Lithium superoxide
| Identifiers | |
|---|---|
| Properties | |
| LiO2 | |
| Molar mass | 38.94 g/mol |
| Density | g/cm3, solid |
| Melting point | <25 °C (decomposes) |
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Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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| Infobox references | |
Lithium superoxide (LiO2) is an inorganic compound which has only been isolated in matrix isolation experiments at 15-40 K. It is an unstable free radical that has been analyzed using infrared (IR), Raman, electronic, electron spin resonance, soft X-ray spectroscopies, and a variety of theoretical methods.
Experimental studies indicate that the LiO2 molecule contains highly ionic bonds. Eighteen different values were attained using six isotopic species. This indicated that the force constant between the two oxygen atoms corresponds with the constant found for the O2− ion. Studies indicate that there is little to no covalent character in the LiO2 molecule.
The bond length for the O-O bond was determined to be 1.34 Å. Using a simple crystal structure optimization, the Li-O bond was calculated to be approximately 2.10 Å. Lithium superoxide is extremely reactive because of the odd electron present in the π* molecular orbital.
There have been quite a few studies regarding the clusters formed by LiO2 molecules. The most common dimer has been found to be the cage isomer. Second to it is the singlet bypyramidal structure. Studies have also been done on the chair complex and the planar ring, but these two are less favorable, though not necessarily impossible.
In a lithium-ion battery, when there is a one electron reduction during discharge, lithium superoxide is formed as seen in the following reaction:
This product will then react and proceed to form lithium peroxide, Li2O2:
The mechanism for this last reaction has not been confirmed and chemists are having difficulties developing a theory of what may be happening. Another significant challenge of these batteries is finding an ideal solvent in which to perform these reactions; ether- and amide-based solvents are currently used, but these compounds readily react with oxygen and decompose. A suitable solvent would need to be able to resist autoxidation to enable a long life cycle for the battery.
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