Binary lithium alloy systems

A series of experiments have been undertaken to evaluate the relevant thermodynamic properties of a number of binary lithium alloy systems. The early work was directed towards determination of their behavior at about 400 °C because of interest in their potential use as components in molten salt batteries operating in that general temperature range. Data for a number of binary lithium alloy systems at about 400 °C are presented in Table 1. These were mostly obtained by the use of an experimental arrangement employing the LiCl-KCl eutectic molten salt as a lithiumconducting electrolyte. 

Because of the interest in its use in elevated-temperature molten salt electrolyte batteries, one of the first binary alloy systems studied in detail was the lithium-aluminium system. As shown in Fig. 1, the potential-composition behavior shows a long plateau between the lithium-saturated terminal solid solution and the intermediate P phase "LiAl", and a shorter one between the composition limits of the P and y phases, as well as composition-dependent values in the single-phase regions [35], This is as expected for a binary system with complete equilibrium. The potential of the first plateau varies linearly with temperature, as shown in Fig. 2. 

Other common anode materials for thermal batteries are lithium alloys, such as Li/Al and Li/B, lithium metal in a porous nickel or iron matrix, magnesium and calcium. Alternative cathode constituents include CaCr04 and the oxides of copper, iron or vanadium. Other electrolytes used are binary KBr-LiBr mixtures, ternary LiF-LiCl-LiBr mixtures and, more generally, all lithium halide systems, which are used particularly to prevent electrolyte composition changes and freezing out at high rates when lithium-based anodes are employed. 

Estimated data on a number of ternary lithium systems theoretically investigated as extensions of the Li-Si binary system are included in Table 2. Also included are comparable data for the binary Li-Si alloy... 

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