Lithium Alloy Electrodes

Coin and Button Cell Commercial Systems. Initial commercialization of rechargeable lithium technology has been through the introduction of coin or button cells. The eadiest of these systems was the Li—C system commercialized by Matsushita Electric Industries (MEI) in 1985 (26,27). The negative electrode consists of a lithium alloy and the positive electrode consists of activated carbon [7440-44-0J, carbon black, and binder. The discharge curve is not flat, but rather slopes from about 3 V to 1.5 V in a manner similar to a capacitor. Use of lithium alloy circumvents problems with cycle life, dendrite formation, and safety. However, the system suffers from generally low energy density. 

Whereas there had been a significant amount of work on the properties of lithium alloys in the research community for a number of years, this alternative did not receive much attention in the commercial world until about 1990, when Sony began producing batteries with lithium-carbon negative electrodes. Since then, there has been a large amount of work on the preparation, structure, and properties of various carbons in lithium cells. 

The first use of lithium alloys as negative electrodes in commercial batteries to operate at ambient temperatures was the employment of Wood s metal alloys in lithium-conducting button-type cells by Matsushita in Japan. Development work on the use of these alloys started in 1983 [10], and they became commercially available somewhat later. 

There are some other matters that should be considered when comparing metallic lithium alloys with the lithium-carbons. The specific volume of some of the metallic alloys can be considerably lower than that of the carbonaceous materials. As will be seen later, it is possible by selection among the metallic materials to find good kinetics and electrode potentials that are sufficiently far from that of pure lithium for there to be a much lower possibility of the potentially dangerous forma-... 

The recent development of the convertible oxide materials at Fuji Photo Film Co. will surely cause much more attention to be given to alternative lithium alloy negative electrode materials in the near future from both scientific and technological standpoints. This work has shown that it may pay not only to consider different known materials, but also to think about various strategies that might be used to form attractive materials in situ inside the electrochemical cell. 

It is now well established that in lithium batteries (including lithium-ion batteries) containing either liquid or polymer electrolytes, the anode is always covered by a passivating layer called the SEI. However, the chemical and electrochemical formation reactions and properties of this layer are as yet not well understood. In this section we discuss the electrode surface and SEI characterizations, film formation reactions (chemical and electrochemical), and other phenomena taking place at the lithium or lithium-alloy anode, and at the Li. C6 anode/electrolyte interface in both liquid and polymer-electrolyte batteries. We focus on the lithium anode but the theoretical considerations are common to all alkali-metal anodes. We address also the initial electrochemical formation steps of the SEI, the role of the solvated-electron rate constant in the selection of SEI-building materials (precursors), and the correlation between SEI properties and battery quality and performance. 

Wang J., Raistrick ID., Huggins RA., Behavior of some Binary Lithium Alloys as Negative Electrodes in Organic Solvent-Based Electrolytes. J. Electrochem. Soc. 1986 133 457-60. 

Anani A., Crouch-Baker S., Huggins RA. Kinetic and Thermodynamic Properties of Several Binary Lithium Alloy Negative Electrode Materials at Ambient Temperature. J. Electrochem. Soc. 1987 134 3098-101. 

The physical properties of lithium metal were given in Table 4.4. Despite its obvious attractions as an electrode material, there are severe practical problems associated with its use in liquid form at high temperatures. These are mainly related to the corrosion of supporting materials and containers, pressure build-up and the consequent safety implications. Such difficulties were experienced in the early development of lithium high temperature cells and led to the replacement of pure lithium by lithium alloys, which despite their lower thermodynamic potential remained solid at the temperature of operation and were thus much easier to use. 

Huggins RA. Lithium alloy negative electrodes. J Power Sources 1999 81-82 13-19. 

Wang J, Raistrick ID, Huggins RA. Behavior of some binary lithium alloys as negative electrodes in organic solvent-based electrolyte. J Electrochem Soc 1986 133 457-460. 

Anani A, Crouch-Baker S, Huggins RA. Kinetic and thermodynamic parameters of several binary lithium alloy negative electrode materials at ambient temperature. J Electrochem Soc 1987 134 3098-3102. 

Lithium insertion negative electrodes — (i) Some transition-metal oxides or chalcogenides insert Li ion reversibly at low redox potentials, for example, TiC>2, LL I iOy, M0S2, M0O2. (ii) Lithium alloys - in this case lithium ions, react with other elements polarized to low potentials to reversibly form Li alloys. The reaction usually proceeds reversibly according to the... 

Higher OCV values can be attained with lithium alloys (Figure 16), which are under study as negative insertion electrode materials for their high specific capacity... 

Switching to lithium-alloy negative electrodes, some voltage loss must be noted. LiAl has Uu = -1-385 mV, Li4.5Pb has Uu = 388 mV. Entries 18-20 in Table 10(b) represent three examples of rechargeable cells, which have been, at least temporarily, commercialized. The first (No. 18) is due to a lithium alloy/carbon black battery conunercialized by the Matsushita Co. [248]. The lithium alloy components are Pb -I- Cd -I- Bi -h Sn (Wood s alloy). Button cells in the range 0.3 to 2.5 mAh were offered. The electrolyte was LiC104 in an unknown solvent. The practical energy densities, 2Wh/kg, were rather low. The c.b. positive electrode acts as a double... 

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