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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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The success of rechargeable lithium ion batteries may be largely attributed to the surface films on the carbon anodes, which provide the anodes with adequate protection against continued reaction with electrolyte while permitting charge transfer.
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There has been increasing interest in developing lithium-ion electrolytes that possess enhanced safety characteristics, while still able to provide the desired stability and performance. Toward this end, our efforts have been focused on the development of lithium-ion electrolytes which contain partially and fully fluorinated carbonate solvents. The advantage of using such solvents is that they possess the requisite stability demonstrated by the hydrocarbon-based carbonates, while also possessing more desirable physical properties imparted by the presence of the fluorine substituents, such as lower melting points, increased stability toward oxidation, and favorable SEI film forming Characteristics on carbon. Specifically, we have demonstrated the beneficial effect of electrolytes which contain the following fluorinated carbonate-based solvents: methyl 2,2,2-trifluoroethyl carbonate (MTFEC), ethyl-2,2,2 trifluoroethyl carbonate (ETFEC), propyl 2,2,2-trifluoroethyl carbonate (PTFEC), methyl-2,2,2,2',2',2' -hexafluoro-i-propyl carbonate (MHFPC), ethyl- 2,2,2,2',2',2' -hexafluoro-i-propyl carbonate (EHFPC), and di-2,2,2-trifluoroethyl carbonate (DTFEC). These solvents have been incorporated into multi-component ternary and quaternary carbonate-based electrolytes and evaluated in lithium-carbon and carbon-LiNio.8Coo.202 cells (equipped with lithium reference electrodes). In addition to determining the charge/discharge behavior of these cells, a number of electrochemical techniques were employed (i.e., Tafel polarization measurements, linear polarization measurements, and electrochemical impedance spectroscopy (EIS)) to further characterize the performance of these electrolytes, including the SEI formation characteristics and lithium intercalatiodde-intercalation kinetics. In addition to their evaluation in experimental cells, cyclic voltammetry (CV) and conductivity measurements were performed on select electrolyte formulations to further our understanding of the trends in stability and ionic mobility imparted by different alkyl substituents in linear carbonates.
In order to enable future missions involving the exploration of the surface of Mars with Landers and Rovers, NASA desires long life, high energy density rechargeable batteries which can operate well at very low temperature (down to 40(deg)C). Lithium-ion technology has been identified as being the most promising chemistry, due to high gravimetric and volumetric energy densities, as well as, long life characteristics. However, the state-of-art (SOA) technology is not sufficient to meet the needs of many applications that require excellent low temperature capabilities. To further improve this technology, work at JF'L has been focused upon developing electrolytes that result in lithium-ion cells with wider temperature ranges of operation. These efforts have led to the identification of a number of ternary and quaternary, all carbonate-based electrolytes that have been demonstrated to result in improved low temperature performance in experimental three-electrode MCMB carbon/LiNio.sCoo.zOz cells. A number of electrochemical characterization techniques were performed on these cells (i.e., Tafel polarization measurements, linear polarization measurements, and electrochemical impedance spectroscopy (EIS)) to further enhance our understanding of the performance limitations at low temperature. The most promising electrolyte formulations, namely 1 .O M LiPF6EC+DEC+DMC+EMC (1 : 1: 1 :2 v/v) and 1 .O M LiPF6 EC+DEC+DMC+EMC (1 : 1 : 1 :3 v/v), were incorporated into SAFT prototype DD-size (9 Ahr) lithium- cells for evaluation. A number of electrical tests were performed on these cells, including rate characterization as a function of temperature, cycle life characterization at different temperatures, as well as, many mission specific characterization test to determine their viability to enable future missions to Mars. Excellent performance was observed with the prototype DD-size cells over a wide temperature range (-50 to 4OoC), with high specific energy being delivered at very low temperatures (i.e, over 95 WHrKg being delivered at 40(deg)C using a C/10 discharge rate).
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In this paper, we will describe the performance charateristics of the Li-ion rechargeable batteries during launch, cruise phase and on the surface of Mars thus far.
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.
NASA has interest in secondary energy storage batteries that display high specific energy, high energy density, long life characteristics, and perform well over a wide range of temperatures, in order to enable a number of future applications.
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This paper gives an overview of the energy storage technologies that are being used in space applications.
Lithium-ion batteries have contributed significantly to the success of NASA's Mars Rovers, Spirit and Opportunity that have been exploring the surface of Mars for the last two years and performing astounding geological studies to answer the ever-puzzling questions of life beyond Earth and the origin of our planets. Combined with the triple-junction solar cells, the lithium-ion batteries have been powering the robotic rovers, and assist in keeping the rover electronics warm, and in supporting nighttime experimentation and communications. The use of Li-ion batteries has resulted in significant benefits in several categories, such as mass, volume, energy efficiency, self discharge, and above all low temperature performance. Designed initially for the primary mission needs of 300 cycles over 90 days of surface operation, the batteries have been performing admirably, over the last two years. After about 670 days of exploration and at least as many cycles, there is little change in the end-of discharge (EOD) voltages or capacities of these batteries, as estimated from the in-flight data and corroborated by ground testing. Aided by such impressive durability from the Li-ion batteries, both from cycling and calendar life stand point, these rovers are poised to extend their exploration well beyond two years. In this paper, we will describe the performance characteristics of these batteries during launch, cruise phase and on the surface of Mars thus far.
NASA's Mars Rovers, Spirit and Opportunity, have been roving on the surface of Mars, capturing impressive images of its terrain and analyzing the drillings from Martian rocks, to answer the ever -puzzling questions of life beyond Earth and origin of our planets. These rovers are being enabled by an advanced rechargeable battery system, lithium-ion, for the first time on a space mission of this scale, for keeping the rover electronics warm, and for supporting nighttime experimentation and communications. These rover Li-ion batteries are characterized by their unique low temperature capability, in addition to the usual advantages associated with Li-ion chemistry in terms of mass, volume and energy efficiency. To enable a rapid insertion of this advanced Li-ion chemistry into flight missions, we have performed several performance assessment studies on several prototype cells over the last few years. These tests mainly focused primarily on the long-term performance characteristics, such as cycling and storage, as described in our companion paper. In addition, various tests have been performed on MER cells and engineering and proto flight batteries; under conditions relevant to these missions. For example, we have examined the performance of the cells in: a) an inverted orientation, as during integration and launch, and b) conditions of low rate discharge, between 3.0-2.5 V to support the mission clock. Likewise, we have determined the impedance of the proto-flight Rover battery assembly unit in detail, with a view to asses whether a current-limiting resistor would be unduly stressed, in the event of a shorting induced by a failed pyro. In this paper we will describe these studies in detail, as well as the performance of Li-ion batteries in Spirit and Opportunity rovers, during cruise and on Mars.
NASA's 2003 Mars Exploration Rover (MER) missions, Spirit and Opportunity, have been performing exciting surface exploration studies for the past six months. These two robotic missions were aimed at examining the presence of water and, thus, any evidence of life, and at understanding the geological conditions of Mars, These rovers have been successfully assisted by primary lithium-sulfur dioxide batteries during the critical entry, descent, and landing (EDL) maneuvers. These batteries were located on the petals of the lander, which, unlike in the Mars Pathfinder mission, was designed only to carry the rover. The selection of the lithium-sulfur dioxide battery system for this application was based on its high specific energy and high rate discharge capability, combined with low heat evolution, as dictated by this application. Lithium-sulfur dioxide batteries exhibit voltage delay, which tends to increase at low discharge temperatures, especially after extended storage at warm temperatures, In the absence of a depassivation circuit, as provided on earlier missions, e.g., Galileo, we were required to depassivate the lander primary batteries in a unique manner. The batteries were brought onto a shunt-regulated bus set at pre-selected discharge voltages, thus affecting depassivation during constant discharge voltages. Several ground tests were preformed, on cells, cell strings and battery assembly with five parallel strings, to identify optimum shunt voltages and durations of depassivation. We also examined the repassivation of lithium anodes, subsequent to depassivation. In this paper, we will describe these studies, in detail, as well as the depassivation of the lander flight batteries on both Spirit and Opportunity rover prior to the EDL sequence and their performance during landing on Mars.
n early 2004 JPL successfully landed two Rovers, named Spirit and Opportunity, on the surface of Mars after traveling >300 million miles over a 6-7 month period. In order to operate for extended duration on the surface of Mars, both Rovers are equipped with rechargeable Lithium-ion batteries, which were designed to aid in the launch, correct anomalies during cruise, and support surface operations in conjunction with a triple-junction deployable solar arrays. The requirements of the Lithium-ion battery include the ability to provide power at least 90 sols on the surface of Mars, operate over a wide temperature range (-20 C to +40 C), withstanding long storage periods (e.g., cruise period), operate in an inverted position, and support high currents (e.g., firing pyro events). In order to determine the viability of Lithium-ion technology to meet these stringent requirements, a comprehensive test program was implemented aimed at demonstrating the performance capability of prototype cells fabricated by Lithion, Inc. (Yardney Technical Products, Inc.). The testing performed includes, determining the (a) room temperature cycle life, (b) pulse capability as a function of temperature, (e) self-discharge and storage characteristics mission profile capability, (f) cycle life under mission simulation conditions, (g) impedance characteristics, (h) impact of cell orientation, and (i) performance in 8-cell engineering batteries. As will be discussed, the Lithium-ion prototype cells and batteries were demonstrated to meet, as well as, exceed the requirements defined by the mission.
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SAFT prismatic wound 5 Ahr MP series cells were evaluated for potential application in a lithium ion battery designed for Tactical Mobile Robots (TMR). In order to satisfy battery design requirements, a 10 Ahr battery containing two parallel 8-cell strings was proposed. The proposed battery has a weight and volume of approximately 3.2kg and 1.6 liters, respectively. Cell qualification procedures include initial characterization, followed by charge/discharge cycling at 100% DOD with intermittent EIS measurements at various state of charge. Certain cells were also subjected to extreme operational temperatures for worst-case analysis. Excellent specific energy (>130 Whr/kg) was obtained with initial characterization cycles. Even at abusive thermal conditions, the cell capacity fade was less than Ahr after 300 cycles. Rate characterization showed good cell discharge behavior with minimal decrease in capacity. At various state of charge, impedance measurements suggest that the cathode play a more significant role in capacity. At various state of charge impedance measurements suggest that the cathode play a more significant role in capacity fade than the anode.
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