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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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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS1990

Reactivity of nonaqueous organic electrolytes towards lithium

The successful operation of an ambient temperature secondary lithium cell is primarily dependent on the stability of the electrolyte towards lithium. The lithium electrode on open circuit must be inert towards the electrolyte to achieve a long shelf life. The reactivity of tetrahydrofuran and 2-methyltetrahydrofuran based electrolytes with additives such as 2-methylfuran, ethylene carbonate, propylene carbonate, and 3-methylsulfolane was investigated by microcalorimetry and ac impedance spectroscopy techniques. Also the stability of electrolytes by open circuit stand tests was studied. Addition of ethylene carbonate and 2-methylfuran additives was found to improve the stability of tetrahydrofuran and 2-methyltetrahydrofuran based electrolytes. Long term microcalorimetry and ac impedance data clearly confirmed the higher stability of ethylene carbonate/2-methyltetrahydrofuran electrolyte compared to the 2-methyltetrahydrofuran and propylene carbonate/2-methyltetrahydrofuran electrolytes.

Shen, D. H.↗
NASA NTRS1994

Composite Solid Electrolyte For Lithium Cells

Composite solid electrolyte material consists of very small particles, each coated with thin layer of Lil, bonded together with polymer electrolyte or other organic binder. Material offers significant advantages over other solid electrolytes in lithium cells and batteries. Features include high ionic conductivity and strength. Composite solid electrolyte expected to exhibit flexibility of polymeric electrolytes. Polymer in composite solid electrolyte serves two purposes: used as binder alone, conduction taking place only in AI2O3 particles coated with solid Lil; or used as both binder and polymeric electrolyte, providing ionic conductivity between solid particles that it binds together.

Peled, Emmanuel↗
NASA NTRS1991

Mixed solvent electrolytes for ambient temperature secondary lithium cells

The present invention comprises an improved electrolyte for secondary lithium-based cells as well as batteries fabricated using this electrolyte. The electrolyte is a lithium containing salt dissolved in a non-aqueous solvent, which is made from a mixture of ethylene carbonate, ethylene propylene diene terpolymer, 2-methylfuran, and 2-methyltetrahydrofuran. This improved, mixed solvent electrolyte is more conductive than prior electrolytes and much less corrosive to lithium anodes. Batteries constructed with this improved electrolyte utilize lithium or lithium alloy anodes and cathodes made of metal chalcogenides or oxides, such as TiS.sub.2, NbSe.sub.3, V.sub.6 O.sub.13, V.sub.2 O.sub.5, MoS.sub.2, MoS.sub.3, CoO.sub.2, or CrO.sub.2, dissolved in a supporting polymer matrix, like EPDM. The preferred non-aqueous solvent mixture comprises approximately 5 to 30 volume percent ethylene carbonate, approximately 0.01 to 0.1 weight percent ethylene propylene diene terpolymer, and approximately 0.2 to 2 percent 2-methylfuran, with the balance being 2-methyltetrahydrofuran. The most preferred solvent comprises approximately 10 to 20 volume percent ethylene carbonate, about 0.05 weight percent ethylene propylene diene terpolymer, and about 1.0 percent 2-methylfuran, with the balance being 2-methyltetrahydrofuran. The concentration of lithium arsenic hexafluoride can range from about 1.0 to 1.8 M; a concentration 1.5 M is most preferred. Secondary batteries made with the improved electrolyte of this invention have lower internal impedance, longer cycle life, higher energy density, low self-discharge, and longer shelf life.

Shen, David H.↗
NASA NTRS2007

Norbornene-Based Polymer Electrolytes for Lithium Cells

Norbornene-based polymers have shown promise as solid electrolytes for lithium-based rechargeable electrochemical cells. These polymers are characterized as single-ion conductors. Single-ion-conducting polymers that can be used in lithium cells have long been sought. Single-ion conductors are preferred to multiple-ion conductors as solid electrolytes because concentration gradients associated with multiple-ion conduction lead to concentration polarization. By minimizing concentration polarization, one can enhance charge and discharge rates. Norbornene sulfonic acid esters have been synthesized by a ring-opening metathesis polymerization technique, using ruthenium-based catalysts. The resulting polymer structures (see figure) include sulfonate ionomers attached to the backbones of the polymer molecules. These molecules are single-ion conductors in that they conduct mobile Li+ ions only; the SO3 anions in these polymers, being tethered to the backbones, do not contribute to ionic conduction. This molecular system is especially attractive in that it is highly amenable to modification through functionalization of the backbone or copolymerization with various monomers. Polymers of this type have been blended with poly(ethylene oxide) to lend mechanical integrity to free-standing films, and the films have been fabricated into solid polymer electrolytes. These electrolytes have been demonstrated to exhibit conductivity of 2 10(exp -5)S/cm (which is high, relative to the conductivities of other solid electrolytes) at ambient temperature, plus acceptably high stability. This type of norbornene-based polymeric solid electrolyte is in the early stages of development. Inasmuch as the method of synthesis of these polymers is inherently flexible and techniques for the fabrication of the polymers into solid electrolytes are amenable to optimization, there is reason to anticipate further improvements.

Cheung, Iris↗
NASA NTRS2002

Improved performance and safety of lithium ion cells with the use of fluorinated carbonate-based electrolytes

There has been increasing interest in developing lithium-ion electrolytes that possess enhanced safety characteristics, while still able to provide the desired stability and performance. Toward this end, our efforts have been focused on the development of lithium-ion electrolytes which contain partially and fully fluorinated carbonate solvents. The advantage of using such solvents is that they possess the requisite stability demonstrated by the hydrocarbon-based carbonates, while also possessing more desirable physical properties imparted by the presence of the fluorine substituents, such as lower melting points, increased stability toward oxidation, and favorable SEI film forming Characteristics on carbon. Specifically, we have demonstrated the beneficial effect of electrolytes which contain the following fluorinated carbonate-based solvents: methyl 2,2,2-trifluoroethyl carbonate (MTFEC), ethyl-2,2,2 trifluoroethyl carbonate (ETFEC), propyl 2,2,2-trifluoroethyl carbonate (PTFEC), methyl-2,2,2,2',2',2' -hexafluoro-i-propyl carbonate (MHFPC), ethyl- 2,2,2,2',2',2' -hexafluoro-i-propyl carbonate (EHFPC), and di-2,2,2-trifluoroethyl carbonate (DTFEC). These solvents have been incorporated into multi-component ternary and quaternary carbonate-based electrolytes and evaluated in lithium-carbon and carbon-LiNio.8Coo.202 cells (equipped with lithium reference electrodes). In addition to determining the charge/discharge behavior of these cells, a number of electrochemical techniques were employed (i.e., Tafel polarization measurements, linear polarization measurements, and electrochemical impedance spectroscopy (EIS)) to further characterize the performance of these electrolytes, including the SEI formation characteristics and lithium intercalatiodde-intercalation kinetics. In addition to their evaluation in experimental cells, cyclic voltammetry (CV) and conductivity measurements were performed on select electrolyte formulations to further our understanding of the trends in stability and ionic mobility imparted by different alkyl substituents in linear carbonates.

li-ion batteries fluorinated carbonate electrolyte↗
NASA NTRS2019

Novel Electrolytes for Use in Li-Air Batteries for NASA Electric Aircraft

Li-Air batteries are a unique fit for electric aircraft due to their high theoretical energy densities and their potential to leverage on-board oxygen systems. The electrolyte and cathode are the limiting factors for advancing this technology. We are investigating novel "electrolyte and cathode engineering" concepts to enable Li-Air batteries with high practical energy densities, rechargeability and safety. New stable electrolytes and cathodes are being designed and fabricated for Li-Air batteries. An array of various electrolytes were screened and analyzed using NMR and DEMS analysis techniques to understand the fundamental decomposition mechanisms at the cathode surface and within the porous polymer separator. (NMR) spectroscopy has yielded mechanistic insight into decomposition pathway, which is vital to the development of future stable electrolyte candidates. Thus far, five new electrolytes have been screened with 2 showing promising results.

Li-Air↗
NASA NTRS2012

Improved Wide Operating Temperature Range of LiNiCoAiO2-based Li-ion Cells with Methyl Propionate-based Electrolytes

Demonstration of wide operating temperature range Li-ion electrolytes Methyl propionate-based wide operating temperature range electrolytes were demonstrated to provide dramatic improvement of the low temperature capability of Quallion prototype Li-ion cells (MCMB-LiNiCoAlO2). Some formulations were observed to deliver over 60% of the room temperature capacity using a 5C rate at - 40oC !! Represents over a 4-fold improvement over the baseline electrolyte system. Demonstrated operational capability of a number of systems over a wide temperature range (-40 to +70 C) Demonstrated reasonably good long term cycle life performance at high temperature (i.e., at +40deg and +50 C) A number of formulations containing electrolytes additives (i.e., FEC, VC, LiBOB, and lithium oxalate) have been shown to have enhanced lithium kinetics at low temperature and promising high temperature resilience. Demonstrated good performance in larger capacity (12 Ah) Quallion Li-ion cells with methyl propionate-based electrolytes. Current efforts focused upon performing life studies and the impact upon low temperature capability.

Li-ion electrolytes↗
NASA NTRS1974

Influence of ultrasounds on electrolytic polishing

On the basis of study of the electrolytic polishing of metal pieces, the following conclusions can be drawn: (1) Utilization of ultrasonically irradiated electrolytes in the electrolytic polishing of copper and steel pieces leads to enhanced polishing quality. (2) Polishing time for the reference pieces was twice as long as for the test pieces. (3) The chemical attack exerted on the surface of the test pieces in order to get the structure of the respective metal lasted less than half as long and yielded superior qualitative results in the copper as well as in the OT 60-2 steel test pieces polished with ultrasonically irradiated electrolytes. (4) The utilization of higher polishing current densities can be explained by the fact that the cavitational effect that arises in the electrolyte owing to ultrasounds contributes to an increase in the solution's electrical conductivity and elimination of gases from the electrolyte.

Gavrila, I.↗
NASA NTRS1991

Improved Li-TiS2 cell cycling in ether-based electrolytes with synergistic additives

Results of the application of 2-MeF and KOH additives to improve the lithium stability in THF, dioxolane, and THF/2-MeTHF solvent-based electrolytes are presented. The stability of these electrolytes with and without additives is evaluated by microcalorimetry and AC impedance spectroscopy. A novel method, cathode turnover number, is proposed to represent the electrolyte performance in a given system. The lithium cycling efficiency and cathode turnover number of the electrolytes are calculated from the cycle life data in experimental Li-TiS2 cells. Overall, THF/2-MeTHF electrolyte containing 2-MeF and/or KOH exhibited higher stability, lithium cycling efficiency, and cathode turnover number compared to THF and dioxolane electrolytes with and without additives.

Shen, D. H.↗
NASA NTRS2004

Lithium Polymer Electrolytes and Solid State NMR

Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for participation on a variety of other projects, including aero-gels and carbon graphite mat en als. The goals of the polymer electrolyte research are to improve the physical properties of the polymers. This includes improving conductivity, durability, and expanding the temperature range over which it is effective. Currently, good conductivity is only present at high temperatures. My goals are to experiment with different arrangements of rods and coils to achieve these desirable properties. Some of my experiments include changing the number of repeat units in the polymer, the size of the diamines, and the types of coil. Analysis of these new polymers indicates improvement in some properties, such as lower glass transition temperature; however, they are not as flexible as desired. With further research we hope to produce polymers that encompass all of these properties to a high degree.

Berkeley, Emily R.↗
NASA NTRS1984

Fuel cell and system for supplying electrolyte thereto with wick feed

An electrolyte distribution and supply system for use with a fuel cell having a means for drawing electrolyte therein is formed by a set of containers of electrolyte joined to respective fuel cells in a stack of such cells. The electrolyte is separately stored so as to provide for electrical isolation between electrolytes of the individual cells of the stack. Individual storage compartments are coupled by tubes containing wicking fibers, the ends of the respective tubes terminating on the means for drawing electrolyte in each of the respective fuel cells. Each tube is heat shrunk to tightly bind the fibers therein.

Cohn, J. Gunther↗
NASA NTRS2010

Supercapacitor Electrolyte Solvents with Liquid Range Below -80 C

A previous NASA Tech Brief ["Low-Temperature Supercapacitors" (NPO-44386) NASA Tech Briefs, Vol. 32, No 7 (July 2008), page 32] detailed ongoing efforts to develop non-aqueous supercapacitor electrolytes capable of supporting operation at temperatures below commercially available cells (which are typically limited to charging and discharging at > or equal to -40 C). These electrolyte systems may enable energy storage and power delivery for systems operating in extreme environments, such as those encountered in the Polar regions on Earth or in the exploration of space. Supercapacitors using these electrolytes may also offer improved power delivery performance at moderately low temperatures (e.g. -40 to 0 C) relative to currently available cells, offering improved cold-cranking and cold-weather acceleration capabilities for electrical or hybrid vehicles. Supercapacitors store charge at the electrochemical double-layer, formed at the interface between a high surface area electrode material and a liquid electrolyte. The current approach to extending the low-temperature limit of the electrolyte focuses on using binary solvent systems comprising a high-dielectric-constant component (such as acetonitrile) in conjunction with a low-melting-point co-solvent (such as organic formates, esters, and ethers) to depress the freezing point of the system, while maintaining sufficient solubility of the salt. Recent efforts in this area have led to the identification of an electrolyte solvent formulation with a freezing point of -85.7 C, which is achieved by using a 1:1 by volume ratio of acetonitrile to 1,3-dioxolane

Brandon, Erik↗
NASA NTRS2004

Safer Electrolytes for Lithium-Ion Cells

A number of nonvolatile, low-flammability liquid oligomers and polymers based on aliphatic organic carbonate molecular structures have been found to be suitable to be blended with ethylene carbonate to make electrolytes for lithium-ion electrochemical cells. Heretofore, such electrolytes have often been made by blending ethylene carbonate with volatile, flammable organic carbonates. The present nonvolatile electrolytes have been found to have adequate conductivity (about 2 mS/cm) for lithium ions and to remain liquid at temperatures down to -5 C. At normal charge and discharge rates, lithiumion cells containing these nonvolatile electrolytes but otherwise of standard design have been found to operate at current and energy densities comparable to those of cells now in common use. They do not perform well at high charge and discharge rates -- an effect probably attributable to electrolyte viscosity. Cells containing the nonvolatile electrolytes have also been found to be, variously, nonflammable or at least self-extinguishing. Hence, there appears to be a basis for the development of safer high-performance lithium-ion cells.

Kejha, Joe↗
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 NTRS2014

Lithium-Ion Electrolytes Containing Flame Retardant Additives for Increased Safety Characteristics

The invention discloses various embodiments of Li-ion electrolytes containing flame retardant additives that have delivered good performance over a wide temperature range, good cycle life characteristics, and improved safety characteristics, namely, reduced flammability. In one embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a fluorinated co-solvent, a flame retardant additive, and a lithium salt. In another embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a flame retardant additive, a solid electrolyte interface (SEI) film forming agent, and a lithium salt.

Smart, Marshall C.↗
NASA NTRS2019

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.↗
NASA NTRSDate not supplied

Elucidation of Electrolyte Decomposition Pathways in Li--O2 Batteries using Ab Initio Computations

Li-O2 batteries offer exciting possibilities for energy-storage applications requiring higher energy content than current Li-ion battery technologies. However, development of commercial Li-O2 batteries faces many challenges including electrolyte decomposition in order to realize the full potential of this emerging technology. In this work, we present ab initio calculations that probe the role of reactive oxygen species including singlet oxygen, superoxide, and peroxides on electrolyte decomposition for potential organic electrolytes for use in Li-O2 batteries. We investigate the influence that the harsh electrochemical environment near the cathode plays in promoting electrolyte decomposition by using increasingly detailed computational models. Our results highlight existing problems with organic electrolytes for Li-O2 battery development and suggest potential design strategies for reducing electrolyte decomposition.

Li-O2 Batteries↗
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↗