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At least 109 records · Page 6

Wide Operating Temperature Range Electrolytes for High Voltage and High Specific Energy Li-Ion Cells

A number of electrolyte formulations that have been designed to operate over a wide temperature range have been investigated in conjunction with layered-layered metal oxide cathode materials developed at Argonne. In this study, we have evaluated a number of electrolytes in Li-ion cells consisting of Conoco Phillips A12 graphite anodes and Toda HE5050 Li(1.2)Ni(0.15)Co(0.10)Mn(0.55)O2 cathodes. The electrolytes studied consisted of LiPF6 in carbonate-based electrolytes that contain ester co-solvents with various solid electrolyte interphase (SEI) promoting additives, many of which have been demonstrated to perform well in 4V systems. More specifically, we have investigated the performance of a number of methyl butyrate (MB) containing electrolytes (i.e., LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + MB (20:20:60 v/v %) that contain various additives, including vinylene carbonate, lithium oxalate, and lithium bis(oxalato)borate (LiBOB). When these systems were evaluated at various rates at low temperatures, the methyl butyrate-based electrolytes resulted in improved rate capability compared to cells with all carbonate-based formulations. It was also ascertained that the slow cathode kinetics govern the generally poor rate capability at low temperature in contrast to traditionally used LiNi(0.80)Co(0.15)Al(0.05)O2-based systems, rather than being influenced strongly by the electrolyte type.

Li-ion Battery↗

Sol-Gel Synthesis of La(0.6)Sr(0.4)CoO(3-x) and Sm(0.5)Sr(0.5)CoO(3-x) Cathode Nanopowders for Solid Oxide Fuel Cells

Nanopowders of La(0.6)Sr(0.4)CoO(3-x) (LSC) and Sm(0.5)Sr(0.5)CoO(3-x) (SSC) compositions, which are being investigated as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFC) with La(Sr)Ga(Mg)O(3-x) (LSGM) as the electrolyte, were synthesized by low-temperature sol-gel method using metal nitrates and citric acid. Thermal decomposition of the citrate gels was followed by simultaneous DSC/TGA methods. Development of phases in the gels, on heat treatments at various temperatures, was monitored by x-ray diffraction. Solgel powders calcined at 550 to 1000 C consisted of a number of phases. Single perovskite phase La(0.6)Sr(0.4)CoO(3-x) or Sm(0.5)Sr(0.5)CoO(3-x) powders were obtained at 1200 and 1300 C, respectively. Morphological analysis of the powders calcined at various temperatures was done by scanning electron microscopy. The average particle size of the powders was approx.15 nm after 700 C calcinations and slowly increased to 70 to 100 nm after heat treatments at 1300 to 1400 C.

Bansal, Narottam P.↗

All-Climate and Ultrafast Rechargeable Aluminum Batteries Enabled By Ternary Eutectic Electrolytes

For Rechargeable Aluminum Batteries (RABs), electrolytes emerge as the most crucial and decisive component due to the following aspects: (i) Sluggish reaction kinetics due to high gravimetric density of Al (2.70 g/cm 3 vs. 0.53 g/cm 3 for Li) and high surface charge density, (ii) a limited safe potential window owing to moderate standard redox potential values. The state-of-the-art electrolytes in the field exhibits a limited stability window (<2.6V vs. Al/Al +3 ), leading to undesired side reactions, such as Cl 2 gas generation, and self-discharge in RABs. Exploration of RABs low-temperature performance is restricted by electrolyte limitations.

Raju Vadthya↗

ECAS Phase I fuel cell results

This paper summarizes and discusses the fuel cell system results of Phase I of the Energy Conversion Alternatives Study (ECAS). Ten advanced electric powerplant systems for central-station baseload generation using coal were studied by NASA in ECAS. Three types of low-temperature fuel cells (solid polymer electrolyte, SPE, aqueous alkaline, and phosphoric acid) and two types of high-temperature fuel cells (molten carbonate, MC, and zirconia solid electrolyte, SE) were studied. The results indicate that (1) overall efficiency increases with fuel cell temperature, and (2) scale-up in powerplant size can produce a significant reduction in cost of electricity (COE) only when it is accompanied by utilization of waste fuel cell heat through a steam bottoming cycle and/or integration with a gasifier. For low-temperature fuel cell systems, the use of hydrogen results in the highest efficiency and lowest COE. In spite of higher efficiencies, because of higher fuel cell replacement costs integrated SE systems have higher projected COEs than do integrated MC systems. Present data indicate that life can be projected to over 30,000 hr for MC fuel cells, but data are not yet sufficient for similarly projecting SE fuel cell life expectancy.

Warshay, M.↗

Li-Ion Cell Development for Low Temperature Applications

JPL is involved in the development of rechargeable Li-ion cells for future Mars Exploration Missions. The specific objectives are to improve the Li-ion cell cycle life performance and rate capability at low temperature (<<-20 C) in order to enhance survivability of the Mars lander and rover batteries. Poor Li-ion rate capability at low temperature has been attributed to: (1) the electrolytes becoming viscous or freezing and/or (2) reduced electrode capacity that results from decreased Li diffusivity. Our efforts focus on increasing the rate capability at low temperature for Li-ion cells. In order to improve the rate capability we evaluated the following: (1) cathode performance at low temperatures, (2) electrode active material particle size on low temperature performance and (3) Li diffusivity at room temperature and low temperatures. In this paper, we will discuss the results of our study.

Huang, C.-K.↗

High-Energy-Density, Low-Temperature Li/CFx Primary Cells

High-energy-density primary (nonrechargeable) electrochemical cells capable of relatively high discharge currents at temperatures as low as -40 C have been developed through modification of the chemistry of commercial Li/CFx cells and batteries. The commercial Li/CFx units are not suitable for high-current and low-temperature applications because they are current limited and their maximum discharge rates decrease with decreasing temperature. The term "Li/CFx" refers to an anode made of lithium and a cathode made of a fluorinated carbonaceous material (typically graphite). In commercial cells, x typically ranges from 1.05 to 1.1. This cell composition makes it possible to attain specific energies up to 800 Wh/kg, but in order to prevent cell polarization and the consequent large loss of cell capacity, it is typically necessary to keep discharge currents below C/50 (where C is numerically equal to the current that, flowing during a charge or discharge time of one hour, would integrate to the nominal charge or discharge capacity of a cell). This limitation has been attributed to the low electronic conductivity of CFx for x approx. 1. To some extent, the limitation might be overcome by making cathodes thinner, and some battery manufacturers have obtained promising results using thin cathode structures in spiral configurations. The present approach includes not only making cathodes relatively thin [.2 mils (.0.051 mm)] but also using sub-fluorinated CFx cathode materials (x < 1) in conjunction with electrolytes formulated for use at low temperatures. The reason for choosing sub-fluorinated CFx cathode materials is that their electronic conductivities are high, relative to those for which x > 1. It was known from recent prior research that cells containing sub-fluorinated CFx cathodes (x between 0.33 and 0.66) are capable of retaining substantial portions of their nominal low-current specific energies when discharged at rates as high as 5C at room temperature. However, until experimental cells were fabricated following the present approach and tested, it was not known whether or to what extent low-temperature performance would be improved.

Whitacre, Jay↗

Development of Highly-Conductive Polyelectrolytes for Lithium Batteries

Future NASA and Air Force missions require reliable and safe sources of energy with high specific energy and energy density that can provide thousands of charge-discharge cycles at more than 40% depth- of-discharge and that can operate at low temperatures. All solid-state batteries have substantial advantages with respect to stability, energy density, storage fife and cyclability. Among all solid-state batteries, those with flexible polymer electrolytes offer substantial advantages in cell dimensionality and commensurability, low temperature operation and thin film design. The above considerations suggest that lithium-polymer electrolyte systems are promising for high energy density batteries and should be the systems of choice for NASA and US Air Force applications. Polyelectrolytes (single ion conductors) are among most promising avenues for achieving a major breakthrough 'in the applicability of polymer- based electrolyte systems. Their major advantages include unit transference number for the cation, reduced cell polarization, minimal salt precipitation, and favorable electrolyte stability at interfaces. Our research is focused on synthesis, modeling and cell testing of single ion carriers, polyelectrolytes. During the first year of this project we attempted the synthesis of two polyelectrolytes. The synthesis of the first one, the poly(ethyleneoxide methoxy acrylateco-lithium 1,1,2-trifluorobutanesulfonate acrylate, was attempted few times and it was unsuccessful. We followed the synthetic route described by Cowie and Spence. The yield was extremely low and the final product could not be separated from the impurities. The synthesis of this polyelectrolyte is not described in this report. The second polyelectrolyte, comb polysiloxane polyelectrolyte containing oligoether and perfluoroether sidechains, was synthesized in sufficient quantity to study the range of properties such as thermal stability, Li- ion- conductivity and stability toward lithium metal. Also, the batteries containing this polyelectrolyte were assembled and tested. The results are detailed below. The synthesis of another polyelectrolyte similar to polysiloxane polyelectrolyte has been started, however, the synthesis was not completed due to termination of the project.

Shriver, D. F.↗

Alkyl Pyrocarbonate Electrolyte Additives for Performance Enhancement of Li Ion Cells

Lithium ion rechargeable batteries are being developed for various aerospace applications under a NASA-DoD Interagency program. These applications require further improvements in several areas, specifically in the cycle life for LEO and GEO satellites and in the low temperature performance for the Mars Lander and Rover missions. Accordingly, we have been pursuing research studies to achieve improvement in the low temperature performance, long cycle life and active life of Li ion cells. The studies are mainly focused on electrolytes, to identify newer formulations of new electrolyte additives to enhance Li permeability (at low temperatures) and stability towards the electrode. The latter approach is particularly aimed at the formation suitable SEI (solid electrolyte interphase) on carbon electrodes. In this paper, we report the beneficial effect of using alkyl pyrocarbonates as electrolyte additives to improve the low temperature performance of Li ion cells.

Smart, M. C.↗

4-Vinyl-1,3-Dioxolane-2-One as an Additive for Li-Ion Cells

Electrolyte additive 4-vinyl-1,3-dioxolane-2-one has been found to be promising for rechargeable lithium-ion electrochemical cells. This and other additives, along with advanced electrolytes comprising solutions of LiPF6 in various mixtures of carbonate solvents, have been investigated in a continuing effort to improve the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. In contrast to work by other researchers who have investigated the use of this additive to improve the high-temperature resilience of Li-ion cells, the current work involves the incorporation of 4-vinyl-1,3-dioxolane-2-one into quaternary carbonate electrolyte mixtures, previously optimized for low-temperature applications, resulting in improved low-temperature performance. The benefit afforded by 4-vinyl-1,3- dioxolane-2-one can be better understood in the light of relevant information from a number of prior NASA Tech Briefs articles about electrolytes and additives for such cells. To recapitulate: The loss of performance with decreasing temperature is attributable largely to a decrease of ionic conductivity and the increase in viscosity of the electrolyte. What is needed to extend the lower limit of operating temperature is a stable electrolyte solution with relatively small lowtemperature viscosity, a large electric permittivity, adequate coordination behavior, and appropriate ranges of solubilities of liquid and salt constituents. Whether the anode is made of graphitic or non-graphitic carbon, a film on the surface of the anode acts as a solid/electrolyte interface (SEI), the nature of which is critical to low-temperature performance. Desirably, the surface film should exert a chemically protective (passivating) effect on both the anode and the electrolyte, yet should remain conductive to lithium ions to facilitate intercalation and de-intercalation of the ions into and out of the carbon during discharging and charging, respectively. The additives investigated previously include alkyl pyrocarbonates. Those additives help to improve low-temperature performances by giving rise to the formation of SEIs having desired properties. The formation of the SEIs is believed to be facilitated by products (e.g., CO2) of the decomposition of these additives. These decomposition products are believed to react to form Li2CO3-based films on the carbon electrodes. The present additive, 4-vinyl-1,3-dioxolane-2-one, also helps to improve lowtemperature performance by contributing to the formation of SEIs having desired properties, but probably in a different manner: It is believed that, as part of the decomposition process, the compound polymerizes on the surfaces of carbon electrodes.

Smart, Marshall↗

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↗

High power, gel polymer lithium-ion cells with improved low temperature performance for NASA and DoD applications

Both NASA and the U.S. Army have interest in developing secondary energy storage devices that are capable of meeting the demanding performance requirements of aerospace and man-portable applications. In order to meet these demanding requirements, gel-polymer electrolyte-based lithium-ion cells are being actively considered, due to their promise of providing high specific energy and enhanced safety aspects.

high power li-ion batteries↗

Electrolytes for Use in High Energy Lithium-Ion Batteries with Wide Operating Temperature Range

Objectives of this work are: (1) Develop advanced Li -ion electrolytes that enable cell operation over a wide temperature range (i.e., -30 to +60C). (2) Improve the high temperature stability and lifetime characteristics of wide operating temperature electrolytes. (3) Improve the high voltage stability of these candidate electrolytes systems to enable operation up to 5V with high specific energy cathode materials. (4) Define the performance limitations at low and high temperature extremes, as well as, life limiting processes. (5) Demonstrate the performance of advanced electrolytes in large capacity prototype cells.

voltage stability↗

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↗

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.↗

Low Temperature Double-layer Capacitors with Improved Energy Density: An Overview of Recent Development Efforts

Electrochemical double-layer capacitors are finding increased use in a wide range of energy storage applications, particularly where high pulse power capabilities are required. Double-layer capacitors store charge at a liquid/solid interface, making them ideal for low temperature power applications, due to the facile kinetic processes associated with the rearrangement of the electrochemical double-layer at these temperatures. Potential low temperature applications include hybrid and electric vehicles, operations in polar regions, high altitude aircraft and aerospace avionics, and distributed environmental and structural health monitoring. State-of-the-art capacitors can typically operate to -40 C, with a subsequent degradation in power performance below room temperature. However, recent efforts focused on advanced electrolyte and electrode systems can enable operation to temperatures as low as -70 C, with capacities similar to room temperature values accompanied by reasonably low equivalent series resistances. This presentation will provide an overview of recent development efforts to extend and improve the wide temperature performance of these devices.

energy storage↗

NASA Tech Briefs, February 2010

Topics covered include: Insulation-Testing Cryostat With Lifting Mechanism; Optical Testing of Retroreflectors for Cryogenic Applications; Measuring Cyclic Error in Laser Heterodyne Interferometers; Self-Referencing Hartmann Test for Large-Aperture Telescopes; Measuring a Fiber-Optic Delay Line Using a Mode-Locked Laser; Reconfigurable Hardware for Compressing Hyperspectral Image Data; Spatio-Temporal Equalizer for a Receiving-Antenna Feed Array; High-Speed Ring Bus; Nanoionics-Based Switches for Radio-Frequency Applications; Lunar Dust-Tolerant Electrical Connector; Compact, Reliable EEPROM Controller; Quad-Chip Double-Balanced Frequency Tripler; Ka-Band Waveguide Two-Way Hybrid Combiner for MMIC Amplifiers; Radiation-Hardened Solid-State Drive; Use of Nanofibers to Strengthen Hydrogels of Silica, Other Oxides, and Aerogels; Two Concepts for Deployable Trusses; Concentric Nested Toroidal Inflatable Structures; Investigating Dynamics of Eccentricity in Turbomachines; Improved Low-Temperature Performance of Li-Ion Cells Using New Electrolytes; Integrity Monitoring of Mercury Discharge Lamps; White-Light Phase-Conjugate Mirrors as Distortion Correctors; Biasable, Balanced, Fundamental Submillimeter Monolithic Membrane Mixer; ICER-3D Hyperspectral Image Compression Software; and Context Modeler for Wavelet Compression of Spectral Hyperspectral Images.

Source record↗

Low temperature double-layer capacitors

Double-layer capacitors capable of operating at extremely low temperatures (e.g., as low as -75.degree. C.) are disclosed. Electrolyte solutions combining a base solvent (e.g., acetonitrile) and a cosolvent are employed to lower the melting point of the base electrolyte. Example cosolvents include methyl formate, ethyl acetate, methyl acetate, propionitrile, butyronitrile, and 1,3-dioxolane. An optimized concentration (e.g., 0.10 M to 0.75 M) of salt, such as tetraethylammonium tetrafluoroborate, is dissolved into the electrolyte solution. In some cases (e.g., 1,3-dioxolane cosolvent) additives, such as 2% by volume triethylamine, may be included in the solvent mixture to prevent polymerization of the solution. Conventional device form factors and structural elements (e.g., porous carbon electrodes and a polyethylene separator) may be employed.

Brandon, Erik J.↗