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Quarternary lithium-ion battery electrolyte solutions containing ester co-solvents in mixtures of carbonates have been demonstrated to have high conductivity at low temperatures (<-20 degrees Celcius).
Quarternary lithium-ion battery electrolyte solutions containing ester co-solvents in mixtures of carbonates have been demonstrated to have high conductivity at low temperatures (< -20C). However, in some cases the presence of such co-solvents does not directly translate into improved low temperature cell performance, presumably due to the formation of ionically resistive surface films on carbonaceous anodes. In order to understand this behavior, a number of lithium-graphite cells have been studied containing electrolytes with various ester co-solvents, including methyl acetate (MA), ethyl acetate (EA), ethyl propionate (EP), and ethyl butyrate (EB). The charge/discharge characterization of these cells indicates that the higher molecular weight esters result in electrolytes which possess superior low temperature performance in contrast to the lower molecular weight ester-containing solutions, even though these solutions display lower conductivity values.
Although many methods are available for producing single-walled carbon nanotubes (SWNTs), the conventional carbon arc process remains the most popular due to its simplicity and large production rate. In the carbon arc, SWNTs are catalytically synthesized by rapidly evaporating a graphite anode impregnated with NiN metal catalyst from which the nanotubes grow in an inert atmosphere. However, high temperatures inside the carbon arc generate strong buoyancy driven convection, and it is hypothesized that the non-uniform environment created by this flow has a large effect on the growth and morphology of the SWNTs. To study the effect of buoyancy on the arc process, a miniature carbon arc apparatus was developed to synthesize SWNTs in a microgravity environment substantially free from these strong convective flows. The reactor was operated for either 2.2 or 5 seconds during free-fall in the drop towers at the NASA Glenn Research Center. Two apparatus designs differing mainly in their production rate and power capacity were investigated. The first consisted of a miniaturized carbon arc employing a 1 mm diameter graphite anode and powered by a 0.54 F capacitor bank charged to 65 V. The second, larger apparatus employed a 4 mm diameter anode and was powered by a portable battery pack capable of providing in excess of 300 amps at 30 volts to the arc for the duration of a 5 second drop. Initial results indicated that transient heating is a very large effect in the short-duration drop tower carbon arcs, and thermal equilibrium of the arc plasma, buffer gas, and apparatus was not attained during the short microgravity periods. In addition, removal of the buoyant convection by the microgravity now allowed clear observation of large jets of evaporated carbon vapor streaming from the anode and mixing with the inert buffer gas. The initial mixing of these jets with the cold buffer gas combined with the thermal transient made it difficult to establish a uniform high temperature environment around the arc in the 2.1 to 5 second microgravity time interval, and even with a very high-powered arc, the arc region was cooler than in continuously operated arcs. Despite these difficulties, the miniature arc produced SWNTs in microgravity. However, given the large thermal transient to overcome, no dramatic difference in sample yield or composition was noted between normal gravity and q2-,andL%econd long microgravity runs.
Single wall carbon nanotubes are produced using the arc discharge process. Graphite anodes are filled with a mixture of nickel and yttrium metallic powders, then vaporized by creating a high current arc. By varying the current, gap distance, and ambient pressure it is shown that the best yield of single wall carbon nanotubes is obtained within a narrow range of conditions. The relative yield and purity of the product are indicated semi-quantitatively from scanning electric microscopy (SEM) and thermogravimetric analysis (TGA). Two types of anodes have been investigated. The first is hollow and filled with a powder mixture of graphite, nickel and yttrium. The second is filled with a paste made of a mixture of metal nitrates, graphite powder and carbon adhesive, then reduced in an argon atmosphere at high temperature. Product purity and yield will be compared for the two types of anodes. The graphite in the anodes may have hydrogen attached in the pores. To remove this impurity anodes have been baked up to 1400 - 1500 C. The effect of baking the anodes on impurities in the product will be given.
The following guantities were measured on a high-intensity electric arc with tungsten cathode and transpiration-cooled graphite anode burning in argon: electric current and voltage, cooling gas flow rate (argon), surface temperature of the anode and of the anode holder, and temperature profile in three cross-sections of the arc are column. The last mentioned values were obtained from spectroscopic photographs. From the measured quantities, the following values were calculated: the heat flux into the anode surface, the heat loss of the anode by radiation and conduction, and the heat which was regeneratively transported by the cooling gas back into the arc space. Heat balances for the anode were also obtained. The anode losses (which are approximately 80% of the total arc power for free burning arcs) were reduced by transpiration cooling to 20%. The physical processes of the energy transfer from the arc to the anode are discussed qualitatively.
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.
NASA is developing high specific energy and high specific capacity lithium-ion battery (LIB) technology for future NASA missions. Current state-of-art LIBs have issues in terms of safety and thermal stability, and are reaching limits in specific energy capability based on the electrochemical materials selected. For example, the graphite anode has a limited capability to store Li since the theoretical capacity of graphite is 372 mAh/g. To achieve higher specific capacity and energy density, and to improve safety for current LIBs, alternative advanced anode, cathode, and electrolyte materials are pursued under the NASA Advanced Space Power System Project. In this study, the nanostructed metal oxide, such as Fe2O3 on carbon nanotubes (CNT) composite as an LIB anode has been investigated.
A vacuum arc from a spot at the face of a graphite cathode to a graphite anode produces a beam of carbon ions and atoms. A carbon coating from this beam is deposited on an ion beam sputtered target to produce diamond-like carbon flakes. A graphite tube encloses the cathode, and electrical isolation is provided by an insulating sleeve. The tube forces the vacuum arc spot to be confined to the surface on the outermost end of the cathode. Without the tube the arc spot will wander to the side of the cathode. This spot movement results in low rates of carbon deposition, and the properties of the deposited flakes are more graphite-like than diamond-like.
Understanding the factors limiting Li+ charge transfer kinetics in Li-ion batteries is essential in improving the rate performance, especially at lower temperatures. The Li+ charge transfer process involved in the lithium intercalation of graphite anode includes the step of de-solvation of the solvated Li+ in the liquid electrolyte and the step of transport of Li+ in the preformed solid electrolyte interphase (SEI) on electrodes until the Li+ accepts an electron at the electrode and becomes a Li in the electrode. Whether the de-solvation process or the Li+ transport through the SEI is a limiting step depends on the nature of the interphases at the electrode and electrolyte interfaces. Several examples involving the electrode materials such as graphite, lithium titanate (LTO), lithium iron phosphate (LFP), lithium nickel cobalt aluminum oxide (NCA) and solid Li+ conductor such as lithium lanthanum titanate or Li-Al-Ti-phosphate are reviewed and discussed to clarify the conditions at which either the de-solvation or the transport of Li+ in SEI is dominating and how the electrolyte components affect the activation energy of Li+ charge transfer kinetics. How the electrolyte additives impact the Li+ charge transfer kinetics at both the anode and the cathode has been examined at the same time in 3-electrode full cells. The resulting impact on Li+ charge transfer resistance, Rct, and activation energy, Ea, at both electrodes are reported and discussed.
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.
Future NASA missions require high specific energy battery technologies, greater than 400 Wh/kg. Current NASA missions are using "state-of-the-art" (SOA) Li-ion batteries (LIB), which consist of a metal oxide cathode, a graphite anode and an organic electrolyte. NASA Glenn Research Center is currently studying the physical and electrochemical properties of the anode-electrolyte interface for ionic liquid based Li-air batteries. The voltage-time profiles for Pyr13FSI and Pyr14TFSI ionic liquids electrolytes studies on symmetric cells show low over-potentials and no dendritic lithium morphology. Cyclic voltammetry measurements indicate that these ionic liquids have a wide electrochemical window. As a continuation of this work, sp2 carbon cathode and these low flammability electrolytes were paired and the physical and electrochemical properties were studied in a Li-air battery system under an oxygen environment.
In the present work, a number of additives have been investigated for their effect on the charge characteristics of cells containing low temperature, high ester content electrolytes (1.0 M LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + methyl propionate (MP) 20:20:60 vol % + X additive). These experimental three-electrode cells are composed of graphite anodes, LiNiCoAlO2 cathodes, and a lithium metal reference electrode. Cells were first subjected to electrochemical characterization at various temperatures, consisting of performing Electrochemical Impedance Spectroscopy (EIS), linear micropolarization and Tafel polarization measurement to determine the kinetic parameters for both the anodes and cathodes. Following electrochemical characterization, the cells were subjected to charging at decreasing temperatures using C/5 rates to 4.10V, with a constant potential C/50 current taper. Analysis of the C/20 discharge following the charge at low temperature revealed either the presence or absence of a high voltage plateau during the initial stages of the discharge. This plateau has been linked to the presence of lithium metal on the anode previously and was used as a measure for the extent of lithium plating in the cell. Differential analysis (dV/dQ) was applied as well to more clearly visualize the position of the high voltage plateau and use the peak position (x-axis) in the dV/dQ plot as a gauge for the amount of plating which took place in the cell on the prior charge. Most additives investigated increased the resistance of the anode and decreased the resistance of the cathode, thereby leading to an overall increase in plating observed at low temperature. One additive, LiFSI, was found to be beneficial during low temperature charging, however studies of electrode kinetics from the cell containing LiFSI did not reveal significant improvements compared to the baseline.
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.
Silicon is a promising and attractive anode material to replace graphite for high capacity lithium ion cells since its theoretical capacity is approximately 10 times of graphite and it is an abundant element on earth. However, there are challenges associated with using silicon as Li-ion anode due to the significant first cycle irreversible capacity loss and subsequent rapid capacity fade during cycling. In this paper, cyclic voltammetry and electrochemical impedance spectroscopy are used to build a fundamental understanding of silicon anodes. The results show that it is difficult to form the SEI film on the surface of Si anode during the first cycle, the lithium ion insertion and de-insertion kinetics for Si are sluggish, and the cell internal resistance changes with the state of lithiation after electrochemical cycling. These results are compared with those for extensively studied graphite anodes. The understanding gained from this study will help to design better Si anodes.
Silicon is a promising and attractive anode material to replace graphite for high capacity lithium ion cells since its theoretical capacity is ~10 times of graphite and it is an abundant element on Earth. However, there are challenges associated with using silicon as Li-ion anode due to the significant first cycle irreversible capacity loss and subsequent rapid capacity fade during cycling. Understanding solid electrolyte interphase (SEI) formation along with the lithium ion insertion/de-insertion kinetics in silicon anodes will provide greater insight into overcoming these issues, thereby lead to better cycle performance. In this paper, cyclic voltammetry and electrochemical impedance spectroscopy are used to build a fundamental understanding of silicon anodes. The results show that it is difficult to form the SEI film on the surface of a Si anode during the first cycle; the lithium ion insertion and de-insertion kinetics for Si are sluggish, and the cell internal resistance changes with the state of lithiation after electrochemical cycling. These results are compared with those for extensively studied graphite anodes. The understanding gained from this study will help to design better Si anodes, and the combination of cyclic voltammetry with impedance spectroscopy provides a useful tool to evaluate the effectiveness of the design modifications on the Si anode performance.
Spectral radiance of low current graphite arc anode determined, using high accuracy spectroradiometer
Papers presented in these proceedings are on the state of the art in high-power lithium batteries, a design analysis of high-power Li-TiS2 battery, the performance and safety features of spiral wound lithium/thionyl chloride cells, the feasibility of a superhigh energy density battery of the Li/BrF3 electrochemical system, and an enhanced redox process of disulfide compounds and their application in high energy storage. Attention is also given to the structure and charge-discharge characteristics of mesophase-pitch based carbons, a study of carbons and graphites as anodes for lithium rechargeable cells, Li metal-free rechargeable Li(1+x)Mn2O4/carbon cells, and rechargeable lithium batteries using V6O13/V5O5 as the positive electrode material. Other papers discuss the electrochemical stability of organic electrolytes in contact with solid inorganic cathode materials, the electrochemical behavior of methyl formate solutions, and the interface between a solid polymer electrolyte and lithium anode.
A simple optical setup has been devised to enable safe viewing of the arc and measurement of the interelectrode gap in a process in which carbon nanotubes are produced in an arc between a catalyst-filled carbon anode and a graphite cathode. This setup can be used for visually guided manual positioning of the anode to maintain the interelectrode gap at a desired constant value, possibly as a low-technology alternative to the automatic position/voltage control described in Automatic Control of Arc Process for Making Carbon Nanotubes (MSC-23134), NASA Tech Briefs, Vol. 28, No. 3 (March 2004), page 51. The optical setup consists mainly of lenses for projecting an image of the arc onto a wall, plus a calibrated grid that is mounted on the wall so that one can measure the superimposed image of the arc. To facilitate determination of the end point of the process, the anode is notched, by use of a file, at the end of the filled portion that is meant to be consumed in the process. As the anode is consumed and the notch comes into view in the scene projected onto the wall, the process operator switches off the arc current.