NASA continues to have an interest in developing high specific energy and high power rechargeable batteries that can operate well over a wide temperature range. Potential applications that could be enabled or enhanced by such technology include: (i) future Mars and Lunar landers, (ii) future Mars and Lunar rovers, (iii) small robotic missions, and (iv) future planetary aerial vehicles, where high specific energy, high power and wide operating temperature range is desired. Future missions to some of the distant icy moons of Jupiter and Saturn are also anticipated to benefit from improved ultra-low temperature rechargeable batteries with high specific energy.¹ A number of terrestrial applications, including automotive and aviation Li-ion batteries, also benefit from having wide temperature range capability. To meet these needs, the Electrochemical Research, Technology, and Engineering Group at the Jet Propulsion Laboratory (JPL) has developed a number of low temperature Li-ion electrolytes utilizing various approaches. Broadly speaking, the performance targets of this work are to provide operation over the temperature range of +60^oC to -60^oC (delivering over 100 Wh/kg at -40^oC at reasonable rates).

This paper will provide an overview of the low temperature electrolyte development activities that have taken place at JPL, with a focus on enabling ultra-low temperature operation for extreme environments. The electrolytes evaluated included blends which contain elements of various approaches, including (i) the use of ester co-solvents, (ii) low ethylene carbonate content-based blends, (iii) the use of electrolyte additives, and (iv) the use of mixed lithium electrolyte salts. Experimental studies were performed utilizing three-electrode cells to determine the influence that the electrolyte type has upon the electrode kinetics as a function of temperature. A number of electrochemical techniques were employed to study these cells, including Electrochemical Impedance Spectroscopy (EIS), Tafel polarization, and linear micro-polarization.

Improved low temperature capability has been demonstrated in small and large capacity prototype cells with a number of chemistries (i.e., NCO, NCA, NMC, LCO and LFP-based chemistries), including the ability to deliver high specific energy down to -60^oC, good charge acceptance at low temperature, and high-power capability at -40^oC. Prototype cells incorporating JPL developed electrolytes were obtained from a number of vendors, including (i) Eagle Pitcher Technologies-Yardney Division, (ii) Enersys/Quallion, LLC, (iii) E-One Moli Energy Ltd., (iv) Saft America, and (iv) Navitas/A123. Emphasis was devoted to establishing the charge acceptance characteristics of the cells at very low temperatures, especially below -20^oC. Given that lithium plating when charging at low temperatures is a known degradation mode of Li-ion cells in general, attention was focused upon characterizing the conditions in which its likelihood may be more pronounced, determining the influence of electrolyte type, and attempting to detect its occurrence indirectly.

Early generations of electrolytes have been utilized in a number of NASA missions, including the 2003 Mars Exploration Rover, 2007 Phoenix Lander, 2011 Mars Science Laboratory (MSL) Curiosity Rover, 2018 Mars InSight Lander, and a JPL/CSUN CubeSat.^1-5 Previous work has also targeted improved low temperature performance of Li-ion cells for automotive applications. Current work is focused primarily upon providing higher specific energy coupled with good power characteristics at very low temperatures. Studies have also been performed demonstrating operational capability down to -90^oC in some systems, and survival capability to temperatures as low as -135^oC.

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). The information in this document is pre-decisional and is provided for planning and discussion only.

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