Improving interfacial stability of ultrahigh-voltage lithium metal batteries with single-crystal Ni-rich cathode via a multifunctional additive strategy.

Abstract Electrode (including cathode and anode) /electrolyte interfaces play a vital role in determining battery performance. Especially, high-voltage lithium metal batteries (HVLMBs) with the Ni-rich layered oxide ternary cathode (NCM) can be considered a promising energy storage technology due to their outstanding energy density. However, it is still extremely challenging to address the unstable electrode/electrolyte interface and structural collapse of polycrystalline NCM at high voltage, greatly restraining its practical applications. In this work, a novel electrolyte additive, tris(2-cyanoethyl) borate (TCEB), has been used to construct the robust nitrogen (N) and boron (B)-rich protective films on single-crystal LiNi0.6Co0.1Mn0.3O2 (SNCM) cathode and lithium metal anode surfaces, which could effectively mitigate parasitic reactions against electrolyte corrosion and retain the structural integrity of electrode. Remarkably, the SNCM||Li metal cell using TCEB-containing electrolyte maintains unprecedentedly superb capacity retention of 80 % after 100 cycles at an ultrahigh charging voltage of 4.7 V (versus Li/Li+). This finding provides a valuable reference to construct a stable electrode/electrolyte interface for the HVLMBs with achieving high-energy density.