This manuscript introduced a strategy of using multivalent cation salts as electrolyte additives in exemplary [TFSI]-/EC-PC electrolytes. These additives induce strong Coulomb interactions that alter the solvation environment in the electrolyte, promoting the direct coordination of cations with [TFSI]-. And this strategy increases the desolvation energy, effectively slowing down the Li+ depletion at the electrode surface and flattening the deposition morphology. Systematic research on electrolyte, Cu foil electrodes after deposition and LiFePO4||Li cells is performed by MD, XPS and other characterization methods. Therefore, I consider that a minor revision is necessary before the publication of this manuscript. Some opinions are listed as follows.
(1) In figure 2b, what causes an increase of voltage in the deposition curves at the 10th cycle? And why is no such phenomenon in the first circle?
(2) In Figure 6g, please support the curves of Coulomb efficiency of LiFePO4||Li cells with the Li and Li-La electrolytes like Figure 6a.
(3) Some recent progresses of Li metal anodes and batteries also benefit from cation and tailored additives and electrolyte formulation, e.g. Mater. Horiz. 11, 2169-2179, 2024; Angew. Chem. Int. Ed., 60, 23256-23266, 2021; Energy Environ. Sci., 14, 3621-3631, 2021; ACS Appl. Mater. Interfaces, 10, 12678-12689, 2018. These highly related works are suggested to serve as references.
(4) Please provide the radial distribution function and coordination curve obtained by MD to prove Figure 5d.
(5) Please supplement the voltage profiles at different current densities for LiFePO4||Li cells.
(6) Please supplement the curves of the Li metal symmetric cells with Li and Li-La electrolytes and explain the difference between them.