50 Years with Lithium Batteries

The discovery of 7 still available primary battery systems involving the lithium anode occurred some 50 years ago in the period of 1970 to 1973. The discoveries (and many others which did not survive competition) were made in a number of industrial and academic laboratories, including Union Carbide’s Parma Technical Center, where I led the lithium research group. These studies were part of a world-wide search to find satisfactory cathodes and electrolytes to take advantage of the remarkable properties of lithium as an anode. The well-known advantages of lithium give it almost ideal properties as a battery anode except that it is very difficult to handle in air due to reaction with both oxygen and nitrogen and reacts with any solvent containing dissociable protons to form hydrogen gas. The work by W.S. Harris in 1958 1 established that solvents such as propylene carbonate, ethylene carbonate and butyrolactone were stable in the presence of lithium metal giving impetus to the search for appropriate lithium battery cathodes. The anodes all utilized thin lithium foil (usually in the range of 100 to 200 μm) contacted by a nickel, copper or stainless steel tab, or container body, while the cathodes and electrolytes were of three types: 1.) solid cathode with liquid electrolytes, 2.) solid cathode with solid electrolyte and 3.) liquid cathode with liquid electrolyte. Two solid cathodes with liquid electrolyte were carbon monofluoride and manganese dioxide in the 3V class came from laboratories in Japan. A third solid cathode in the 1.5V class was iron disulfide (the mineral pyrites) came from our laboratory in the U.S. in this period, but was not disclosed until 1978. This cathode was first discussed in a high temperature cell with lithium alloy anodes by Argonne National Laboratory in the U.S. The lithium iodine cell with an in-situ formed LiI solid electrolyte was discovered in the laboratories of the Jet Propulsion Laboratory of NASA and developed independently by several U.S. companies, mainly Catalyst Research Corp. and Wilson Greatbatch Ltd. A key component of the cell is polyvinylpyridine which is mixed with iodine under heat to form a liquid slurry, which is poured into the cathode compartment of the cell Lithium/sulfur dioxide was the first liquid cathode-liquid electrolyte cell and was patented by American Cyanimid Co.in the U.S. in 1971 2 . An example in the patent corresponds closely to the present contents involving a lithium sheet anode with a carbon collector for the cathode and an electrolyte containing LiBr salt with sulfur dioxide and acetonitrile solvents. Work at our laboratory discovered the lithium/thionyl chloride and lithium/sulfuryl chloride systems. The patent was filed in 1971, but patent acceptance was delayed by an interference proceeding until 1983 3 . The feature of these systems was the absence of any co-solvent such as acetonitrile which allowed higher energy density. The properties of these batteries as available will be discussed and the systems compared for advantages and disadvantages References: S. Harris, Electrochemical Studies in Cyclic Esters, PhD thesis, University of California, Berkeley, 1958. L. Maricle and J.P. Mohns, U.S. Patent 3,567,515, March 2, 1971. E. Blomgren and M.L. Kronenberg, U.S. Patent 4,400,453, August 23, 1983