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Solvent and lithium salt decomposition products on LiNi x Mn y O 4 -type electrodes are known to be ROM, ROCO 2 M (M = Li, Ni, Mn), LiF, Li x PF y O z , polycarbonates and polyethers. These compounds are chemically formed due to the high nucleophilic character of spinel oxide and LiPF 6 decomposition. The high potentials (> 4.7 V vs. Li/Li + ) may cause EC and PC polymerization, while DMC forms oligomers. The use of carbon black-based electrodes highlights electronic and, surprisingly, chemical contributions to the cathode-electrolyte interface. A comparison between EC/DMC (1:1 in weight) 1 M LiPF 6 and PC/DMC (1:1 in weight) 1 M LiPF 6 electrolytes for Li/carbon black-PVdF cells demonstrated a superior ability of the EC/DMC solution to form a well-covering passivation film via faradaic reactions thanks to a higher stability toward oxidation. Electrochemical cycling in Li/LiNi 0.4 Mn 1.6 O 4 cells confirms this EC/DMC superiority when it comes to forming passivation films, in turn leading to reduced capacity losses and a higher Columbic efficiency.

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