Control of interfacial reactivity at high-voltage is a key to high-energy-density Li-ion batteries. 2-aminoethyldiphenyl borate was investigated as an electrolyte additive to stabilize surface and bulk of both NCM851005 and graphite in the cell with upper cut-off voltage of 4.4 V vs Li+/Li. AEDB almost completely eliminated the “cross-talk” in the cell, by significantly reducing metal leaching from the cathode, preventing their deposition at the anode, and further electrolyte decomposition.