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NASA is developing safe, high energy and high capacity lithium-ion cell designs and batteries for future missions under NASAs Advanced Space Power System (ASPS) project. Advanced cell components, such as high specific capacity silicon anodes and low-flammable electrolytes have been developed for improving the cell specific energy and enhancing safety. To advance the technology readiness level, we have developed large-format flight-type hermetically sealed battery cells by incorporating high capacity silicon anodes, commercially available lithium nickel, cobalt, aluminum oxide (NCA) cathodes, and low-flammable electrolytes. In this report, we will present the performance results of these various battery cells. In addition, we will also discuss the post-test cell analysis results as well.

Met programmatic milestones for program. Demonstrated improved performance with wide operating temperature electrolytes containing ester co-solvents (i.e., methyl butyrate) containing electrolyte additives in A123 prototype cells: Previously demonstrated excellent low temperature performance, including 11C rates at -30 C and the ability to perform well down to -60 C. Excellent cycle life at room temperature has been displayed, with over 5,000 cycles being demonstrated. Good high temperature cycle life performance has also been achieved. Demonstrated improved performance with methyl propionate-containing electrolytes in large capacity prototype cells: Demonstrated the wide operating temperature range capability in large cells (12 Ah), successfully scaling up technology from 0.25 Ah size cells. Demonstrated improved performance at low temperature and good cycle life at 40 C with methyl propionate-based electrolyte containing increasing FEC content and the use of LiBOB as an additive. Utilized three-electrode cells to investigate the electrochemical characteristics of high voltage systems coupled with wide operating temperature range electrolytes: From Tafel polarization measurements on each electrode, it is evident the NMC-based cathode displays poor lithium kinetics (being the limiting electrode). The MB-based formulations containing LiBOB delivered the best rate capability at low temperature, which is attributed to improved cathode kinetics. Whereas, the use of lithium oxalate as an additive lead to the highest reversible capacity and lower irreversible losses.

Demonstrated improved performance with wide operating temperature electrolytes containing ester co - solvents (i.e., methyl propionate and ethyl butyrate) in a number of prototype cells: center dot Successfully scaled up low temperature technology to 12 Ah size prismatic Li - ion cells (Quallion, LCC), and demonstrated good performance down to - 60 o C. center dot Demonstrated wide operating temperature range performance ( - 60 o to +60 o C) in A123 Systems LiFePO 4 - based lithium - ion cells containing methyl butyrate - based low temperature electrolytes. These systems were also demonstrated to have excellent cycle life performance at ambient temperatures, as well as the ability to be cycled up to high temperatures.

(1) NASA is actively pursuing the development of advanced electrochemical energy storage and conversion devices for future lunar and Mars missions; (2) The Exploration Technology Development Program, Energy Storage Project is sponsoring the development of advanced Li-ion batteries and PEM fuel cell and regenerative fuel cell systems for the Altair Lunar Lander, Extravehicular Activities (EVA), and rovers and as the primary energy storage system for Lunar Surface Systems; (3) At JPL, in collaboration with NASA-GRC, NASA-JSC and industry, we are actively developing advanced Li-ion batteries with improved specific energy, energy density and safety. One effort is focused upon developing Li-ion battery electrolyte with enhanced safety characteristics (i.e., low flammability); and (4) A number of commercial applications also require Li-ion batteries with enhanced safety, especially for automotive applications.

Objectives of this work are: (1) Develop advanced Li -ion electrolytes that enable cell operation over a wide temperature range (i.e., -30 to +60C). (2) Improve the high temperature stability and lifetime characteristics of wide operating temperature electrolytes. (3) Improve the high voltage stability of these candidate electrolytes systems to enable operation up to 5V with high specific energy cathode materials. (4) Define the performance limitations at low and high temperature extremes, as well as, life limiting processes. (5) Demonstrate the performance of advanced electrolytes in large capacity prototype cells.

With the intent of improving the performance of lithium-ion cells at high temperatures, we have investigated the use of a number of electrolyte additives in experimental MCMB- Li(x)Ni(y)Co(1-y)O2 cells, which were exposed to temperatures as high as 80 C. In the present work, we have evaluated the use of a number of additives, namely vinylene carbonate (VC), dimethyl acetamide (DMAc), and mono-fluoroethylene carbonate (FEC), in an electrolyte solution anticipated to perform well at warm temperature (i.e., 1.0M LiPF6 in EC+EMC (50:50 v/v %). In addition, we have explored the use of novel electrolyte additives, namely lithium oxalate and lithium tetraborate. In addition to determining the capacity and power losses at various temperatures sustained as a result of high temperature cycling (cycling performed at 60 and 80 C), the three-electrode MCMB-Li(x)Ni(y)Co(1-y)O2 cells (lithium reference) enabled us to study the impact of high temperature storage upon the solid electrolyte interphase (SEI) film characteristics on carbon anodes (MCMB-based materials), metal oxide cathodes, and the subsequent impact upon electrode kinetics.

NASA requires lightweight rechargeable batteries for future missions to Mars and the outer planets that are capable of operating over a wide range of temperatures, with high specific energy and energy densities. Due to the attractive performance characteristics, Li-ion batteries have been identified as the battery chemistry of choice for a number of future applications. For example, JPL is planning to launch another unmanned rover mission to the planet Mars. This mission, referred to as the Mars Science Laboratory (MSL), will involve the use of a rover that is much larger than the previously developed Spirit and Opportunity Rovers for the 2003 Mars Exploration Rover (MER) mission, that are currently still in operation on the surface of the planet after more than five years. Part of the reason that the MER rovers have operated so successfully, far exceeding the required mission duration of 90 sols, is that they possess robust Li-ion batteries, manufactured by Yardney Technical Products, which have demonstrated excellent life characteristics. Given the excellent performance characteristics displayed, similar Li-ion batteries have been projected to successfully meet the mission requirements of the up-coming MSL mission. In addition to future missions to Mars, Li-ion technology is attractive for a number of other future NASA applications which require high specific energy, rechargeable batteries. To ascertain the viability of using Li-ion batteries for these applications, a number of performance validation tests have been performed on both Yardney cells and batteries of various sizes. These tests include mission simulation tests, charge and discharge rate characterization testing, cycle life testing under various conditions, and storage testing.

Due to their attractive properties and proven success, Li-ion batteries have become identified as the battery chemistry of choice for a number of future NASA missions. A number of these applications would be greatly benefited by improved performance of Li-ion technology over a wider operating temperature range, especially at low temperatures, such as future ESMD missions. In many cases, these technology improvements may be mission enabling, and at the very least mission enhancing. In addition to aerospace applications, the DoE has interest in developing advanced Li-ion batteries that can operate over a wide temperature range to enable terrestrial HEV applications. Thus, our focus at JPL in recent years has been to extend the operating temperature range of Li-ion batteries, especially at low temperatures. To accomplish this, the main focus of the research has been devoted to developing improved lithium-ion conducting electrolytes. In the present paper, we would like to present some of the results we have obtained with six different ethylene carbonate-based electrolytes optimized for low temperature. In addition to investigating the behavior in experimental cells initially, the performance of these promising low temperature electrolytes was demonstrated in large capacity, aerospace quality Li-ion prototype cells, manufactured by Yardney Technical Products and Saft America, Inc. These cells were subjected to a number of performance tests, including discharge rate characterization, charge rate characterization, cycle life performance at various temperatures, and power characterization tests.

This viewgraph presentation reviews the development of co-solvents for Li-ion cells. The future planned NASA Missions to explore Mars, the Moon, and the outer planets require rechargeable batteries that can operate at low temperatures. The applications for these batteries include landers, rovers and penetraters. This presentation reviews the work on optimizing the ester-based electrolyte formulations, with the intent of providing the best performance at temperatures ranging from -60 to +60 C.

Rechargeable Lithium-ion batteries have been operating successfully on both Spirit and Opportunity rovers for the last two years, which includes six months of Assembly Launch and Test Operations (ATLO), seven months of cruise and about eleven months of surface operations. The Battery Control Boards designed and fabricated in-house would protect cells against overcharge and over-discharge and provide cell balance. Their performance has thus far been quite satisfactory. The ground data o the mission simulation battery project little capacity loss of less than 3% during cruise and 180 sols. Batteries are poised to extend the mission beyond six months, if not a couple of years.

In 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 (>9 months), both Rovers are equipped with rechargeable Lithium-ion batteries, which have enabled operation for over 854 and 834 Sols of operation, respectively, to date. Given that the batteries were required to support the mission for 90 Sols of operation by design, it is significant that the batteries have demonstrated over a nine fold increase in life over mission objectives. In addition to supporting the surface operations in conjunction with a triple-junction deployable solar arrays, the batteries were designed to aid in the launch and the EDL pyros, and allow for anomalies during cruise. In summary, 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 +30 C), withstand long storage periods (e.g., cruise period), operate in an inverted orientation, and support high current pulses (e.g., firing pyro events). In order to determine the viability of meeting these requirements, ground testing was performed on a Rover Battery Assembly Unit (RBAU), consisting of two 8-cell 10 Ah lithium-ion batteries connected in parallel. The RBAU upon which the performance testing was performed is nearly identical to the batteries incorporated into the two Rovers currently on Mars. The testing includes, (a) performing initial characterization tests (discharge capacity at different temperatures), (b) simulating the launch conditions, (c) simulating the cruise phase conditions (including trajectory correction maneuvers), (d) simulating the entry, decent, and landing (EDL) pulse load profile (required to support the pyros) (e) simulating the Mars surface operation mission simulation conditions, as well as, (f) assessing capacity loss and impedance characteristics as a function of temperature and life. This paper provides further detail to previously reported results1 of the RBAU testing program, especially with regard to the life characteristics. To date, the lithium-ion batteries (fabricated by Lithion/Yardney, Inc.) have been demonstrated to far exceed the requirements defined by the mission, both on Mars and on the ground, and are projected to support an extended mission (> 4 years).

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.

In 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(deg)C to +4O(deg)C), withstand 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 meeting these requirements, ground testing was performed on a Rover Battery Assembly Unit (RBAU), consisting of two 8-cell 8 Ah lithium-ion batteries connected in parallel. The RBAU upon which the performance testing was performed is nearly identical to the batteries incorporated into the two Rovers currently on Mars. The testing performed includes, (a) performing initial characterization tests (discharge capacity at different temperatures), (b) simulating the launch conditions, (c) simulating the cruise phase conditions (including trajectory corrections), (d) simulating the entry, decent, and landing pulse load profile (if required to support the pyros) (e) simulating the Mars surface operation mission simulation conditions, as well as, (f) assessing performance capacity loss and impedance characteristics as a function of temperature and life. As will be discussed, the lithium-ion batteries (fabricated by LithiodYardney, Inc.) were demonstrated to far exceed the requirements defined by the mission, and are projected to support an extended mission (> 2 years) with margin to spare.

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 preselected discharge voltages, thus affecting depassivation during constant discharge voltage. Several ground tests were performed, 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. IIn this paper, we will describe these studies, in detail, as well as the depassivation of the lander flight batteries on both Spirit and 0pportunity rovers prior to the EDL sequence and their performance during landing on Mars.

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.