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ABSTRACT:  The high capacity of the layered Li−excess oxide cathode is always
accompanied by extraction of a signi fi cant amount of oxygen from the structure.
The e ff ects of oxygen on the electrochemical cycling are not well understood.
Here, the detailed reaction scheme following oxygen evolution was established
using real-time gas analysis and ex situ chemical analysis of the surface of the
electrodes. A series of electrochemical/chemical reactions involving oxygen radicals
constantly produced and decomposed lithium carbonate during cell operation.
Moreover, byproducts, including water, a ff ected the cycle life and rate capability:
hydrolysis of the electrolyte salt formed hydro fl uoric acid that attacked the surface of the electrode. This fi nding implies that protection of the electrode surface from damage, for example, by a coating or removal of oxygen radicals by scavengers, will be critical to widespread usage of Li−excess transition metal oxides in rechargeable lithium batteries.
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