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Properties and Performance Attributes of Novel Co-Extruded Polyolefin Battery Separator Materials: Mechanical Properties - Part 1

As NASA prepares for its next era of manned spaceflight missions, advanced energy storage technologies are being developed and evaluated to address future mission needs and technical requirements and to provide new mission-enabling technologies. Cell-level components for advanced lithium-ion batteries possessing higher energy, more reliable performance and enhanced, inherent safety characteristics are actively under development within the NASA infrastructure. A key component for safe and reliable cell performance is the cell separator, which separates the two energetic electrodes and functions to prevent the occurrence of an internal short-circuit while enabling ionic transport. Recently, a new generation of co-extruded separator films has been developed by ExxonMobil Chemical and introduced into their battery separator product portfolio. Several grades of this new separator material have been evaluated with respect to dynamic mechanical properties and safety-related performance attributes. This paper presents the results of these evaluations in comparison to a current state-ofthe-practice separator material. The results are discussed with respect to potential opportunities to enhance the inherent safety characteristics and reliability of future, advanced lithium-ion cell chemistries.

Baldwin, Richard S.

Lithium-Based High Energy Density Flow Batteries

Systems and methods in accordance with embodiments of the invention implement a lithium-based high energy density flow battery. In one embodiment, a lithium-based high energy density flow battery includes a first anodic conductive solution that includes a lithium polyaromatic hydrocarbon complex dissolved in a solvent, a second cathodic conductive solution that includes a cathodic complex dissolved in a solvent, a solid lithium ion conductor disposed so as to separate the first solution from the second solution, such that the first conductive solution, the second conductive solution, and the solid lithium ionic conductor define a circuit, where when the circuit is closed, lithium from the lithium polyaromatic hydrocarbon complex in the first conductive solution dissociates from the lithium polyaromatic hydrocarbon complex, migrates through the solid lithium ionic conductor, and associates with the cathodic complex of the second conductive solution, and a current is generated.

Bugga, Ratnakumar V.

Properties and Performance Attributes of Novel Co-extruded Polyolefin Battery Separator Materials: Electrical Properties - Part 2

As NASA prepares for its next era of manned spaceflight missions, advanced energy storage technologies are being developed and evaluated to address and enhance future mission needs and technical requirements. Cell-level components for advanced lithium-ion batteries possessing higher energy, more reliable performance and enhanced, inherent safety characteristics have been under development within the NASA infrastructure. A key component for safe and reliable cell performance is the cell separator, which separates the two energetic electrodes and functions to inhibit the occurrence of an internal short circuit but preserves an ionic current. Recently, a new generation of co-extruded separator films has been developed by ExxonMobil Chemical and introduced into their battery separator product portfolio. Several grades of this new separator material were evaluated with respect to dynamic mechanical properties and safety-related performance attributes, and the results of these evaluations were previously reported in "Part 1: Mechanical Properties" of this publication. This current paper presents safety-related performance results for these novel materials obtained by employing a complementary experimental methodology, which involved the analysis of separator impedance characteristics as a function of temperature. The experimental results from this study are discussed with respect to potential cell safety enhancement for future aerospace as well as for terrestrial energy storage needs, and they are compared with pertinent mechanical properties of these materials, as well as with current state-of-the practice separator materials.

Baldwin, Richard S.

Quality control during IC processing

Manual gives detailed test procedures for controlling silicon-wafer processing in manufacture of integrated circuits. Included among 43 test procedures are: ionic, bacterial, and solids contamination of high-purity water needed for wafer processing; crystallographic reflection, purity, and orientation; substrate dimensions and finish; thickness of deposited epitaxial films; oxide quality; photoresist characteristics; pinholes in insulating layers; metallized adhesion; and quality of ohmic contact.

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Characteristics of switching plasma in an inverse-pinch switch

Characteristics of the plasma that switches on tens of giga volt-ampere in an inverse-pinch plasma switch (INPIStron) have been made. Through optical and spectroscopic diagnostics of the current carrying plasma, the current density, the motion of current paths, dominant ionic species have been determined in order to access their effects on circuit parameters and material erosion. Also the optimum operational condition of the plasma-puff triggering method required for azimuthally uniform conduction in the INPIStron has been determined.

Lee, Ja H.

Early Burn-In Parasitic Conduction in 500 °C Durable SiC JFET ICs

All prior reports of long-term 500 °C operation of SiC JFET-R ICs have noted the existence of an initial “burn-in” period of changes in measured electrical characteristics for the first few hundred hours oven-testing. This work reports measurements of “burn-in parasitic MOSFET conduction” that can substantially impact the performance of some circuits during initial heat-up of JFET ICs, but then subsequently disappears after a few hours of operation at 500 °C. The behavior appears generally consistent with the known MOS phenomenon of bias-temperature driven redistribution of mobile ionic contamination. Approaches for further mitigating this initial burn-in conduction mechanism are discussed.

silicon carbide

Ionic Liquids and New Proton Exchange Membranes for Fuel Cells

There is currently a great surge of activity in fuel cell research as laboratories across the world seek to take advantage of the high energy capacity provided by &el cells relative to those of other portable electrochemical power systems. Much of this activity is aimed at high temperature fie1 cells, and a vital component of such &el cells must be the availability of a high temperature stable proton-permeable membrane. NASA Glenn Research Center is greatly involved in developing this technology. Other approaches to the high temperature fuel cell involve the use of single- component or almost-single-component electrolytes that provide a path for protons through the cell. A heavily researched case is the phosphoric acid fuel cell, in which the electrolyte is almost pure phosphoric acid and the cathode reaction produces water directly. The phosphoric acid fie1 cell delivers an open circuit voltage of 0.9 V falling to about 0.7 V under operating conditions at 170 C. The proton transport mechanism is mainly vehicular in character according to the viscosity/conductance relation. Here we describe some Proton Transfer Ionic Liquids (PTILs) with low vapor pressure and high temperature stability that have conductivities of unprecedented magnitude for non-aqueous systems. The first requirement of an ionic liquid is that, contrary to experience with most liquids consisting of ions, it must have a melting point that is not much above room temperature. The limit commonly suggested is 100 C. PTILs constitute an interesting class of non-corrosive proton-exchange electrolyte, which can serve well in high temperature (T = 100 - 250 C) fuel cell applications. We will present cell performance data showing that the open circuit voltage output, and the performance of a simple H2(g)Pt/PTIL/Pt/O2(g) fuel cell may be superior to those of the equivalent phosphoric acid electrolyte fuel cell both at ambient temperature and temperatures up to and above 200 C. My work at NASA Glenn Research Center during this summer is to develop and characterize proton exchange membranes doped with ionic liquids. The main techniques used to characterize these materials are: Impedance Spectroscopy, NMR, DSC, TGA, DMA, IR, and SEM ...

Belieres, Jean-Philippe

Applications of SPICE for modeling miniaturized biomedical sensor systems

This paper proposes a model for a miniaturized signal conditioning system for biopotential and ion-selective electrode arrays. The system consists of three main components: sensors, interconnections, and signal conditioning chip. The model for this system is based on SPICE. Transmission-line based equivalent circuits are used to represent the sensors, lumped resistance-capacitance circuits describe the interconnections, and a model for the signal conditioning chip is extracted from its layout. A system for measurements of biopotentials and ionic activities can be miniaturized and optimized for cardiovascular applications based on the development of an integrated SPICE system model of its electrochemical, interconnection, and electronic components.

Microelectrodes

Exploring the cell: Sodium (beta-alumina) cupric chloride - Aluminum chloride - Sodium chloride between 136 and 200 C

Experiments were done with a molten-salt catholyte (initially CuCl2 in AlCl3-NaCl) separated from molten Na by beta alumina. The open-circuit reduction potentials were 4.3 and 3 volts for Cu++ and Cu+, respectively. High polarization and nonrechargeability characterized the cell's operation. The cell's ohmic resistance during discharge was higher than what would be expected from only the ionic resistance of the beta-alumina.

Miller, R. O.

NASA Tech Briefs, June 2009

Topics covered include: Device for Measuring Low Flow Speed in a Duct, Measuring Thermal Conductivity of a Small Insulation Sample, Alignment Jig for the Precise Measurement of THz Radiation, Autoignition Chamber for Remote Testing of Pyrotechnic Devices, Microwave Power Combiners for Signals of Arbitrary Amplitude, Synthetic Foveal Imaging Technology, Airborne Antenna System for Minimum-Cycle-Slip GPS Reception, Improved Starting Materials for Back-Illuminated Imagers, Multi-Modulator for Bandwidth-Efficient Communication, Some Improvements in Utilization of Flash Memory Devices, GPS/MEMS IMU/Microprocessor Board for Navigation, T/R Multi-Chip MMIC Modules for 150 GHz, Pneumatic Haptic Interfaces, Device Acquires and Retains Rock or Ice Samples, Cryogenic Feedthrough Test Rig, Improved Assembly for Gas Shielding During Welding or Brazing, Two-Step Plasma Process for Cleaning Indium Bonding Bumps, Tool for Crimping Flexible Circuit Leads, Yb14MnSb11 as a High-Efficiency Thermoelectric Material, Polyimide-Foam/Aerogel Composites for Thermal Insulation, Converting CSV Files to RKSML Files, Service Management Database for DSN Equipment, Chemochromic Hydrogen Leak Detectors, Compatibility of Segments of Thermoelectric Generators, Complementary Barrier Infrared Detector, JPL Greenland Moulin Exploration Probe, Ultra-Lightweight Self-Deployable Nanocomposite Structure for Habitat Applications, and Room-Temperature Ionic Liquids for Electrochemical Capacitors.

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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.

New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications

Future sustainable energy generation technologies such as photovoltaic and wind farms require advanced energy storage systems on a massive scale to make the alternate (green) energy options practical. The daunting requirements of such large-scale energy systems such as long operating and cycle life, safety, and low cost are not adequately met by state-of-the-art energy storage technologies such as vanadium flow cells, lead-acid, and zinc-bromine batteries. Much attention is being paid to redox batteries specifically to the vanadium redox battery (VRB) due to their simplicity, low cost, and good life characteristics compared to other related battery technologies. NASA is currently seeking high-specific- energy and long-cycle-life rechargeable batteries in the 10-to-100-kW range to support future human exploration missions, such as planetary habitats, human rovers, etc. The flow batteries described above are excellent candidates for these applications, as well as other applications that propose to use regenerative fuel cells. A new flow cell technology is proposed based on coupling two novel electrodes in the form of solvated electron systems (SES) between an alkali (or alkaline earth) metal and poly aromatic hydrocarbons (PAH), separated by an ionically conducting separator. The cell reaction involves the formation of such SES with a PAH of high voltage in the cathode, while the alkali (or alkaline earth metal) is reduced from such an MPAH complex in the anode half-cell. During recharge, the reactions are reversed in both electrodes. In other words, the alkali (alkaline earth) metal ion simply shuttles from one M-PAH complex (SES) to another, which are separated by a metal-ion conducting solid or polymer electrolyte separator. As an example, the concept was demonstrated with Li-naphthalene//Li DDQ (DDQ is 2,3-Dichloro-5,6-dicyano- 1,4-benzoquinone) separated by lithium super ion conductor, either ceramic or polymer (solid polymer or gel polymer) electrolytes. The reactants are Li-naphthalene dissolved in tetrahydrofuran (THF) with a lithium salt of 1M LiBF4 (lithium tetra fluoroborate) in the anode compartment, and DDQ again dissolved in THF and also containing 1M LiBF4 salt in the cathode half-cell. The solid electrolyte separator used in the first set of experiments is a ceramic solid electrolyte, available from a commercial source. The open circuit voltage of the cells is close to 3.0 V, as expected from the individual half-cell voltages of Li-naphthalene and Li-DDQ. Upon discharge, the cell shows steady discharge voltage of 2.7 V, which confirms that the electrochemical processes do involve lithium ion shuttling from the anodic compartment to the cathode half-cell. The reversibility or rechargeability is demonstrated by charging the partially discharged cells (i.e., with lithium present in the DDQ half). Once again, a steady voltage close to 3.0 V was observed during charge, indicating that the system is quite reversible. In the subsequent concept-demonstration studies, the ceramic electrolyte has been replaced with a gel polymer electrolyte, e.g., PVDF-HFP (poly vinylene difluoride hexafluoropropene) gel, which has several advantages such as high ionic conductivity (almost comparable to liquid electrolyte and about 2 orders of magnitude better than the ceramic equivalent), lower cost, and possibly higher chemical stability at the anode. In addition, it can be bonded to the electrode by thermal fusion to form membrane electrode assemblies (MEAs), as is done in fuel cells.

Bugga, Ratnakumar V.

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.

batteries