An Update on the Skutterudite-Based Thermoelectric Technology Maturation Project for the Proposed eMMRTG
No abstract available
Caillat, T.↗
Engineering topics
Huang, C.-K.
Publications and source records attributed to Huang, C.-K..
Investigation of the properties of electrochemically depositied semiconductor materials for thermoelectric applications
At JPL, it is our desire to fabricate thermoelectric micro-devices for power generation and cooling applications using an electrochemical deposition (ECD) technique. We believe that the performance of our current micro-device developed is limited by the properties of the ECD materials.
Fleurial, J.-P.↗
Solid-State Power Generating Microdevices for Distributed Space System Architectures
Deep space missions have a strong need for compact, high power density, reliable and long life electrical power generation and storage under extreme temperature conditions. Conventional power generating devices become inefficient at very low temperatures (temperatures lower than 200 K encountered during Mars missions for example) and rechargeable energy storage devices cannot be operated thereby limiting mission duration. At elevated temperatures (for example for planned solar probe or Venus lander missions), thin film interdiffusion destroys electronic devices used for generating and storing power. Solar power generation strongly depends upon the light intensity, which falls rapidly in deep interplanetary missions (beyond 5 AU), and in planetary missions in the sun shadow or in dusty environments (Mars, for example). Radioisotope thermoelectric generators (RTGs) have been successfully used for a number of deep space missions RTGs. However, their energy conversion efficiency and specific power characteristics are quite low, and this technology has been limited to relatively large systems (more than 100 W). The National Aeronautics and Space Administration (NASA) and the Jet Propulsion Laboratory (JPL) have been planning the use of much smaller spacecrafts that will incorporate a variety of microdevices and miniature vehicles such as microdetectors, microsensors, and microrovers. Except for electrochemical batteries and solar cells, there are currently no available miniaturized power sources. Novel technologies that will function reliably over a long duration mission (ten years and over), in harsh environments (temperature, pressure, and atmosphere) must be developed to enable the success of future space missions. It is also expected that such micropower sources could have a wide range of terrestrial applications, in particular when the limited lifetime and environmental limitations of batteries are key factors. Additional information is contained in the original extended abstract.
Fleurial, J.-P.↗
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.↗
Effect of cycling on the lithium/electrolyte interface in organic electrolytes
Nondestructive methods such as ac impedance spectroscopy and microcalorimetry are used to study the effect of cell cycling on the lithium/electrolyte interface. The reactivity of both uncycled and cycled lithium towards various electrolytes is examined by measuring the heat evolved from the cells under open-circuit conditions at 25 C by microcalorimetry. Cycled cells at the end of charge/discharge exhibited considerably higher heat output compared with the uncycled cells. After 30 d of storage, the heat output of the cycled cells is similar to that of the uncycled cells. The cell internal resistance increases with cycling, and this is attributed to the degradation of the electrolyte with cycling.
Surampudi, S.↗
Design considerations for rechargeable lithium batteries
Viewgraphs of a discussion of design considerations for rechargable lithium batteries. The objective is to determine the influence of cell design parameters on the performance of Li-TiS2 cells. Topics covered include cell baseline design and testing, cell design and testing, cell design parameters studies, and cell cycling performance.
Shen, D. H.↗
Secondary lithium cells for space applications
It is concluded that secondary lithium batteries are suitable for planetary missions requiring high specific energy, long active shelf life, and limited cycle life. Titanium disulfide cathode material meet all the requirements for rechargeable lithium cell, including high intrinsic reversibility and realizable specific energy. Secondary lithium technology is still evolving, although low capacity cells have been demonstrated and greater than 700 cycle life was achieved. Work is in progress to improve the cycle life and safety of the electrolytes, alternate lithium anode, and the separators.
Surampudi, S.↗
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 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.↗
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.↗
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.↗