Lithium alloy negative electrodes

• Published in: Journal of power sources 1999-09, Vol.81, p.13-19
• Main Author: Huggins, Robert A.
• Format: Article
• Language: English
• Subjects: Alloy; Applied sciences; Composite microstructure; Convertible metal oxides; Direct energy conversion and energy accumulation; Electrical engineering. Electrical power engineering; Electrical power engineering; Electrochemical conversion: primary and secondary batteries, fuel cells; Exact sciences and technology; Li–Sn; Mixed-conductor matrix; Near-equilibrium; Nucleation; Solid electrolyte matrix
• ISSN: 0378-7753; 1873-2755
• DOI: 10.1016/S0378-7753(99)00124-X

The 1996 announcement by Fuji Photo Film of the development of lithium batteries containing convertible metal oxides has caused a great deal of renewed interest in lithium alloys as alternative materials for use in the negative electrode of rechargeable lithium cells. The earlier work on lithium alloys, both at elevated and ambient temperatures is briefly reviewed. Basic principles relating thermodynamics, phase diagrams and electrochemical properties under near-equilibrium conditions are discussed, with the Li–Sn system as an example. Second-phase nucleation, and its hindrance under dynamic conditions plays an important role in determining deviations from equilibrium behavior. Two general types of composite microstructure electrodes, those with a mixed-conducting matrix, and those with a solid electrolyte matrix, are discussed. The Li–Sn–Si system at elevated temperatures, and the Li–Sn–Cd at ambient temperatures are shown to be examples of mixed-conducting matrix microstructures. The convertible oxides are an example of the solid electrolyte matrix type. Although the reversible capacity can be very large in this case, the first cycle irreversible capacity required to convert the oxides to alloys may be a significant handicap.