Impact of LiF Particle Morphology on Overpotential and Structure of Li Metal Deposition

It has been widely suggested in literature that a lithium fluoride (LiF)-rich solid electrolyte interphase (SEI) affects Coulombic efficiency (CE) of the Li metal anode used with liquid electrolytes. Yet, the influence of LiF on Li metal deposition has been challenging to examine. Herein, we developed a method to synthesize LiF nanoscale particles with tunable sizes (30–300 nm) on Cu electrodes by electrochemical reduction of fluorinated gases under controlled discharge rates and capacities. The impact of LiF nanoparticles on overpotential and morphology of Li deposition was further studied in a conventional carbonate electrolyte. By cyclic voltammetry, Li plating overpotentials exhibit a clear correlation with the total surface area of LiF particles. Additionally, Li metal deposits (10 μ Ah cm −2 ) nucleated under galvanostatic conditions (0.5 mA cm −2 ) on Cu/LiF showed increasing feature sizes with a lower average LiF particle size and higher coverage of LiF. However, no significant improvement in CE was observed for LiF-coated Cu. Our findings provide evidence that a particle-based mode of SEI fluorination can influence early-stage Li nucleation to a modest degree, and this effect is maximized when LiF is uniformly and densely distributed. However, sparser and larger LiF have vanishing or even detrimental effect on cycling performance.