Review Reports

Round 1

Reviewer 1 Report

Comments and Suggestions for Authors

Comments for transmission to the authors of the manuscript

Manuscript Title: Electrocrystallization in rechargeable batteries: a review

Summary: This manuscript reviews electrocrystallization phenomena in rechargeable batteries, focusing on the electrodeposition mechanisms of reactive metals (alkali metals, Al, Mg, and Si) in non-aqueous organic electrolytes. The authors explore how key deposition parameters such as current density, potential, electrolyte formulation, substrate chemistry, and temperature dictate initial nucleation kinetics and crystal growth regimes. Overall, the article is well organized, thus I suggest acceptance of the paper after addressing these minor comments.

Minor Comments:

1) To further elevate the impact and original contribution of this review, the authors are encouraged to include 1-2 original conceptual schematics. For example, a unified diagram that directly contrasts the electrocrystallization, desolvation pathways, and SEI dynamics across alkali (Li, Na) and multivalent (Mg, Al, Zn) metals would offer tremendous value over simple literature compilations.

2) Section 5 (Conclusions and Outlook) is currently written in broad, qualitative terms. Please expand this section to provide concrete, actionable research directions. Specifically, incorporate practical cell-level target metrics required for realistic metal-anode commercialization (e.g., lean electrolyte conditions <3g/Ah, low N/P ratios <2 , and high areal capacities >3 mAh/cm2 ).

3) The text classifies LiTFSI and LiFSI as "fluorosulphonate electrolytes". This is chemically inaccurate, as fluorosulfonates refer to FSO3- derivatives (such as LiFSO3). LiTFSI and LiFSI are imide or sulfonimide salts. Please update this phrasing to "sulfonylimide electrolytes" or "sulfonimide-based salts".

4) The subfigure labels and axis text in Figure 6 (panels a-d) are low-resolution and difficult to read. Please replace these with high-resolution vector graphics or images with a minimum resolution of 300 DPI.

5) The discussion attributes the unstable SEI and low-overpotential dendrite formation on Na metal to its higher chemical reactivity compared to Li. To make this comparison rigorous, please incorporate fundamental thermodynamic and kinetic metrics such as the standard reduction potentials ( -2.71V vs. SHE for Na vs. -3.04V for Li), relative self-diffusion barriers, and mechanical shear moduli to explain why Na interfaces degrade more rapidly during galvanostatic plating.

 

Comments for author File: Comments.pdf

Author Response

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Author Response File: Author Response.docx

Reviewer 2 Report

Comments and Suggestions for Authors

This review summarizes electrocrystallization in rechargeable batteries, covering nucleation and growth theory, electrochemical kinetics, crystal growth mechanisms, and dendrite-related issues and regulation strategies in Li, Na, Zn, Al, and Mg metal anode systems. The topic is clearly significant. Dendrite growth on metal anodes is one of the key bottlenecks for next-generation high-energy-density batteries, and understanding and regulating this process from the perspective of fundamental electrocrystallization theory is of considerable academic value and engineering significance. The manuscript is well-organized. However, several aspects still require further clarification. Therefore, the manuscript can be accepted after addressing the following issues.

1. In the “Introduction” and “Theoretical principles of electrodeposition” sections, more relevant references should be cited to substantiate the rigor of the statements. In addition, recent references should be cited throughout the manuscript to reflect the latest research progress, such as 10.1126/science.aax6873, 10.1016/j.ensm.2021.06.019.
2. “2 Electrochemical nucleation” should be Section 3. The numbering is inconsistent.
3. A considerable amount of the content is a compilation of other literature. Some parts should be condensed. There is a lack of in-depth discussion of contradictions in the literature, applicability boundaries, and uncertainties.
4. The copyright permission statements for the figures are inconsistent.
5. The Li and Na sections are relatively detailed, whereas the Zn, Al, and Mg sections are relatively brief and largely remain at the level of phenomenological description.
6. In the Conclusion section, the outlook should be further strengthened.

Author Response

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Author Response File: Author Response.docx

Reviewer 3 Report

Comments and Suggestions for Authors

The presented review describes the process of metal electrocrystallization, using the growth of lithium dendrites as an example. The study is theoretical in nature and is based on a review of existing dendrite growth models. However, the manuscript has a number of minor shortcomings that need to be addressed before publication:

1. The preliminary report and the abstract do not reflect the essence of the work and require substantial revision to clearly articulate the novelty and scientific significance of the theoretical research conducted.
2. The article does not address the spillover mechanism that would help explain the proposed mechanism of dendrite growth. Why?
3. The mechanism of 2D nucleus formation is not presented in the review.
4. The review contains very few references to the original articles that substantiate the conclusions of this theoretical study. It is advisable to provide 150–200 references on the subject.
5. The models discussed are not described in sufficient detail, and the calculation component is missing; consequently, it is unclear why the authors included the Scharifker-Hills [72], Heerman–Tarallo [69], and Sluyters–Rehbach [67] models. The validity of using these models in the study requires a more detailed discussion.
6. The density functional theory (DFT) calculation approach needs to be described in greater detail.

Author Response

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Author Response File: Author Response.docx

Round 2

Reviewer 3 Report

Comments and Suggestions for Authors

The submitted manuscript can be published in the journal without modifications.