Stable cycling and uniform lithium deposition in anode-free lithium-metal batteries enabled by a high-concentration dual-salt electrolyte with high LiNO3 content

Abstract Despite their potential for achieving high energy density, anode-free batteries (AFBs) suffer from poor cycling stability caused by uncontrollable Li-metal deposition. To improve the reversibility of Li by physically preventing Li dendrite growth and minimizing the side reaction area between Li and the free solvent, two representative salts, lithium bis(fluorosulfonyl)imide (LiFSI) forming a robust/conductive LiF-based solid electrolyte interphase (SEI) layer, and LiNO3 altering the deposited Li morphology from dendritic to spherical, are widely used as salts for electrolyte. However, the depletion of LiNO3 by continuous consumption during cycling is a problem due to its low solubility. Thus, here, we report the use of high-concentration dual-salt electrolyte consisting of LiFSI and LiNO3 for AFBs to circumvent these issues. Experimental and theoretical studies reveal that electrolytes with high-concentration LiNO3 (up to 2 M) can be prepared by suppressing the agglomeration of LiNO3 in 1,2-dimethoxyethane (DME) in the presence of LiFSI. Because of the densely packed Li without dendrite, the formation of a protective SEI layer, and the alleviation of electrolyte oxidation as well as Al corrosion, the AFBs with this electrolyte achieve good cycling performance by reversible operation of Li. This work demonstrates the importance of electrolyte engineering for highly stable AFBs.