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Lithium oxide is a white, solid, ionic compound. It has a relative density of 2.013, melting and boiling points of 1567 and 2600 degC respectively and is highly soluble in water where it forms lithium hydroxide (LiOH). It has a tetrahedral coordination structure for the two lithium atoms and a cubic antifluorite crystal structure. It is a strong base and reacts vigorously with acids. It is also corrosive and can etch glass and certain metals at high temperatures.

When lithium metal is introduced into polar aprotic solvents the native surface films that surround it undergo a variety of reactions and interactions with the solvent molecules. This results in the formation of primary and secondary species that are insoluble or in soluble form in the mother solution. In most cases these species are reduced by the salt anions (LixAXy where A is the high oxidation state element and X is a halide) to form lithium compounds.

This set of primary and secondary surface reactions makes lithium oxide a very dynamic chemical compound that is easily influenced by the environment in which it exists. For this reason, it is very difficult to obtain pure lithium oxide. However, it is important in ceramic glazes for its low expansion and in light weight structural applications such as aerospace and electrochemical applications such as fuel cells where it exhibits ionic conductivity. Lithium oxide can be found in the mineral spodumene as well as being synthesized from the chemical slurries lithium peroxide and lithium carbonate.