Synergy of an In Situ-Polymerized Electrolyte and a Li₃N–LiF-Reinforced Interface Enables Long-Term Operation of Li-Metal Batteries

The long-term operation of a Li-metal anode remains a great challenge due to the severe dendrite growth in an organic liquid electrolyte. To protect a Li-anode surface from continuous corrosion by an electrolyte, a consistent and robust solid electrolyte interface (SEI) is an essential prerequisite. This work proposes a secure gel polymer electrolyte, which is in situ constructed via a facile polymerization process of vinylidene carbonate inside Li-metal batteries. The liquid components that are not involved in polymerization are well entrapped in the poly(vinyl carbonate) framework, leading to a high oxidative stability of up to 4.5 V (vs Li/Li+). A Li3N–LiF-reinforced SEI resulting from the reduction of fluoroethylene carbonate and lithium nitrate additives has a synergistic effect on the suppression of Li-dendrite growth. The densely packed Li deposition behavior is revealed by in situ/ex situ microscopic observations. Steady cycling of over 2500 h with a relatively low voltage hysteresis is achieved by the Li||Li symmetric cells. A Coulombic efficiency above 96% upon long-term cycling is available for the asymmetric Li||Cu cells. The smooth operation of batteries with commercial LiFePO4 cathodes further indicates that the SEI with homogeneity in composition and structure prompts Li deposition with alleviative dendrites.