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At least 73 records · Page 4

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NASA NTRS1993

Evaluation of Carbon Anodes for Rechargeable Lithium Cells

Both liquid phase intercalation technique and electrochemical intercalation technique were examined for the Li-carbon material preparation. The electrochemical techniques include a intermittent discharge method and a two step method. These two electrochemical techniques can ensure to achieve the maximum reversible Li capacity for common commercially available carbon materials. The carbon materials evaluated by the intercalacation method includes: pitch coke, petroleum cole, PAN fiber and graphite materials. Their reversible Li capacity were determined and compared. In this paper, we also demonstrate the importance of EPDM binder composition in the carbon electrode. Our results indicated that it can impact the Li intercalation and de-intercalation capacity in carbon materials. Finally, two possibilities that may help explain the capacity degradation during practical cell cycling were proposed.

carbon anodes rechargeable lithium cells material ↗

NASA NTRS2013

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.↗

NASA NTRSDate not supplied

Predicting Thermal Response in a Li-ion Cell on a UAV Fight Profile

As the energy storage devices continue to "pack" more energy in a small space, any damage, battery component failure, manufacturing defect, or electrically abusing the battery can lead to catastrophic thermal runaway events. A catastrophic thermal event in a cell leads to high temperature, in some instances spewing of battery materials due to gas development from side reactions initiated due to high internal temperatures. Also, a thermal runaway event can propagate from a single "failed" cell to the pack in a battery pack, leading to a more significant event. Mitigating a thermal runaway event is important in the commercial and automotive sectors. However, preventing such events in an electric aircraft (or air taxis) is paramount due to the lack of alternatives in the event of a failure. Battery prognostics algorithms allow the prediction of state-of-charge (SOC) and end-of-life (EOL) of a Li-ion battery in a UAV (unmanned air vehicle) [1]. For this presentation, we will extend this two-level battery predictive algorithm to predict SOC, EOL, and estimated maximum temperature during a simulated flight. The model is extended by integrating a lumped physics-driven thermal model for high current densities [2]. The parameters used to control SOC and EOL are maximum storable charge, time constant for Li-ion diffusivity in the carbon particles, and internal cell resistance. Cycling leads to an increase in the heat generated by an aged Li-ion cell with a LiyCoO2 (LCO) cathode and a LixC6 (MCMB) anode. The aging of a cell leads to increase in SEI layer thickness, the diffusion time for the lithium ions inside the electrodes, and the local reaction rates, in addition to the thermodynamic abuse caused by fixed cycling voltages controlled by a Battery Management System. As the battery ages, the cell resistance increases, while the onset temperature of the thermal runaway decreases (depends on the cell chemistry and cell abuse history). Any large deviation of the cell temperature from the estimated (expected) value can identify a faulty cell. Since SEI decomposition has the lowest onset temperature in the series of reactions leading to thermal runaway, the model considers the self-heating rate of the SEI decomposition as onset temperature (similar to Ref. [3]). The parameters in the Arrhenius equation for the SEI heating rate depend on the number of cycles, the cell's operating temperature, and the cell's abuse history [4,5]. Coupling the electrochemical, thermal, and aging model allow the prognostic algorithm to estimate a typical cell voltage and temperature as a function of age (cycling and calendar), whose departure from measured values from the BMS is used to identify a safety event. In addition, we will present the results from two simulated flight scenarios for a UAV: typical and extreme, since the power requirements vary significantly during take-off, landing, and changing altitudes, while the power requirements remain low during the cruise. For this presentation, the power requirement for a battery pack in a UAV is scaled to a single cell. This cell is cycled through a simulated profile, and the data is collected and used to predict a safety event.

Li-ion↗

NASA NTRS2010

Optimized Li-Ion Electrolytes Containing Fluorinated Ester Co-Solvents

A number of experimental lithium-ion cells, consisting of MCMB (meso-carbon microbeads) carbon anodes and LiNi(0.8)Co(0.2)O2 cathodes, have been fabricated with increased safety and expanded capability. These cells serve to verify and demonstrate the reversibility, low-temperature performance, and electrochemical aspects of each electrode as determined from a number of electrochemical characterization techniques. A number of Li-ion electrolytes possessing fluorinated ester co-solvents, namely trifluoroethyl butyrate (TFEB) and trifluoroethyl propionate (TFEP), were demonstrated to deliver good performance over a wide temperature range in experimental lithium-ion cells. The general approach taken in the development of these electrolyte formulations is to optimize the type and composition of the co-solvents in ternary and quaternary solutions, focusing upon adequate stability [i.e., EC (ethylene carbonate) content needed for anode passivation, and EMC (ethyl methyl carbonate) content needed for lowering the viscosity and widening the temperature range, while still providing good stability], enhancing the inherent safety characteristics (incorporation of fluorinated esters), and widening the temperature range of operation (the use of both fluorinated and non-fluorinated esters). Further - more, the use of electrolyte additives, such as VC (vinylene carbonate) [solid electrolyte interface (SEI) promoter] and DMAc (thermal stabilizing additive), provide enhanced high-temperature life characteristics. Multi-component electrolyte formulations enhance performance over a temperature range of -60 to +60 C. With the need for more safety with the use of these batteries, flammability was a consideration. One of the solvents investigated, TFEB, had the best performance with improved low-temperature capability and high-temperature resilience. This work optimized the use of TFEB as a co-solvent by developing the multi-component electrolytes, which also contain non-halogenated esters, film forming additives, thermal stabilizing additives, and flame retardant additives. Further optimization of these electrolyte formulations is anticipated to yield improved performance. It is also anticipated that much improved performance will be demonstrated once these electrolyte solutions are incorporated into hermetically sealed, large capacity prototype cells, especially if effort is devoted to ensure that all electrolyte components are highly pure.

Prakash, G. K. Surya↗

NASA NTRS2000

Cycling and Low Temperature Performance of Li Ion Cells

Lithium-ion cells, of DD and D size, are being developed under a contract with the USAF for NASA's Mars Rover Missions. The cells contain spirally wound electrodes of LiNi02 positive electrode material and graphite anode in cylindrical stainless steel hardware.

Li-Ion↗

NASA NTRS1993

Mg2Si As Li-Intercalation Host For Li Cells

Compound Mg2Si shows promise as lithium-intercalation host for ambient-temperature rechargeable lithium electrochemical cells. As anode reactant material, LiXMg2Si chemically stable in presence of organic electrolyte used in such cells and stores large amounts of lithium. Intercalation reactions highly reversible at room temperature. Also retains sufficient mechanical strength during charge/discharge cycling. Lithium cells containing LixMg2Si anodes prove useful in spacecraft, military, communications, automotive, and other applications in which high energy-storage densities of lithium cells in general and rechargeability of cells needed.

Huang, Chen-Kuo↗

NASA NTRS1994

Development of Carbon Anode for Rechargeable Lithium Cells

Conventionally, rechargeable lithium cells employ a pure lithium anode. To overcome problems associated with the pure lithium electrode, it has been proposed to replace the conventional electrode with an alternative material having a greater stability with respect to the cell electrolytes. For this reason, several graphitic and coke based carbonaceous materials were evaluated as candidate anode materials...In this paper, we summarize the results of the studies on Li-ion cell development.

rechargeable batteries batteries lithium cells lit↗

NASA NTRS2015

Mesoporous Silicon-Based Anodes

For high-capacity, high-performance lithium-ion batteries. A new high-capacity anode composite based on mesoporous silicon is being developed. With a structure that resembles a pseudo one-dimensional phase, the active anode material will accommodate significant volume changes expected upon alloying and dealloying with lithium (Li).

Peramunage, Dharmasena↗

NASA NTRS1991

Advances in Li-TiS2 cell technology

JPL is involved in a NASA sponsored program to develop ambient temperature secondary cells for future space missions. After several years of research on various cathode materials, Titanium Disulfide (TiS2) was selected in view of its intrinsic reversibility and high faradaic utilization. In the last two years, the efforts were focused on improving the cycle life of the system and developing 1 Ah cells. Several approaches including the use of mixed solvent electrolytes, the operation of cells at low temperature, and the cycling of cells under different voltage limits, were initially examined to improve the cycle life performance of the Li-TiS2 system. Spiral wound 1 Ah cells fabricated incorporating the improvements from the above studies have delivered more than 600 cycles at 50% DOD. Work is in progress to identify alternate anode materials that can improve the cycle life of the cells to 1000 cycles at 50% DOD. This paper summarizes the advances made in the Li-TiS technology at JPL since 1989.

S Surampudi↗

NASA NTRS1991

Advances In Li-TiS2 Cell Techno1ogy

JPL is involved in a NASA sponsored program to develop ambient temperature secondary Lithium - Titanium Disulfide Cells for future space missions. After several years of research on various lithium systems, the Li-TiS2 system was selected for development in view of its practically realizable high specific energy. In the last two years, the efforts were focused on improving the cycle life of the system and optimizing the cell design. A number of approaches, such as the use of mixed solvent electrolytes, the use of alternate anode materials, the operation of cells at low temperature, and the cycling of cells under optimized voltage limits, are examined to improve cycle life performance of this system. Cycling studies in small 150 mAh cell have identified 1.5 M LiAsF6/2-MeTHF, 1.5 M LiAsF6/EC+2-eTHF, and 1.5 M LiAsF6/THF+2-MeTHF+2-MeF as promising electrolytes for Li-TiS2 cells. Li-Al and Li-C were selected for further assessment as candidate anode materials after a detailed theoretical and experimental evaluation. Cycling of the cells at low temperature did not result in improving the cycle life of the cells. Charge and discharge voltage limits were found to have significant influence on the cycle life of the cells activated with 1.5 M LiAsF6/THF+2-MeTHF+2-MeF electrolyte. The influence of design variables, such as ratio of electrode capacity, quantity of electrolyte, pack tightness, cell configuration, etc., on the cycle life performance are being examined as a part of the design optimization study. Spiral-wound 1 Ah cells fabricated for the design studies have completed more than 500 cycles at 50% DOD. This paper summarizes the advances made in the Li-TiS2 technology at JPL since 1989.

Surampudi, S.↗

NASA NTRS2013

Li-Ion Electrolytes with Improved Safety and Tolerance to High-Voltage Systems

Given that lithium-ion (Li-ion) technology is the most viable rechargeable energy storage device for near-term applications, effort has been devoted to improving the safety characteristics of this system. Therefore, extensive effort has been devoted to developing nonflammable electrolytes to reduce the flammability of the cells/battery. A number of promising electrolytes have been developed incorporating flame-retardant additives, and have been shown to have good performance in a number of systems. However, these electrolyte formulations did not perform well when utilizing carbonaceous anodes with the high-voltage materials. Thus, further development was required to improve the compatibility. A number of Li-ion battery electrolyte formulations containing a flame-retardant additive [i.e., triphenyl phosphate (TPP)] were developed and demonstrated in high-voltage systems. These electrolytes include: (1) formulations that incorporate varying concentrations of the flame-retardant additive (from 5 to 15%), (2) the use of mono-fluoroethylene carbonate (FEC) as a co-solvent, and (3) the use of LiBOB as an electrolyte additive intended to improve the compatibility with high-voltage systems. Thus, improved safety has been provided without loss of performance in the high-voltage, high-energy system.

Smart, Marshall C.↗

NASA NTRS2008

Chemical Passivation of Li(exp +)-Conducting Solid Electrolytes

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.

West, William↗

NASA NTRS2007

The use of Electrolyte Additives to Improve the High Temperature Resilience of Li-Ion Cells

This viewgraph presentation reviews the use of electrolyte additves to improve the resillience of Lithium ion cells. The objective of this work is to identify lithium-ion electrolytes, which will lead to Li-ion cells with a wide operational temperature range (+60 to -60 C), and to develop Li-ion electrolytes which result in cells that display improved high temperature resilience. Significant improvement in the high temperature resilience of Li-ion cells containing these additives was observed, with the most dramatic benefit being displayed by addition of DMAc. When the electrochemical properties of the individual electrodes were analyzed, the degradation of the anode kinetics was slowed most dramatically by the incorporation of DMAc into the electrolytes. Whereas, the greatest retention in the cathode kinetics was observed in the cell containing the electrolyte with VC added.

Li-ion electrolytes↗

NASA NTRS1986

Performance and properties of arsenic passivated lithium-titanium disulfide cells

In order to inhibit chemical degradation associated with the lithium-electrolyte interaction in ambient temperature lithium cells, an attempt was made to synthetically passivate the anode via ion implantation of arsenic. Solvent reduction is reduced although salt reaction with lithium is still present. The performance of the Li-TiS2 cell differs from those with standard electrodes, but further work is necessary to clarify the efficacy of this mode of passivation.

Yen, S. P. S.↗

NASA NTRS2009

The Effect of Electrolyte Additives upon the Lithium Kinetics of Li-Ion Cells Containing MCMB and LiNi(x)Co(1-x)O2 Electrodes and Exposed to High Temperatures

With the intent of improving the performance of lithium-ion cells at high temperatures, we have investigated the use of a number of electrolyte additives in experimental MCMB- Li(x)Ni(y)Co(1-y)O2 cells, which were exposed to temperatures as high as 80 C. In the present work, we have evaluated the use of a number of additives, namely vinylene carbonate (VC), dimethyl acetamide (DMAc), and mono-fluoroethylene carbonate (FEC), in an electrolyte solution anticipated to perform well at warm temperature (i.e., 1.0M LiPF6 in EC+EMC (50:50 v/v %). In addition, we have explored the use of novel electrolyte additives, namely lithium oxalate and lithium tetraborate. In addition to determining the capacity and power losses at various temperatures sustained as a result of high temperature cycling (cycling performed at 60 and 80 C), the three-electrode MCMB-Li(x)Ni(y)Co(1-y)O2 cells (lithium reference) enabled us to study the impact of high temperature storage upon the solid electrolyte interphase (SEI) film characteristics on carbon anodes (MCMB-based materials), metal oxide cathodes, and the subsequent impact upon electrode kinetics.

High Temperture Resilience↗

NASA NTRS1997

Microstructure Characterization and Stress Corrosion Evaluation of Autogenous and Hybrid Friction Stir Welded Al-Cu-Li 2195 Alloy

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.

Li, Zhixian↗

NASA NTRS1987

Electrochemical generation of useful chemical species from lunar materials

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Sammells, Anthony F.↗

NASA NTRS1988

The electrochemical generation of useful chemical species from lunar materials

Sammells, Anthony F.↗