The authors systematically explores the effects of multivalent cation additives (Ca²⁺, Ba²⁺, La³⁺, Ce³⁺) on solvation structures, SEI composition, and lithium deposition morphology. This work provides novel insights into the interaction of multivalent cations with SEI formation and lithium cycling behavior. The results, particularly the superior performance of La³⁺ in suppressing dendrite growth and improving Coulombic efficiency, are scientifically significant and lay the groundwork for further developments in advanced battery electrolytes. However, several major concerns need to be addressed before it can be published in the Journal of Materials Chemistry A:

1. The authors should explain why the LiTFSI system was chosen for investigation and how these multivalent cation additives would perform in other lithium salt systems, such as LiPF₆.

2. The study lacks a control group with a commercial electrolyte (e.g., 1M LiPF₆/EC-DMC), making it difficult to assess the practical performance of these additives.

3. The authors focused on only four multivalent cations. Other commonly studied multivalent ions (e.g., Mg²⁺, Al³⁺) should have been included or at least discussed for broader applicability. The findings suggest that cations with higher valence states may be more effective in enhancing lithium metal deposition. Could a more cost-effective cation, such as Al³⁺, provide similar benefits?

4. In Fig. 6b, the authors report high initial capacity loss in Li-La electrolytes, but do not explore solutions to mitigate this issue. Additionally, concentration-dependent studies for each additive are missing, which would help determine the optimal concentration for practical use.

5. The rate performance of different electrolytes needs to be provided for practical evaluation.

6. There are some formatting issues and mistakes in the manuscript. The authors should carefully review and correct them.

The revised manuscript is suitable for publication as it is.