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Subbarao, S.

Publications and source records attributed to Subbarao, S..

At least 19 records

Design analysis of bipolar Li-TiS2 batteries

The present study uses an empirical model to assess the feasibility of using the Li-TiS2 bipolar battery for high power applications. Predicted performance outputs at a variety of conditions were calculated. The effects of the design parameters on the performance of bipolar Li-TiS2 batteries are presented. Specific energies greater than 150 Wh/kg can be achieved at low rates. Specific power levels in excess of 100 W/kg can be reached at high rates but with a reduction of the specific energy to less than 70 Wh/kg.

Shen, D. H.↗

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.↗

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.↗

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.↗

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.↗

Symposium on Rechargeable Lithium Batteries, Hollywood, FL, Oct. 19-24, 1989, Proceedings

Recent advances in the technology and applications of rechargeable Li cells are discussed in reviews and reports. A general overview of the field is provided, and sections are devoted to organic electrolyte systems, polymeric electrolyte systems, inorganic electrolytes systems, and molten-salt electrolytes. Particular attention is given to electrolyte stabilization, the effects of organic additives on electrolyte performance, a cycle-life sensor, consumer-product applications, in situ measurements of gas evolution in Li secondary cells, ultrathin polymer cathodes, electrochemical growth of conducting polymers, and sealing Li/FeS(x) cells for a bipolar battery.

Subbarao, S.↗

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.↗

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.↗

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.↗

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.↗

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.↗

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.↗

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.↗

Development of ambient temperature secondary lithium cells

JPL is developing ambient temperature secondary lithium cells for future spacecraft applications. Prior studies on experimental laboratory type Li-TiS2 cells yielded promising results in terms of cycle life and rate capability. To further assess the performance of this cell, 5 Ah engineering model cells were developed. Initially baseline cells were designed and fabricated. Each cell had 15 cathodes and 16 anodes and the ratio of anode to cathode capacity is 6:1. A solution of 1.5 molar LiAsF6 in 2Me-THF was used as the electrolyte. Cells were evaluated for their cycle life at C/1 and C/5 discharge rates and 100 percent depth of discharge. The cells were cycled between voltage limits 1.7 and 2.8 volts. The rate of charge in all cases is C/10. The results obtained indicate that cells can operate at C/10 to C/2 discharge rates and have an initial energy density of 70 Wh/kg. Cells delivered more than 100 cycles at C/2 discharge rate. The details of cell design, the test program, and the results obtained are described.

Subbarao, S.↗

Low temperature safety of lithium-thionyl chloride cells

The use of lithium thionyl chloride cells for low-temperature applications is presently restricted because of their unsafe behavior. An attempt is made in the present investigation to identify the safe/unsafe low temperature operating conditions and to understand the low temperature cell chemistry responsible for the unsafe behavior. Cells subjected to extended reversal at low rate and -40 C were found to explode upon warm-up. Lithium was found to deposit on the carbon cathodes during reversal. Warming up to room temperature may be accelerating the lithium corrosion in the electrolyte. This may be one of the reasons for the cell thermal runaway.

Subbarao, S.↗

Capacity decline of ambient temperature secondary lithium battery

The use of ambient temperature secondary lithium cells is limited primarily because of the poor cycle life performance. Much of the cell capacity is irreversibly lost upon cycling. Studies have been undertaken to understand the problem of capacity decline. Experimental Li-TiS2 cells were fabricated and tested for their cycle life performance. Cells were disassembled at different stages of cycle life, and cell active components were analyzed by various analytical techniques. The results of this study indicate that all the cell's active components/materials are undergoing degradation. Details of the experiments carried out and the results obtained are described.

Shen, D. H.↗

Performance characteristics of ambient temperature secondary lithium cells

State of art ambient temperature secondary lithium cells were evaluated to determine their performance capability and limitations and to assess the present status of the technology of these cells. Li-MoS2, Li-NbSe3 and Li-TiS2 cells were evaluated for their charge/discharge characteristics, rate capability, and cycle life performance. The cells evaluated have a cycle life of 100-250 cycles at moderate discharge rates (C/5). The specific energy of these cells is between 50 and 100 Wh/Kg, depending upon the system. This paper describes the details of the cell designs, the test procedures, and the results of the evaluation studies.

Deligiannis, F.↗