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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 19 records

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

Based on an extensive series of normalized full cell Li/TiS2 cycling studies, open-circuit storage tests, microcalorimetry and AC impedance studies, and chemical precedent, we propose an integrated chemical model consistent with experimental observations concerning the behavior of numerous LiAsF6/cyclic ether electrolytes. The particularly striking potency of certain additives such as 2-methylfuran and the hydroxide action resides in their ability to intercept several different adverse catalytic processes concurrently in the bulk electrolyte as well as the Li anode and TiS2 cathode.

Dominey, L. A.↗

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.↗

The improvement of rechargeable lithium battery electrolyte performance with additives

The deliberate introduction of additives like 2-methylfuran (2-MeF) is known to improve Li cycleability in cyclic ether electrolytes. The authors found that the proclivity of 2-MeF to polymerize in the bulk electrolyte or on a TiS2 cathode was inhibited by the addition of reduced oxygen species, such as O2- and OH-. Additionally, the polymerization of tetrahydrofuran and dioxolane and the destructive processes initiated by AsF6- decomposition to AsF5 and AsF3 were inhibited by the introduction of reduced oxygen species, particularly OH- at the 10-ppm to 100-ppm level.

Dominey, L. A.↗

Polymeric Electrolyte Containing 12-Crown-4 Ether

Experiments show incorporation of 12-crown-4 ether into solid electrolytes based on polyethylene oxide enhances their electrochemical properties. More specifically, 12-crown-4 ether increases Faradaic efficiency for Li+ ions in low-power secondary Li cells and enables operation of these cells at lower temperatures with higher efficiencies.

Nagasubramanian, Ganesa↗

Anion-Assisted Delivery of Multivalent Cations to Inert Electrodes

To understand and control key electrochemical processes - metal plating, corrosion, intercalation, etc. requires molecular-scale details of the active species at electrochemical interfaces and their mechanisms for de-solvation from the electrolyte. Using free energy sampling techniques we reveal the interfacial speciation of divalent cations in ether-based electrolytes and mechanisms for their delivery to an inert graphene electrode interface. Surprisingly, we find that anion solvophobicity drives a high population of anion-containing species to the interface that facilitate the delivery of divalent cations, even to negatively charged electrodes. Our simulations indicate that cation desolvation is greatly facilitated by cation-anion coupling. We propose anion solvophobicity as a molecular-level descriptor for rational design of electrolytes with increased efficiency for electrochemical processes limited by multivalent cation desolvation.

Electrochemical interfaces↗

Effects of 12-Crown-4 ether on the ionic conductivity and electrode kinetics of electrolytes in polyethylene oxide

Results are described of investigations of the electrical and electrochemical properties of thin films of polyethylene oxide (PEO) electrolytes with and without 12-Crown-4 ether (12Cr4) as a function of temperature and in the frequency regime 100 kHz-0.1 Hz. These measurements were made for LiCF3SO3, LiBF4, and LiClO4 salts. At a given temperature, the bulk conductivity, sigma, (S/cm), for a particular salt, depends on the 12Cr4 concentration with sigma reaching a maximum at about 3 mM 12Cr4. Of the three salts studied, the sigma is the highest for PEO/LiBF4 with 3 mM 12Cr4. The ac and dc measurements yield a lower charge transfer resistance for 12Cr4-incorporated samples than for samples without. Plating/stripping of Li occurs at a potential closer to Li(+)/Li for 12Cr4 samples than those without. The conductivities of a thin (about 100 microns) and a thick (400 microns) films are similar.

Nagasubramanian, G.↗

Effects of 12-crown-4 ether on the electrochemical performance of CoO2 and TiS2 cathodes in Li polymer electrolyte cells

The effect of adding 12-crown-4 ether (12Cr4) to the polyethylene oxide (PEO) electrolyte on the electrochemical properties of cells with Li(x)CoO2 or TiS2 as the cathode was investigated. The polymer electrolyte films were: (1) PEO, LiBF4; (2) PEO, LiBF4 with 12Cr4; (3) Li(x)CoO2, PEO, and LiBF4; and (4) Li(x)CoO2, PEO, LiBF4, and 12Cr4. It was found that, although 12Cr4 improved the cell performance over cells without 12Cr4 in the shallow c/d cycles (cyclic voltammetric behavior), it did not seem to prolong the active life of the cell. The cells with CoO2 as the cathode failed after a few c/d cycles, while similar cells with TiS2 did not fail even after 12 c/d cycles. The probable cause of failure in the case of CoO2 is ascribed to the instability of the CoO2 cathode.

Nagasubramanian, G.↗

12-crown-4 ether-assisted enhancement of ionic conductivity and interfacial kinetics in polyethylene oxide electrolytes

The electrical and electrochemical properties of thin films of polyethylene oxide electrolytes with and without 12-crown-4 ether (12Cr4) are studied as a function of temperature and in the frequency regime from 100 kHz to 0.1 Hz. These measurements were made on electrolytes containing LiCF3SO3, LiBF4, or LiClO4 salts. At a given temperature, the bulk conductivity for a particular salt depends on the 12Cr4 concentration, reaching a maximum for a ratio of 12Cr4 to Li of 0.003.

Nagasubramanian, G.↗

Transition Metal Oxides as Cathodes in Li-O2 battery: A First Principles Investigation

Li-O2 batteries have traditionally used carbon based electrodes (graphite, buckypaper) as the cathode of choice due to its good electrical conductivity, stability against non-aqueous electrolytes like Dimethyl ether (DME) and ease of handling. But, the carbon cathode also leads to formation of carbonate by-products that increase overpotentials during charging leading to degradation of cathode and reduction of cyclability. In this work, we investigate some of the well-known oxides as cathodes with focus on the interface between the oxide surfaces and the discharge product: Li2O2, in the Li-O2 battery using first principles computations. Our results show that attention must be paid on choosing the appropriate surface of the oxides. We extend the analysis to suggest other possible oxide chemistries that should be investigated as cathodes in Li-O2 batteries.

Li-O2 battery↗

Alkaline electrochemical cells and method of making

Equilibrated cellulose ether membranes of increased electrolytic conductivity for use as separators in concentrated alkaline electrochemical cells are investigated. The method of making such membranes by equilibration to the degree desired in an aqueous alkali solution mantained at a temperature below about 10 C is described.

Hoyt, H. E.↗

Improved Low Temperature Performance of Supercapacitors

Low temperature double-layer capacitor operation enabled by: - Base acetonitrile / TEATFB salt formulation - Addition of low melting point formates, esters and cyclic ethers center dot Key electrolyte design factors: - Volume of co-solvent - Concentration of salt center dot Capacity increased through higher capacity electrodes: - Zeolite templated carbons - Asymmetric cell designs center dot Continuing efforts - Improve asymmetric cell performance at low temperature - Cycle life testing Motivation center dot Benchmark performance of commercial cells center dot Approaches for designing low temperature systems - Symmetric cells (activated carbon electrodes) - Symmetric cells (zeolite templated carbon electrodes) - Asymmetric cells (lithium titanate/activated carbon electrodes) center dot Experimental results center dot Summary

benchmark↗

Separator for alkaline electric cells and method of making

Modified cellulose ether films having an increased electrolytic conductivity and a useable flexibility and in certain instances an increased flexibility are presented. Battery separator membranes comprising a cellulose ether and a minor proportion of a compatible water soluble base selected from the group consisting of alkali metal and ammonium hydroxides, aliphatic amines, and aliphatic hydroxyamines are used.

Pfluger, H. L.↗

Separator for alkaline electric batteries and method of making

Battery separator membranes of high electrolytic conductivity comprising a cellulose ether and a compatible metallic salt of water soluble aliphatic acids and their hydroxy derivatives are described. It was found that methyl cellulose can be modified by another class of materials, nonpolymeric in nature, to form battery separator membranes of low electrolytic resistance but which have the flexibility of membranes made of unmodified methyl cellulose, and which in many cases enhance flexibility over membranes made with unmodified methyl cellulose. Separator membranes for electrochemical cells comprising a cellulose ether and a modified selected from the group consisting of metallic salts of water soluble alphatic acids and their hydroxy derivatives and to electrochemical cells utilizing said membranes are described.

Pfluger, H. L.↗

Secondary Li battery incorporating 12-Crown-4 ether

A rechargeable lithium battery which utilizes a polyethylene oxide (PEO) solid polymeric electrolyte complexed with a lithium salt is disclosed. The conductivity is increased an order of magnitude and interfacial charge transfer resistance is substantially decreased by incorporating a minor amount of 12-Crown-4 ether in the PEO-lithium salt solid electrolyte film. Batteries containing the improved electrolyte permit operation at a lower temperature with improved efficiency.

Nagasubramanian, Ganesan↗

Lithium Dinitramide as an Additive in Lithium Power Cells

Lithium dinitramide, LiN(NO2)2 has shown promise as an additive to nonaqueous electrolytes in rechargeable and non-rechargeable lithium-ion-based electrochemical power cells. Such non-aqueous electrolytes consist of lithium salts dissolved in mixtures of organic ethers, esters, carbonates, or acetals. The benefits of adding lithium dinitramide (which is also a lithium salt) include lower irreversible loss of capacity on the first charge/discharge cycle, higher cycle life, lower self-discharge, greater flexibility in selection of electrolyte solvents, and greater charge capacity. The need for a suitable electrolyte additive arises as follows: The metallic lithium in the anode of a lithium-ion-based power cell is so highly reactive that in addition to the desired main electrochemical reaction, it engages in side reactions that cause formation of resistive films and dendrites, which degrade performance as quantified in terms of charge capacity, cycle life, shelf life, first-cycle irreversible capacity loss, specific power, and specific energy. The incidence of side reactions can be reduced through the formation of a solid-electrolyte interface (SEI) a thin film that prevents direct contact between the lithium anode material and the electrolyte. Ideally, an SEI should chemically protect the anode and the electrolyte from each other while exhibiting high conductivity for lithium ions and little or no conductivity for electrons. A suitable additive can act as an SEI promoter. Heretofore, most SEI promotion was thought to derive from organic molecules in electrolyte solutions. In contrast, lithium dinitramide is inorganic. Dinitramide compounds are known as oxidizers in rocket-fuel chemistry and until now, were not known as SEI promoters in battery chemistry. Although the exact reason for the improvement afforded by the addition of lithium dinitramide is not clear, it has been hypothesized that lithium dinitramide competes with other electrolyte constituents to react with lithium on the surface of the anode to form a beneficial SEI. Apparently, nitrides and oxides that result from reduction of lithium dinitramide on the anode produce a thin, robust SEI different from the SEIs formed from organic SEI promoters. The SEI formed from lithium dinitramide is more electronically insulating than is the film formed in the presence of an otherwise identical electrolyte that does not include lithium dinitramide. SEI promotion with lithium dinitramide is useful in batteries with metallic lithium and lithium alloy anodes.

Gorkovenko, Alexander A.↗

Development of High Conductivity Lithium-Ion Electrolytes for Low Temperature Cell Applications

NASA has continued interest in developing power sources which are capable of operating at low temperatures (-20 C and below) to enable future missions, such as the Mars Rover and Lander. Thus, under a program sponsored by the Mars Exploration Program, we have been involved in developing Li-ion batteries with improved low temperature performance. To accomplish this task, the focus of the research has been upon the development of advanced electrolyte systems with improved low temperature properties. This had led to the identification of a carbonate-based electrolyte, consisting of 1.0 M LiPF6 in EC + DEC + DMC (33:33:34), which has been shown to have excellent performance at -20 C in Li-ion AA-size prototype cells. Other groups are also actively engaged in developing electrolytes which can result in improved low temperature performance of Li-ion cells, including Polystor, Yardney, and Covalent. In addition to developing cells capable of operation at -20 C, there is continued interest in systems which can successfully operate at even lower temperatures (less than -30 C) and at high discharge rates (greater than C/2). Thus, we are currently focusing upon developing advanced electrolytes which are highly conductive at low temperatures and will result in cells capable of operation at -40 C. One approach to improve the low temperature conductivity of ethylene carbonate-based electrolytes involves adding co-solvents which will decrease the viscosity and extend the liquid range. Candidate solvent additives include formates, acetates, cyclic and aliphatic ethers, lactones, as well as other carbonates. Using this approach, we have prepared a number of electrolytes which contain methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), ethyl proprionate (EP), and 1,2-dimethoxyethane (DME), some of which have been characterized and reported. Other groups have also reported electrolytes based on mixtures of carbonates and acetates. In the present study, electrolytes which have been identified to have good low temperature conductivity and stability were incorporated into lithium-graphite cells for evaluation. Using various electrochemical methods, including ac impedence and DC micropolarization techniques, the film formation characteristics of graphite electrodes in contact with various lectrolyte formulations was investigated.

Smart, M. C.↗

Novel Elastomeric Membranes Developed for Polymer Electrolytes in Lithium Batteries

Lithium-based polymer batteries for aerospace applications need to be highly conductive from -70 to 70 C. State-of-the-art polymer electrolytes are based on polyethylene oxide (PEO) because of the ability of its ether linkages to solvate lithium ions. Unfortunately, PEO has a tendency to form crystalline regions below 60 C, dramatically lowering conductivity below this temperature. PEO has acceptable ionic conductivities (10(exp -4) to 10(exp -3) S/cm) above 60 C, but it is not mechanically strong. The room-temperature conductivity of PEO can be increased by adding solvent or plasticizers, but this comes at the expense of thermal and mechanical stability. One of NASA Glenn Research Center s objectives in the Polymer Rechargeable System program (PERS) is to develop novel polymer electrolytes that are highly conductive at and below room temperature without added solvents or plasticizers.

Tigelaar, Dean M.↗

Novel Ordered Crown Ether-Containing Polyimides for Ion Conduction

We report the synthesis and characterization of thermally-stable polyimides for use as battery and fuel cell electrolyte membranes. Dianhydrides used were 1,4,5,8- naphthalenetetracarboxylic dianhydride and/or 4,4'-(hexafluoroisopropylidene)diphthalic anhydride. Diamines used were anti-4,4-diaminodibenzo-l8-crown-6, 4,4'- diaminodibenzo-24-crown-8, 2,2-bis(4-aminophenyl)hexafluoropropane, and/or 2,5- diaminobenzenesulfonic acid. The polymers were characterized using electrochemical impedance spectroscopy (EIS), thermal analysis and X-ray diffraction. Polymers containing the hexafluoroisopropylidene (HFIP) group were soluble in common organic solvents, while polymers without the HFIP group were very poorly soluble. Sulfonation yields polymers that are sparingly soluble in aqueous base and/or methanol. Degree of sulfonation, determined by titration, was between one and three sulfonate groups per repeat unit. Proton conductivity was determined as a function of water content, with a maximum conductivity of l x 10(exp -2) per centimeter when fully hydrated. Crown ether-containing polymers exhibit a high degree of order that may be indicative of crown ether channel formation, which may facilitate Li(+) transport for use in battery membranes.

Irvin, Jennifer A.↗