The Use of Ester Co-Solvent Based Low Temperature Electrolytes in Experimental and Large Capacity Prototype Graphite-LiNiCoAlO₂ Lithium-Ion Cells

The 2003 Mars Exploration Rover (MER) and the Mars Science Laboratory (MSL) Curiosity Rover utilize a large capacity rechargeable Li-ion batteries that have been manufactured by EaglePicher-Yardney Division (Yardney). The cell chemistry adopted for these missions consists of mesocarbon microbeads (MCMB) anodes, LiNixCo1-xO2 cathode materials, and a low temperature ternary all-carbonate-based electrolyte developed at JPL1,2,3 encased in a hermetically sealed prismatic can. The attractiveness of this system is that it displays long life, high specific energy and the ability to operate over a wide temperature range, including charging and discharging at -20oC. Due to favorable performance characteristics and the heritage established, this cell chemistry has been used on other NASA missions, including the 2007 Phoenix Lander, Grail, and the current Juno mission to Jupiter. To meet even more challenging performance requirements, including the ability to be charged and discharged at -30oC, the Mars InSight lander, which is a spacecraft being built by Lockheed Martin Space Systems Company, will utilize the next generation LiNiCoAlO2 (NCA)-based chemistry, which incorporates a JPL developed ester containing low temperature electrolyte. 4,5,6 In the context of supporting possible future missions to the distant icy moons of Jupiter and Saturn, we are currently evaluating the potential of this system to operate at very low temperatures.7 To enable the exploration of the surfaces of these icy moons, one will require power systems that can potentially operate at ultra-low temperatures (down to -180oC) in high radiation environments. To meet these challenging requirements, we are currently developing ultra-low temperature rechargeable batteries with high specific energy and long life and with the ability to operate over the temperature range of +40oC to -60oC. It is preferred that the cells are capable of continuous operation at very low temperatures, so an emphasis has been focused upon demonstrating efficient charge characteristics over a wide temperature range. In this context, we have investigated a number of electrolytes that contain methyl propionate (MP) as a co-solvent, as well as various additives, to determine their influence upon the low temperature capacity (i.e., down to -65oC). In addition to evaluating the charge and discharge characteristics over a wide temperature range in large capacity prismatic cells and prototype pouch cells, experimental graphite - LiNiCoAlO2 three-electrode lithium-ion cells were used to determine the influence of electrolyte type upon the electrode kinetics over a range of temperatures. ACKNOWLEDGEMENT The work described here was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under contract with the National Aeronautics and Space Administration (NASA) and supported by the Ocean Worlds Program Office. REFERENCES 1. M.C. Smart, B.V. Ratnakumar, and S. Surampudi, “Electrolytes for Low Temperature Lithium-Ion Batteries Based on Mixtures of Aliphatic Carbonates”, J. Electrochem.Soc., 146, 486 (1999). 2. M. C. Smart, B. V. Ratnakumar, L. Whitcanack, S. Surampudi, J. Byers, and R. Marsh, IEEE Aerospace and Electronic Systems Magazine, 14: 11, 36-42 (1999). 3. M. C. Smart, B. V. Ratnakumar, L. D. Whitcanack, K. B. Chin, S. Surampudi, R. Gitzendanner, F. J. Puglia, and J. Byers, “Lithium-ion Batteries for Aerospace”, IEEE Aerospace and Electronic Systems Magazine, 19:1, 2004, pp. 18-25. 4. M.C. Smart, and B.V. Ratnakumar, L.D. Whitcanack, K.A. Smith, S. Santee, R. Gitzendanner, V. Yevoli, “Li-Ion Electrolytes Containing Ester Co-Solvents for Wide Operating Temperature Range”, ECS Trans. 11, (29) 99 (2008). 5. M. C. Smart, B. V. Ratnakumar, K. B. Chin, and L. D. Whitcanack, “Lithium-Ion Electrolytes Containing Ester Co-solvents for Improved Low Temperature Performance”, J. Electrochem. Soc., 157 (12), A1361-A1374 (2010). 6. M. C. Smart, S. F. Dawson, R. B. Shaw, L. D. Whitcanack, A. Buonanno, C. Deroy, and R. Gitzendanner, “Performance Validation of Yardney Low Temperature NCA-Based Li-ion Cells for the NASA Mars InSight Mission”, NASA Aerospace Battery Workshop, Huntsville, Alabama, November 18-20, 2014. 7. M. C. Smart, F. C. Krause, J. –P. Jones, L. D. Whitcanack, B. V. Ratnakumar, and E. J. Brandon, “The Use of Low Temperature Electrolytes in High Specific Energy Li-Ion Cells for Future NASA Missions to Icy Moons”, 229th Meeting of the Electrochemical Society, San Diego, May 29-June 2, 2016.

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