, and final load-bearing performance.
Development of Solid-State Li/Sulfur - Selenium as Safe and High Capacity Battery
This is an invited presentation on "Development of Solid-State Li/Sulfur-Selenium as Safe and High Capacity Battery" for The Minerals, Metals and Materials Society 2020 149th Annual Meeting and Exhibition in San Diego, California.
Solid-state battery designed for electric aviation
The demand for higher energy density batteries increases as the demand for portable electronic devices and electric automotive increases, as well as a variety of other applications requiring substantially higher power and energy than attainable with current lithium-ion capabilities which includes the areas of high performance vehicles, military applications, and electric aviation. However, the improvement of energy density is insufficient alone for enabling electric aviation when considering the high flammability and risk of thermal runaway inherent in current state-of-the-art liquid electrolytes. The development of high energy, high power, and safe batteries are required to enable hybrid and fully electric aircraft. Next generation chemistries such as lithium-sulfur provide high theoretical specific energy density suitable for electric aviation without as strict of volumetric requirements observed in the automotive industry. However, due to the phase transition during discharge where sulfur generates a series of soluble intermediate polysulfides, which are lost to the liquid electrolyte, cause detrimental side effects, and severely limit cycle life battery performance is severely reduced. Additionally, the low electrical conductivity of sulfur requires a large amount of inactive carbon dramatically increasing parasitic mass. The dissolution issue make sulfur a desirable candidate to pair with a solid-state electrolyte in order to avoid polysulfide dissolution and shuttling. In addition, inorganic solid-electrolytes have low flammability providing the improved safety required. Combining this chemistry with a solid-state electrolyte provides a path for achieving the energy and safety required for electric aviation. The development of scalable thin solid-state electrolytes paired with lithium-sulfur chemistry will be discussed and how their development will aid in enabling a unique application.
Microstructure Quantification and Random Forest Regression Models for Li4Ti5O12–Ni Property Prediction
All-solid-state structural lithium-ion batteries are sought to enable all-electric propulsion in next generation aerospace concepts through improved safety and systems level weight savings. In this work, the influence of processing conditions on microstructural evolution was evaluated for anode composites of strain-free Li4Ti5O12 and metallic nickel current collector. Beyond size distributions, this study explored methods of quantifying microstructural features that describe changes in the spatial distribution and coalescence of nickel particles as a function of sample composition and sintering conditions. Processing-microstructure-property relationships were described by microstructure quantifiers including nickel particle count per area, nearest neighbor distance distribution, and edge-to-edge distance distribution. Machine learning methods were applied to compare the relative influence of processing conditions and microstructural features on electrical conductivity and mechanical strength to optimize for simultaneous energy storage and load bearing performance. Insights gained from this work inform future evaluation of alternative energy storage materials and microstructures for multifunctional performance, and generation of microstructural descriptors strengthens modeling across length scales.
High Temperature W-band Complex Permittivity Measurements of Thermally Cycled Ceramic-Metal Composites: AlN:Mo with 0.25 vol% to 4.0 vol% Mo from 25 °C to 1000 °C in Air
An apparatus for measuring the W-band (75-110GHz) complex permittivity of dielectrics at 1000 °C was developed. This apparatus allows for measurements at approximately twice the temperature of previously published high temperature free-space measurement systems while maintaining similar precision. Challenges were addressed related to high temperature measurements, including temperature uniformity, the accuracy of temperature measurements, and preventing temperature related changes to mm-wave measurement systems. The details of complex permittivity extraction from the measured S-parameters are discussed. Sources of error related to permittivity measurement and mathematical models were identified and are discussed in detail herein. Thermally-cycled, mm-wave absorbing, aluminum nitride ceramic composites containing varying levels of molybdenum additives were measured over the range of 25-1000 °C. These measurements were compared to the same composites before thermal cycling. It was found that ceramic composites are largely stable after thermal cycling in terms of dielectric properties despite the presence of visible surface modifications.
Design Considerations for Practical Li-S Batteries for Electric Aviation
The development of high-energy, high-safety, and high-power batteries beyond electric automotive standards is critical for future electric aviation applications. Non-volatile solid-state electrolytes (SSE) offer many promising advantages over traditional flammable liquid electrolytes. Solid-state electrolytes may be an enabling technology for certain battery chemistries by preventing detrimental interactions with liquid electrolytes, for example prevention of the dissolution of intermediates in lithium-sulfur common in traditional liquid organic solvents. However, significant manufacturing challenges must be overcome before the adoption of such technology. This research was conducted to identify processing techniques for producing solid-state battery components with practical dimensions and weights for enabling high specific energy cells. Traditional research has identified a range of very high theoretical ionic conductivities but are impractical due to their instability or inability to be manufactured. Electrolytes explored in this study were produced as sulfide-polymer composites with densified thicknesses below 40 micron using a tape-casting technique and thermoplastic elastomer binder. The combination of high chemical compatibility and flexibility produced robust films that had moderate impact on the ionic conductivity but was capable of dramatically reducing the parasitic mass. Despite minimal conductivity losses, films were produced 10-15 times thinner than comparable bulk powder electrolytes thus leading to overall lower film resistance. Conductivity is maintained above 0.2mS/cm for composite electrolytes. Through the analysis of materials based on their physical properties, such as density, practical cells can be designed. Based on this, low density sulfide-solid-state electrolytes are a promising candidate for achieving the energy and safety metrics for electric aviation, however, further optimization of cathode microstructure and composite processing will be required to achieve the high power metrics and will be the focus of further studies. Additionally, fabrication challenges arise when utilizing metallic lithium foil, due to its soft nature, as overflow and mechanical short circuit can occur on assembly which remains a challenge to overcome before metallic lithium anodes can be fully realized.