High Voltage Operation of Ni‐Rich NMC Cathodes Enabled by Stable Electrode/Electrolyte Interphases

Abstract The lithium (Li) metal battery (LMB) is one of the most promising candidates for next‐generation energy storage systems. However, it is still a significant challenge to operate LMBs with high voltage cathodes under high rate conditions. In this work, an LMB using a nickel‐rich layered cathode of LiNi 0.76 Mn 0.14 Co 0.10 O 2 (NMC76) and an optimized electrolyte [0.6 m lithium bis(trifluoromethanesulfonyl)imide + 0.4 m lithium bis(oxalato)borate + 0.05 m LiPF 6 dissolved in ethylene carbonate and ethyl methyl carbonate (4:6 by weight)] demonstrates excellent stability at a high charge cutoff voltage of 4.5 V. Remarkably, these Li||NMC76 cells can deliver a high discharge capacity of >220 mA h g −1 (846 W h kg −1 ) and retain more than 80% capacity after 1000 cycles at high charge/discharge current rates of 2C/2C (1C = 200 mA g −1 ). This excellent electrochemical performance can be attributed to the greatly enhanced structural/interfacial stability of both the Ni‐rich NMC76 cathode material and the Li metal anode using the optimized electrolyte.