New Dielectric Material for High-Performance, Solid-State Ultracapacitors

Materials and Coatings
New Dielectric Material for High-Performance, Solid-State Ultracapacitors (MFS-TOPS-77)
Nanoparticle-based formulations enable many novel energy storage devices & manufacturing methods
Overview
NASA's Marshall Space Flight Center has developed a high-performance dielectric material in the development of ultracapacitors to replace batteries. This new material, formulated as a composite ink or paste, is based on novel high-permittivity dielectric powders. This dielectric material has performance characteristics of rapid charging; ultra-low leakage; and an extremely high dielectric constant. Furthermore, select compositions can offer battery-like discharge behavior. These attributes make the invention a highly desirable dielectric material for the development and manufacture of novel energy storage devices, including ultracapacitors, batteries, and other devices requiring a high dielectric constant and/or high breakdown voltages. The ceramic material also has the advantage of being completely safe as compared to traditional electrochemical batteries. Targeting potential use for satellite propulsion systems, the invention is undergoing continued development at NASA.

The Technology
NASA's technology is a dielectric materials formulation comprising polymers, organic binders, solvents, and surfactants, formulated together with a ceramic perovskite nanopowder. The ceramic nanopowder can be optimized for the required dielectric properties of capacitance, voltage breakdown, and leakage. This involves the addition of dopants or the use of advanced coatings on the powder particulates, and subsequent thermal treatments. The rheology of the formulation can be adjusted to work with a variety of coating or printing methods, from conventional thick-film methods to advanced inkjet or direct-write 3D printing methods used for printed electronics. 3D printing provides the ease of printed manufacturing along with the deposition of thinner layers (e.g., 5 microns in thickness vs. 50-100 micron layer via thick-film methods). Individual devices can then be formed in multilayer arrangements, or stacked and packaged as required for the given device application. The ultracapacitor described in MFS-TOPs-75 uses this dielectric material in its assembly. The ink composition is a careful blend of polyimide or polyvinylidene fluoride (PVDF) polymers, solvents, surfactants, and barium titanate nanopowders. Proper ratios are needed for viscosity and processability (e.g., nanopowder wetting and dispersion), along with the optimal ultracapacitor device performance.
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Benefits
  • Tailorable rheology for use in a range of coating and printing methods, including state-of-the-art aerosol inkjet and direct-write 3D printing systems, as well as traditional thick-film methods
  • Ultra-high capacitance and/or breakdown voltage of tailorable, dielectric compositions in either thick or thin layer formats &#8226 Capacitance range up to 1,000 mF &#8226 Dielectric breakdown range up to 25 MV/m
  • A safe and robust design that eliminates liquid or gel electrolytes used in conventional ultracapacitors or batteries &#8226 Highly resistant to mechanical shock and vibration &#8226 Fire- and explosion-resistant, even in extreme thermal environments &#8226 Nonpolar design provides ease of implementation

Applications
  • Aerospace: space power and propulsion systems
  • Transportation: regenerative braking systems for cars, trucks, buses, and trains; batteries for hybrid and electric cars, as well as fuel cellpowered vehicles
  • Energy: smart grid and renewable energy
  • Defense: backup power supplies, laser weapons, and railguns
  • Health: medical devices
Technology Details

Materials and Coatings
MFS-TOPS-77
MFS-33223-1
9,745,481
-Cortés-Peña, A. Y., T. D. Rolin, and C. W. Hill. A Novel Solid State Ultracapacitor. No. M17-6033. 2017.

-Zhang, L., Shan, X., Bass, P. et al. Process and Microstructure to Achieve Ultra-high Dielectric Constant in Ceramic-Polymer Composites. Sci Rep 6, 35763. 2016.
Similar Results
front image TOPS-46
Solid-State Ultracapacitor for Improved Energy Storage
The NASA solid-state ultracapacitor technology is based on the novel materials design and processes used to make the IBLC-type ultracapacitor. The IBLC concept is known to provide outstanding capacitance behavior but has been difficult to reproduce. NASA has developed a careful process to produce dielectric ink materials to be used in printed electronic applications with reproducibility. An individual cell is created by building electrodes on each side of the dielectric layer, and complete modules can be constructed by stacking multiple cells. Closely related NASA innovations on dielectric and conductive ink (electrode) formulations are key to the ultracapacitor construct, and are included in the technology package. Target performance criteria of this technology include the following: - Use of standard materials and processing methods - Robust solid-state device with no liquid electrolytes - High-energy densitytarget energy densities of 60 J/cc at a minimum operating voltage of 50 V - High dielectric breakdown strength (>250 V) - Excellent pulse-power performance; rapid discharge and charge - Reliable performance under repeated cycling (>500,000 cycles) Additional development work is underway to build and test complete capacitor modules and to further improve material properties and performance.
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Solid-State Ultracapacitor for Improved Energy Storage
NASAs solid-state ultracapacitor technology is based on the novel materials design and processes used to make the IBLC-type ultracapacitor. The IBLC concept is known to provide outstanding capacitance behavior but has been difficult to reproduce. NASA has developed a careful process to produce dielectric materials to be used in printed electronic applications with reproducibility. An individual cell is created by building electrodes on each side of the dielectric layer, and complete modules can be constructed by stacking multiple cells. Closely related NASA innovations on dielectric and conductive ink (electrode) formulations are key to the ultracapacitor construct, and are included in the technology package. Target performance criteria of this technology include the following: &#8226 Use of standard materials and processing methods &#8226 Robust, solid-state device with no liquid electrolytes &#8226 High-energy densitytarget energy densities of 60 J/cc at a minimum operating voltage of 50 V &#8226 High dielectric breakdown strength (> 25 MV/m) &#8226 Excellent pulse-power performance; rapid discharge and charge &#8226 Reliable performance under repeated cycling (> 500,000 cycles) Additional development work is underway to build and test complete capacitor modules and further improve material properties and performance.
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Novel, Solid-State Hybrid Ultracapacitor Battery
The subject technology is an extension of closely related, solid-state ultracapacitor innovations by the same team of inventors. The primary distinction for this specific technology is the addition of co-dopants to affect the dielectric behavior of the barium titanatebased perovskite materials. These co-dopants include lanthanum and other rare earths as well as hydroxyl ions. The materials are processed at the nano scale, and are subjected to carefully designed thermal treatments as well. The presence of the hydroxyl ions has been shown to provide several orders of magnitude increase in the capacitance of the dielectric material. Additionally, these high capacitance values are obtained at relatively low voltages found in current consumer and industrial electronics. The capacitors tested to date are simple, single-layer devices. Ultimately, a range of manufacturing methods are possible for making commercial devices. Features of the technology enable manufacturing via traditional thick-film processing methods widely used in the capacitor industry, or via advanced printing methods for state-of-the-art printed electronics. Future efforts will be made to advance the manufacturing and packaging processes to increase device energy density, including multilayer devices and packages
image of astronaut’s helmet from NASA (for breath detection). https://images.nasa.gov/details/sts103-302-002
Composite Dielectric Inks for Humidity Sensing
The NASA technology is based on a perovskite ceramic developed at MSFC, reduced lanthanum barium titanate (rLBT). rLBT is comprised of reduced barium titanate (BaTiO3) doped with lanthanum (La) and co-doped with potassium hydroxide (KOH). rLBT was developed while exploring the suitability of sintered perovskites to produce screen-printed ultracapacitors; the prototypes unexpectedly demonstrated an extreme sensitivity to moisture, prompting exploration of the material for use as a vapor-sensitive dielectric ink. To eliminate inconvenient high temperature firing necessary to produce capacitors, the inventors developed rLBT-loaded polymer composites capable of curing under low heat (110 degrees C) for epoxy or under ultraviolet (UV) light for UV-sensitive resin. At suitable ceramic particle loading concentrations, thin ink layers (30 micrometers) demonstrate RH sensitivity, instantaneously detecting breath vapor (RH change from 30% to 93%) with a recovery time of only 1s. Prototypes demonstrated near log-linear response curves over three orders of magnitude of capacitance with minimal drift (see Figures 1 and 2). NASA’s low temperature dielectric ink for humidity sensing is at technology readiness level (TRL) 4 (component performance has been validated in a lab setting) and the related patent is now available to license. Please note that NASA does not manufacture products itself for commercial sale.
Image from NASA photo library
SABERS: Solid-State Lithium-Sulfur Battery Technology Portfolio
The SABERS innovators developed novel lithium-sulfur designs, including sulfur-selenium on graphene cathodes, and lightweight bipolar plate stacking and packaging designs. SABERS is unique in several aspects, in particular, it deploys graphene-based manufacturing processes for the cathode and bipolar plates, and it uses a solid-state electrolyte in place of the liquid electrolyte found in other lithium-sulfur battery designs. The team has achieved energy densities over 500 W-hr/kg, with ongoing development targeting further improvements. Coin cell and pouch prototype demonstrations have been successful and are ongoing. Major component technologies in SABERS include the following: • S/Se Cathode – Sulfur/Selenium on graphene scaffold (LEW-20228-1) • Solid Electrolyte – Solid-state electrolyte composites (LEW-20445-1) • Bipolar Stack – Graphene plates (LAR-20257-1) Robust computational models have been developed to support the battery materials design and are available to licensees to evaluate and optimize different materials combinations and performance targets. Further developments in catholyte formulations, anode interlayering, and packaging optimization are presented in SABERS 2.0 (LEW-TOPS-188). Individual technologies can be licensed from either suite, or entire portfolios can be licensed to support solid-state battery development programs.
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