(Keynote) The Introduction of Intercalation into Battery Science: 1968-1990

Abstract

The field of Solid State Ionics was born with the discovery of fast ionic motion in a number of solids, in particular beta alumina in 1967 [1,2]. The challenge of measuring their ionic conductivity was achieved by using mixed ionic and electronic conducting materials such as NaxWO3 and LixV2O5 [3]. It was not until the early 1970s that the critical role of intercalation in batteries was generally recognized. Before then it was thought that reduction of the cathode occurred by the abstraction of oxygen forming Li2O and a lower oxide, rather than the intercalation compound LixV2O5 or MnOOH in a lithium cell or the alkaline cell. [4,5] Exxon in 1972 mounted a corporate research effort in energy beyond petroleum and chemicals. Part of this effort was directed at superconductivity in intercalation reactions, and out of the effort, which was focused on TaS2 came the relevation that significant energy could be stored in intercalation reactions. An effort on (Li,Na)xTiS2 batteries began in 1972, and shortly thereafter a full development and subsequently manufacturing facility was set-up. TiS2 was the preferred cathode of all the layered dichalcogenides because of its light weight and metallic conductivity, so no conducting binder was needed [6]. Large prismatic cells were demonstrated at the 1977 Electric Vehicle show in Chicago, and smaller coin cells were built for marketing purposes. These latter are still operational today, some 40 years later [7]. A challenge with the initial cells was the formation of dendritic lithium, and so pure lithium was not used in the commercial cells but rather a LiAl alloy [8], formed in situ by the reaction of lithium and aluminum foils. Similar lithium battery efforts on intercalation reactions (oxides, sulfides, and selenides) were underway at a number of companies in the 1970s, for example at Bell Labs and in start-ups in the Boston area and later at MoliEnergy in Vancouver. In the mid-1980s Exxon licensed the technology to a Japanese, a European and a US company. In the 1980s Bell Labs described the use of a carbon-based anode [9] and Oxford University described the cathodic behavior of the layered dioxide of cobalt [10]. SONY licensed both these technologies and developed them into the first commercially successful secondary lithium batteries in 1991 [11]. The history of the lithium battery has been well described by Fletcher in the book Bottle Lightening [12], and further in-depth science has been reviewed in Chem. Rev. [13]. [1]. Y. Y. Yao, J. T. Kummer, “Ion transport in beta alumina”, J. Inorg. Nucl. Chem., 29, (1967) 2453. [2]. M. S. Whittingham, R. A. Huggins, “Beta Alumina - Prelude to a Revolution in Solid State Electrochemistry” NBS Special Publications 1972, 364, 139-154. [3] M. S. Whittingham, R. A. Huggins, “Measurement of Sodium Ion Transport in Beta Alumina Using Reversible Solid Electrodes” J. Chem. Phys., 54, (1971) 414. [4]. M. S. Whittingham, “The role of ternary phases in cathode reactions”, Journal of the Electrochemical Society, 123 (1976) 315-320. [5]. M. S. Whittingham “Electrical energy storage and intercalation chemistry”, Science, 192 (1976), 1126-1127. [6]. M. S. Whittingham, “Chemistry of Intercalation Compounds: Metal Guests in Chalcogenide Hosts”, Prog. Solid State Chem., 12 (1978) 41-99. [7]. Nathalie Pereira, Glenn G. Amatucci, M. Stanley Whittingham, Robert Hamlen, “Lithiumtitanium disulfide rechargeable cell performance after 35 years of storage”, J. Power Sources, 280 (2015) 18-22. [8]. B. M. L. Rao, R. W. Francis, H. A. Christopher, “Lithium-Aluminum Electrode” J. Electrochem. Soc. , 124 (1977) 1490-1492. [9]. S. Basu, “Ambient temperature rechargeable battery”, US Patent 4,423,125 1982. [10]. K. Mitzushima, P. C. Jones, P. J. Wiseman, J. B. Goodenough, “LixCoO2 (O<x≤1): A New Cathode Material for Batteries of High Energy Density”, Mater. Res. Bull. 15, (1980) 783. [11]. Y. Nishi, in Lithium Ion Batteries; M. Wakihara, M., O. Yamamoto, Eds.; Kodansha: Tokyo, 1998. [12]. Seth Fletcher, “Bottled Lightening”, (2011) [13]. M. S. Whittingham, “Lithium Batteries and Cathode Materials”, Chem. Rev., 104 (2004) 4271.