Future NASA missions aimed at exploring Mars, the Moon, and the outer planets require rechargeable batteries that can operate over a wide temperature range (–60 to +60 °C) to satisfy the requirements of various applications. In addition, many of these applications will require improved safety, due to their use by humans. Currently, the state-of-the-art lithium-ion (Li-ion) system has been demonstrated to operate over a wide range of temperatures (–40 to +40 °C); however, abuse conditions can often lead to cell rupture and fire. The nature of the electrolyte can greatly affect the propensity of the cell/battery to catch fire, given the flammability of the organic solvents used within.

Li-ion electrolytes have been developed that contain a flame-retardant additive in conjunction with fluorinated co-solvents to provide a safe system with a wide operating temperature range. Previous work incorporated fluorinated esters into multi-component electrolyte formulations, which were demonstrated to cover a temperature range from –60 to +60 °C. This work was described in “Fluoroester Co-Solvents for Low-Temperature Li+ Cells” (NPO-44626), NASA Tech Briefs, Vol. 33, No. 9 (September 2009), p. 37; and “Optimized Li-Ion Electrolytes Containing Fluorinated Ester Co-Solvents” (NPO-45824), NASA Tech Briefs, Vol. 34, No. 3 (March 2010), p. 48.

Other previous work improved the safety characteristics of the electrolytes by adding flame-retardant additives such as triphenyl phosphate (TPhPh), tri-butyl phosphate (TBuPh), triethyl phosphate (TEtPh), and bis(2,2,2-trifluoroethyl) methyl phosphonate (TFMPo). The current work involves further investigation of other types of flame-retardant additives, including tris(2,2,2-trifluoroethyl) phosphate, tris(2,2,2-trifluoroethyl) phosphite, triphenylphosphite, diethyl ethylphosphonate, and diethyl phenylphosphonate added to an electrolyte composition intended for wide operating temperatures.

In general, many of the formulations investigated in this study displayed good performance over a wide temperature range, good cycle life characteristics, and are expected to have improved safety characteristics, such as low flammability. Of the electrolytes studied, 1.0 M LiPF6 in EC+EMC+DEP (20:75:5 v/v %) and 1.0 M LiPF6 in EC+EMC+DPP (20:75:5 v/v %) displayed the best operation at low temperatures, whereas the electrolyte containing triphenylphosphite displayed the best cycle life performance compared to the baseline solution. It is anticipated that further improvements can be made to the life characteristics with the incorporation of a SET promoters (such as VC, vinylene carbonate), which will likely inhibit the decomposition of the flame-retardant additives.

This work was done by Marshall C. Smart, Kiah A. Smith, and Ratnakumar V. Bugga of Caltech and G. K. Surya Prakash of the University of Southern California for NASA’s Jet Propulsion Laboratory. For more information, contact This email address is being protected from spambots. You need JavaScript enabled to view it..

In accordance with Public Law 96-517, the contractor has elected to retain title to this invention. Inquiries concerning rights for its commercial use should be addressed to:

Innovative Technology Assets Management
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Refer to NPO-46599, volume and number of this NASA Tech Briefs issue, and the page number.

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This article first appeared in the October, 2010 issue of NASA Tech Briefs Magazine.

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