Synthesis and Electrochemical Properties of Co₃O₄@Reduced Graphene Oxides Derived from MOF as Anodes for Lithium-Ion Battery Applications

Round 1

Reviewer 1 Report

In this manuscript, Yi-Xuan Guo et al. proposed the preparation and property of a composite anode material Co₃O₄/rGO/C . To solve the poor conductivity and stability of TMOs, nano-sized Co₃O₄ was synthesized from MOF and was further modified with reduced graphene oxide sheets. Inferences of rGO nanosheets on lithium ion diffusion and electrical property were mainly discussed, and improved kinetics and cycling performance were obtained. The following comments and suggestions should be addressed prior to acceptance.

1. In paragraph “ A schematic of electromagnetic wave shielding using GNT10 is presented in Fig. 7(a) ... ”, there is a mismatch between the content and mentioned figure.

2. In Figure 8b, there is a small peak at around 1.25V in the first cycle for Co₃O₄/rGO/C, which could not be observed in the control group. This difference should be discussed and explained.

3. The manuscript needs careful editing and attention to English grammar, spell, and figure detail. For example, in “... the plot of Z' vs. ^−1/2 at low frequency shown in Fig. 9(b) ”, the “ω” is missing; in Figure 9a, Y axe title “Z”/ohm “ should be “ -Z”/ohm “ .

4. Some related literature should be cited, such as Energy Mater. (2022, 2: 200026), Energy Mater. (2021, 1: 100003), and Materials Today Energy (2021, 30: 101163).

Author Response

In this manuscript, Yi-Xuan Guo et al. proposed the preparation and property of a composite anode material Co₃O₄/rGO/C . To solve the poor conductivity and stability of TMOs, nano-sized Co₃O₄ was synthesized from MOF and was further modified with reduced graphene oxide sheets. Inferences of rGO nanosheets on lithium ion diffusion and electrical property were mainly discussed, and improved kinetics and cycling performance were obtained. The following comments and suggestions should be addressed prior to acceptance.

1. In paragraph “ A schematic of electromagnetic wave shielding using GNT10 is presented in Fig. 7(a) ... ”, there is a mismatch between the content and mentioned figure.

Response:

Thank you for reviewer’s comments. It is a typo mistake. We have deleted the sentence in the revised manuscript.

2. In Figure 8b, there is a small peak at around 1.25V in the first cycle for Co₃O₄/rGO/C, which could not be observed in the control group. This difference should be discussed and explained.

Response:

Thank you for reviewer’s comments. The small peak located at 1.25V in the first cycle for Co3O4/rGO/C might be due to SEI formation contributed from rGO. The functional groups in rGO could also contribute the SEI formation during the first discharging process. The corresponding discussion have also been added in the revised manuscript.

 

3. The manuscript needs careful editing and attention to English grammar, spell, and figure detail. For example, in “... the plot of Z' vs. ^−1/2at low frequency shown in Fig. 9(b) ”, the “ω” is missing; in Figure 9a, Y axe title “Z”/ohm “ should be “ -Z”/ohm “ .

Response:

Thank you for reviewer’s comments. We will carefully edit the English grammar, spell and figure detail. The mistakes you mentioned have been corrected in the revise manuscript.

Revised caption in Fig. 9

Figure 9. (a) Nyquist plots for Co₃O₄/C, Co₃O₄/rGO/C electrodes at 2.5 cycles; (b) The relationship lines between Z` vs. w^-1/2 in the low frequency region of Co3O4/C, Co3O4/rGO/C electrodes. Inset in (a): The corresponding Randles equivalent circuit of the electrodes.

Revised Fig. 9

4. Some related literature should be cited, such as Energy Mater. (2022, 2: 200026), Energy Mater. (2021, 1: 100003), and Materials Today Energy (2021, 30: 101163).

Response:

 

Thank you for reviewer’s good suggestions. The related literature have been added in the revised manuscript.

[a1] Jiaqi Wang, Junyi Yao, Wanying Li, Wenhao Zhu, Jie Yang, Jianqing Zhao, Lijun Gao, “Lithium molybdate composited with carbon nanofibers as a high-capacity and stable anode material for lithium-ion batteries,” Energy Mater, 2022, 2, 4, 200026.

[a2] Hui Chang, Yu-Rong Wu, Xiao Han, Ting-Feng Yi, “Recent developments in advanced anode materials for lithium-ion batteries,” Energy Mater, 2021, 1, 1, 100003.

[a3]Shuang Xia, Qi Zhou, Bohao Peng, Xingpeng Zhang, Lili Liu, Fei Guo, Lijun Fu, Tao Wang, Yankai Liu, Yuping Wu, “Co₃O₄@MWCNT modified separators for Li–S batteries with improved cycling performance,” Materials Today Energy, 2021, 30,101163.

Author Response File: Author Response.pdf

Reviewer 2 Report

The use of MOF-derived Co3O4 with reduced 2 graphene oxide for electrode modification to improve reversible capacity in lithium batteries is a very good research topic. The modification of the anodes chosen by the authors was a very effective and critical exercise. The cited article is also appropriate and offers considerable performance improvements over the original anode. The authors' experimental path is also reasonable and workable and their results amply validate this. However, there are problems with the scientific discussion section and the abbreviations and spelling in the article need to be double-checked. The criteria for some of the icons are not clear and standard. The details are as follows：

1. In abstractor (page 1 line 22), the “ZIF67”. This abbreviation is the first time it has appeared, and the author needs to give the full spelling or a description.

2. In thermogravimetric analysis (TGA) figure 3, The weight loss at 356.4 degrees should not be from adsorbed water vapour, more like close to 10% weight loss around 150 degrees. The authors would have been better off doing XPS analysis of the samples before and after treatment near 356.4 degrees, there should have been chemical structural changes.

3. In figure7 (B), The horizontal coordinates in the figure are not clearly labelled and do not correspond to the descriptions.

This is a research paper of publication value. The experimental part is quite complete and appropriate, but there are shortcomings and flaws in the scientific analysis and discussion. It is hoped that corrections will be made and then given for publication.

Author Response

Reviewer 2

 

The use of MOF-derived Co3O4 with reduced 2 graphene oxide for electrode modification to improve reversible capacity in lithium batteries is a very good research topic. The modification of the anodes chosen by the authors was a very effective and critical exercise. The cited article is also appropriate and offers considerable performance improvements over the original anode. The authors' experimental path is also reasonable and workable and their results amply validate this. However, there are problems with the scientific discussion section and the abbreviations and spelling in the article need to be double-checked. The criteria for some of the icons are not clear and standard. The details are as follows：

1. In abstractor (page 1 line 22), the “ZIF67”. This abbreviation is the first time it has appeared, and the author needs to give the full spelling or a description.

Response:

Thank you for reviewer’s comments. We have given a description “Zeolitic Imidazolate Framework-67” in the revised manuscript.

2. In thermogravimetric analysis (TGA) figure 3, The weight loss at 356.4 degrees should not be from adsorbed water vapour, more like close to 10% weight loss around 150 degrees. The authors would have been better off doing XPS analysis of the samples before and after treatment near 356.4 degrees, there should have been chemical structural changes.

Response:

Thank you for reviewer’s comments. It is a typo mistake. We agree with reviewer’s view point. The weight loss around 150 degree was resulted from adsorbed water vapour. Here is the revised description in the revised manuscript.

“The first weight loss during ~130 ^oC should be attributed to evaporation of adsorbed moisture in air. Subsequently, the second weight loss about 50.1% between 356.4 ^oC and 375.8 ^oC presented the consumption of carbon dioxide.”

Thus, we may not need to carried out XPS analyses again. We hope reviewer could satisfy with our response.

3. In figure7 (B), The horizontal coordinates in the figure are not clearly labelled and do not correspond to the descriptions.

Response:

We are very sorry for the mistake. The description “Rate capability tests of as-synthesized Co₃O₄/C, Co₃O₄/rGO/C at 0.1A g^-1, 0.2 A g^-1, 0.5 A g^-1, 1 A g^-1, 2 A g^-1, 5 A g^-1 and 10 A g^-1,” have been added in the revised manuscript. 

This is a research paper of publication value. The experimental part is quite complete and appropriate, but there are shortcomings and flaws in the scientific analysis and discussion. It is hoped that corrections will be made and then given for publication.

Response:

Thank you for reviewer’s valuable comments and suggestions. We will correct the manuscript carefully before submitting.

Author Response File: Author Response.pdf

Reviewer 3 Report

Dear Editor,

The authors have considered nano-sized Co3O4 and reduced graphene oxides for composite anode materials in realizing Li-ion batteries. The manuscript has been well organized and written, also the results support the title and abstract. So, the manuscript can be accepted after addressing the following comment:

1. The novelty and the importance of this work should be highlighted in the last paragraph of the introduction section.

2. Could you explain the lifetime of the proposed composite?

3. The performance of the electrodes for the different temperatures should be considered.

4. In the introduction section, after reference 35, it should be given the new graphene-based structures. The following articles are suitable for showing the excellent features of graphene.

https://doi.org/10.1016/j.diamond.2023.109780, https://doi.org/10.1016/j.optlastec.2022.108436, 

      

Author Response

The authors have considered nano-sized Co₃O₄ and reduced graphene oxides for composite anode materials in realizing Li-ion batteries. The manuscript has been well organized and written, also the results support the title and abstract. So, the manuscript can be accepted after addressing the following comment:

1. The novelty and the importance of this work should be highlighted in the last paragraph of the introduction section.

Response:

Thank you for reviewer’s comments. We have addressed our novelty in the last paragraph of the introduction section in the revised manuscript.

 

2. Could you explain the lifetime of the proposed composite?

Response:

Our lifetime (Cycle number) is ~100 cycles.

 

3. The performance of the electrodes for the different temperatures should be considered.

Response:

Thank you for reviewer’s good suggestion. The performance of the electrodes for the different temperatures is out of the scope in the current manuscript. We will study this important issues in the future work. We hope reviewer could satisfy with our response. 

 

4. In the introduction section, after reference 35, it should be given the new graphene-based structures. The following articles are suitable for showing the excellent features of graphene.

https://doi.org/10.1016/j.diamond.2023.109780, https://doi.org/10.1016/j.optlastec.2022.108680, https://doi.org/10.1016/j.diamond.2022.109594, https://doi.org/10.1016/j.optlastec.2022.108436, https://doi.org/10.1016/j.ijleo.2023.170583

Response:

Thank you for reviewer’s comments. The corresponding references seem not relate to energy storage applications. Because these references are out of the scope in the manuscript. We may not cite these references in the manuscript. We hope reviewer could satisfy with our response.

Author Response File: Author Response.pdf