Engineering topics

Halpert, G.

Publications and source records attributed to Halpert, G..

At least 73 records · Page 4

NASA NTRS1991

Performance characteristics of lithium primary cells after controlled storage

A program was initiated to investigate the effects of storage on the performance of lithium primary cells. Two types of liquid cathode cells were chosen to investigate these effects. The cell types included Li-SOCl2/BCX cells, Li-SO2 cells from two different manufacturers, and a small sample size of 8-year-old Li-SO2 cells. The following measurements are performed at each test interval: open circuit voltage, resistance and weight, microcalorimetry, ac impedance, capacity, and voltage delay. The authors examine the performance characteristics of these cells after one year of controlled storage at two temperatures (10 and 30 C). The Li-SO2 cells experienced little to no voltage and capacity degradation after one year storage. The Li-SOCl2/BCX cells exhibited significant voltage and capacity degradation after 30 C storage. Predischarging shortly prior to use appears to be an effective method of reducing the initial voltage drop. Studies are in progress to correlate ac impedance and microcalorimetry measurements with capacity losses and voltage delay.

Deligiannis, F.↗

NASA NTRS1991

Progress and recent developments in sodium-metal chloride batteries

Significant strides have been made in the development of high-temperature rechargeable sodium batteries utilizing transition metal chloride cathodes in the last decade, mainly due to the expertise available on Na/S batteries. These systems have already performed attractively in the various feasibility studies and have an excellent safety record. Despite the encouraging figures obtained for specific energies, certain design changes such as modifying the geometry of the beta alumina electrolyte and optimization of the porous cathodes for enhanced electrolyte flow need to be made to achieve high power densities required in applications such as electric vehicles and space. The chemistry of MCl2 cathodes, electrode fabrication, and design options are discussed, and performance data are examined.

Ratnakumar, B. V.↗

NASA NTRS1991

The status of rechargeable Li-TiS2 cell technology

Ambient temperature rechargeable lithium-titanium disulfide (Li-TiS2) cells are under development at JPL for future NASA missions. The development of this technology has involved assessment and selection of electrolytes, optimization of cell design, fabrication of cells, preparation of TiS2 cathodes, and evaluation of lithium alloys. This effort has resulted in achieving a major milestone, completing 700 cycles at 50 percent depth of discharge in 1-Ah cells fabricated in house.

Halpert, G.↗

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 NTRS1991

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.↗

NASA NTRS1991

Evaluation of lithium alloy anode materials for Li-TiS2 cells

A study was performed to select candidate lithium alloy anode materials and establish selection criteria. Some of the selected alloy materials were evaluated for their electrochemical properties and performance. This paper describes the criteria for the selection of alloys and the findings of the studies. Li-Si and Li-Cd alloys have been found to be unstable in the EC+2-MeTHF-based electrolyte. The Li-Al alloy system was found to be promising among the alloy systems studied in view of its stability and reversibility. Unfortunately, the large volume changes of LiAl alloys during charge/discharge cycling cause considerable 'exfoliation' of its active mass. This paper also describes ways how to address this problem. The rate of disintegration of this anode would probably be surpressed by the presence of an inert solid solution or a uniform distribution of precipitates within the grains of the active mass. It was discovered that the addition of a small quantity of Mn may improve the mechanical properties of LiAl. In an attempt to reduce the Li-Al alloy vs. Li voltage, it was observed that LiAlPb(0.1)Cd(0.3) material can be cycled at 1.5 mA/sq cm without exfoliation of the active mass.

Huang, C.-K.↗

NASA NTRS1991

A Review of Sodium-Metal Chloride Battery Activity At JPL

Following the disclosures by Coetzer et al. on the use of transition metal chlorides in chloroaluminates as alternate cathodes to sulfur in rechargeable sodium batteries, several laboratories, including the Jet Propulsion Laboratory, focused their attention on these systems. These systems have certain distinct advantages over sodium-sulfur batteries such as increased safety, inherent overcharge capability, and lower operating temperatures. Two systems, i.e., Na/FeCl2 and NaNiCl2, were developed extensively and evaluated in various applications including electric vehicles and space. Their performance has been very encouraging and warrants a detailed fundamental study on these cathodes. At the Jet Propulsion Laboratory a program was initiated two years back to understand the electrochemical behavior of FeCl2 and NiCl2, and to identify and evaluate other transition metal chlorides of promise. The initial efforts focused on the methods of fabrication of the electrodes and their electrochemical characterization. Subsequent studies were aimed at establishing the reaction mechanism, determining the kinetics, and identifying the rate-limiting processes in te reduction of metal chloride cathodes. Nickel chloride emerged form these studies as the most promising candidate material and was taken up for further detailed study on its passivation- a rate limiting process-under different experimental conditions. Also, the feasibility of using copper chloride, which is expected to have a higher energy density, has been assessed. On the basis of the criteria established from the voltammetric response of FeCl2, NiCl2, and CuCl2, several other transition metal chlorides were screened. Of these, molybdenum and cobalt appear promising.

Ratnakumar, B. V.↗

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 NTRS1990

Electrochemistry of metal chloride cathodes in sodium batteries

Fundamental electrochemical studies on three candidate materials, i.e., FeCl2, NiCl2, and CuCl2, were carried out using various techniques, such as cyclic voltammetry, linear polarization, potentiodynamic polarization, and ac impedance. These studies were aimed at identifying various rate processes in the reduction, elucidating the reaction mechanisms, and determining the kinetic parameters for the reduction. The limitations in the performance of these cathode materials in high power density applications were also examined. Finally, recommendations were made from these studies for the selection of a candidate system among these materials for future NASA applications.

Ratnakumar, B. V.↗

NASA NTRS1990

Advances in ambient temperature secondary lithium cells

The goal of the NASA/OAST sponsored program on the development of ambient-temperature secondary lithium cells for future space applications is to develop cells with a 100 W h/kg specific energy and capable of 1000 cycles at 50-percent depth of discharge. This paper examines the performance potentials of Li-TiS2, Li-MoS3, Li-V6O13, and Li-NbSe3 electrochemical systems at ambient temperature, together with cycle life and safety characteristics. Of these four, the Li-TiS2 system was found to be the most promising in terms of achievable specific energy and cycle life. Major advances made on the development of secondary lithium cells, which are in the areas of cathode processing technology, mixed solvent electrolytes, and cell assembly, are summarized.

Subbarao, S.↗

NASA NTRS1990

Studies on the properties and performance of TiS2 cathodes

Influence of raw material source, processing methods, and cell operating voltage limits on the performance of TiS2 cathode was examined. Raw materials obtained from three different sources were investigated. TiS2 electrodes were fabricated by painting, rolling, and pressing methods. Raw materials and electrodes were characterized for their physical, chemical, and electrochemical properties. The results obtained indicated that the performance of TiS2 cathodes was dependent on the purity and stoichiometry of the TiS2 material. Fabrication methods were found to have minimal influence on the performance of cathodes. The capacity loss observed during the early stages of cycling was attributed to the trapping of lithium in TiS2. Operating voltage limits were found to have significant influence on the cycle life performance of the cells.

Huang, C.-K.↗

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 NTRS1990

Fundamental studies on the metal chloride cathodes in sodium batteries

The authors report studies of the passivation of the NiCl2 electrode during reduction, its effect on the electrochemical rate kinetics for the reduction, and its dependence on the state of charge of the electrode. NiCl2 exhibits passive behavior more readily at lower states of charge due to a decrease in the electrochemical area, resulting from NaCl deposited during reduction. The passive behavior is evident from the DC polarization curves as well as AC impedance plots at the same potentials, implying a correlation between them. The results of the studies are presented in detail.

Ratnakumar, B. V.↗

NASA NTRS1990

The influence of temperature on the cycle life performance of rechargeable Li-TiS2 cells

The authors report studies on the influence of low temperature on the properties and cycling performance of six selected electrolytes. The electrolytes investigated were 2-MeTHF, EC/2-MeTHF, THF, THF/2-MeTHF, EC/THF, and EC/THF/2-MeTHF. All the electrolytes contained 1.5M LiAsF6. Open circuit stand tests indicated that organic electrolytes exhibited improved stability towards lithium at 10 C. However, cycling of the cells at 10 C did not result in improved cycle life performance.

Shen, D. H.↗

NASA NTRS1990

Capacity decline of ambient temperature secondary Li-TiS2 cells

The main objective of the study described was to identify the causes responsible for the capacity losses observed during cycling of secondary Li-TiS2 cells. Experimental Li-TiS2 cells were fabricated and tested for their cycle life performance. The open circuit voltage of the cells was monitored during the rest period between the charging and discharging. The polarization at the Li and TiS2 electrodes was also monitored during cycling. Cycled cells were disassembled and the cathodes were analyzed by various analytical techniques. The results of the study indicate that the observed capacity loss is almost entirely due to the increased polarization of the TiS2 electrode with cycling. The electrolyte was found to degrade during cycling and the degradation products were found to deposit at the TiS2 electrode, which probably lead to the higher polarization.

Subbarao, S.↗

NASA NTRS1989

Advances in ambient temperature secondary lithium cells

The goal is to develop secondary lithium cells with a 100 Wh/kg specific energy capable of 1000 cycles at 50 percent DOD. The approach towards meeting this goal initially focused on several basic issues related to the cell chemistry, selection of cathode materials and electrolytes and component development. The performance potential of Li-TiS2, Li-MoS3, Li-V6O13 and Li-NbSe3 electrochemical systems was examined. Among these four, the Li-TiS2 system was found to be the most promising system in terms of achievable specific energy and cycle life. Major advancements to date in the development of Li-TiS2 cells are in the areas of cathode processing technology, mixed solvent electrolytes, and cell assembly. A summary is given of these advances.

Subbarao, S.↗

NASA NTRS1989

Low temperature testing of Li-SOCl2 cells

The performance and safety characteristics Li-SOCl2 cells were evaluated at -40 C. Tests were conducted on cells of several defferent designs to determine the influence of cell design on performance and safety. The cells exhibited low operating voltages, poor voltage regulation, and low capacity at -40 C. The performance of the cells was found to be critically dependent on the cell design. No safety problems were observed during discharge to 2.0 V under constant current and constant load operating conditions. Cells subjected to prolonged periods of continuous drain at constant-load did not vent/rupture upon warm-up. Cells subjected to prolonged reversal were found to be potentially hazardous. Microcalorimetry and electrochemical impedance spectroscopy studies performed on the cells suggested that those containing a catalyst may exhibit poor shelf life.

Subbarao, S.↗

NASA NTRS1989

Advances in ambient temperature secondary lithium cells

The Jet Propulsion Laboratory is involved in a Research and Development program sponsored by NASA/OAST on the development of ambient temperature secondary lithium cells for future space applications. Some of the projected applications are planetary spacecraft, planetary rovers, and astronaut equipment. The main objective is to develop secondary lithium cells with greater than 100 Wh/kg specific energy while delivering 1000 cycles at 50 percent Depth of Discharge (DOD). To realize these ambitious goals, the work was initially focused on several important basic issues related to the cell chemistry, selection of cathode materials and electrolytes, and component development. The performance potential of Li-TiS2, Li-MoS3, Li-V6O13 and Li-NbSe3 electrochemical systems was examined. Among these four, the Li-TiS2 system was found to be the most promising system in terms of realizable specific energy and cycle life. Some of the major advancements made so far in the development of Li-TiS2 cells are in the areas of cathode processing technology, mixed solvent electrolytes, and cell assembly. Methods were developed for the fabrication of large size high performance TiS2 cathodes. Among the various electrolytes examined, 1.5M LiAsF6/EC + 2-MeTHF mixed solvent electrolyte was found to be more stable towards lithium. Experimental cells activated with this electrolyte exhibited more than 300 cycles at 100 percent Depth of Discharge. Work is in progress in other areas such as selection of lithium alloys as candidate anode materials, optimization of cell design, and development of 5 Ah cells. The advances made at the Jet Propulsion Laboratory on the development of secondary lithium cells are summarized.

Subbarao, S.↗