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| Abstract |
The current-potential relationships for the electrochemical oxidation of organic solvent electrolytes on microelectrodes are confirmed for various lithium salts, namely ${\rm LiClO}_4$, ${\rm LiBF}_4$..., ${\rm LiCF}_3{\rm SO}_3$ and ${\rm LiPF}_6$. The oxidation is expected to occur by means of a two stage process; the chemical degradation of the solvent followed by the electrochemical generation of anion radical species, and the direct electrochemical oxidation of the solvent. The dependence of the oxidation current on temperature and the lithium salt concentration confirms this two step reaction feature. In other words, a reaction based on electrochemically generated anion radicals seems to occur below 4.8V vs. Li/Li$^+$ and direct oxidation of the solvent occurs above 4.8V. Above 4.8V, we cannot disregard the distribution of the diffusion-limiting current of the anion radical into the whole oxidation current.show more
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