High potential cathodes are of strong interest to improve lithium-ion battery performances, nevertheless, no compatible electrolyte above 4.5–4.8V vs Li+/Li was found yet. The main strategies involved the use of protective film inhibiting and/or delaying electrolyte degradation. In this context, we focused on the use of adapted modified biphenyls to form a protective film at the positive electrode. Particularly phosphate biphenyl derivatives oxidation permits to produce a protective film which significantly decreases the self-discharge without compromising the lithium intercalation kinetic.