Electronic Modulation and Structural Engineering of Carbon-Based Anodes for Low-Temperature Lithium-Ion Batteries: A Review

Round 1

Reviewer 1 Report

please more emphasis importance of g-C3N4 materials for LIBs. refer Vattikuti et al in this concept. 

Please provide the future perspectives  and outlooks before conclusion

Authors need to polish the sentence formation and revise the typo errors

 

Author Response

Response to Reviewer 1 Comments

 

Point 1: please more emphasis importance of g-C₃N₄ materials for LIBs. refer Vattikuti et al in this concept.

 

Response 1: We thank the reviewer for the constructive suggestions. According to the comment, the introduction of g-C₃N₄ materials and their application in energy related performance have been discussed in the revised manuscript. The related papers have been cited. The specific changes are as below:

Owning to its distinct structure and superior intrinsic physical and chemical properties, graphitic carbon nitride (g-C₃N₄), a typical polymeric organic semiconductor, has recently gained increasing interest as an electrochemical energy storage material [79]. In contrast to graphitic layers, g-C₃N₄ exhibits regular stacking of C₃N₄ layers, which are composed of sp² hybrid conjugated C and N atoms. Additionally, g-C₃N₄ is a strong substance with great chemical stability because it is not dissolved in alkali, acidic solution, or organic solvents. Moreover, g-C₃N₄ is readily synthesized from a variety of nitrogen-rich precursors, including dicyandiamide, urea, melamine, and thiourea, all of which are inexpensive, environmentally friendly, and naturally abundant in the earth. These characteristics make g-C₃N₄ an excellent choice for energy storage materials. However, there aren't many uses for pure g-C₃N₄ at the moment due to its poor electrical conductivity and small interlayer spacing distance. Some studies have used g-C₃N₄ as an electrolyte additive or in combination with other electrode materials to stabilize properties [80,81].

 

Point 2: Please provide the future perspectives and outlooks before conclusion

 

Response 2: Thanks for your valuable comments. As suggested by the reviewer, the future perspectives and outlooks have been included in the revised manuscript. The specific changes are as below:

Despite significant progress, significant challenges remain in utilizing carbon-based materials for low temperature LIBs, and primary focus should be directed towards the following areas: 1): Due to the significant influence of hierarchical porous structure on mass transport during energy storage and conversion, it is crucial to determine its role through theoretical modelling; 2) Electrochemical reaction mechanism; 3) How to adapt battery performance to extreme temperatures; 4) How to use first principles to calculate the electronic structure of carbon-based materials surface/interface and establish a mass transfer model, so as to find a way to reduce the energy barrier of Li⁺ migration.

 

Point 3: Authors need to polish the sentence formation and revise the typo errors

 

Response 3: Thanks for your valuable comments. We have checked the whole manuscript, and make sure to avoid the mistakes you have mentioned above. In addition, We choose MDPI Language Editing Services to improve our language.

 

Reviewer 2 Report

The manuscript "Electronic modulation and structural engineering of carbon-based anodes for low-temperature lithium-ion batteries: a review" is aimed to review the low temperature performance of lithium-ion batteries with anodes from various carbon-based materials.

So far, several reviews are available on the trouble shooting of the low temperature performance of lithium-ion batteries, among them: 

- Rodrigues, M.-T.F. et al. A materials perspective on Li-ion batteries at extreme temperatures (2017) Nature Energy, 2 (8), art. no. 17108

- Zhu, G. et al. Materials insights into low-temperature performances of lithium-ion batteries (2015) Journal of Power Sources, 300, pp. 29-40

- Zhang, N. et al. Critical Review on Low-Temperature Li-Ion/Metal Batteries (2022) Advanced Materials, 34 (15), art. no. 2107899

- Collins, G.A. et al. Alternative anodes for low temperature lithium-ion batteries (2021) Journal of Materials Chemistry A, 9 (25), pp. 14172-14213

- Selinis, P., Farmakis, F. Review - A Review on the Anode and Cathode Materials for Lithium-Ion Batteries with Improved Subzero Temperature Performance (2022) Journal of the Electrochemical Society, 169 (1), art. no. 010526

and several others.  Also, there is a number of reviews on anode carbon materials, among them:

- Roy, P. et al. Nanostructured anode materials for lithium ion batteries (2015) Journal of Materials Chemistry A, 3 (6), pp. 2454-2484

- Zhang, L. et al. Advanced nanostructured carbon-based materials for rechargeable lithium-sulfur batteries (2019) Carbon, 141, pp. 400-416

- Roselin, L.S. et al. Recent advances and perspectives of carbon-based nanostructures as anode materials for Li-ion batteries (2019) Materials, 12 (8), art. no. 1229

In view of this abundance of general literature reviews on the topic, a more detailed and critical review on the sub-topic of carbon materials as anodes in low-temperature batteries could justify a new review paper in the family. In my view, the present manuscript should be carefully revised to make such review interesting and useful for a reader. In particular, the following issues should be addressed by the authors:

- please mention the previous relevant reviews in the introduction section and highlight the novelty of your work;

- please quantify formulations like "excellent conductivity" etc. when you describe materials, so that it could be possible to compare between them;

- please check carefully the language use, there is a lot of mistakes and sometimes the mistakes make the passages incomprehensible; some examples:

lines 59-61: "Under low temperature conditions, high rate charging will cause lithium metal precipitation, so that lithium metal and electrolyte reaction,"

lines 80-85: "The low-temperature performance of LIBs will be impacted from the outside in by factors such the packaging of the LIBs, external temperature, and charging cut-off voltage."

line 247: "Activated carbon performance is good, environmental protection, cheap price."

and in other places;

- please carefully revise the sources to be included in the review; for example, Li1.2Ni0.13Co0.13Mn0.54O2 (line 207) seems to be outside the review scope;

- please use only family names when you mention other researchers, without first names;

- please expand abbreviations when they first appear in the text (e.g., SOC in line 41);

- In conclusion it is stated that "Excellent low temperature performance of LIBs can be obtained by electronic modulation and structural regulation". Please summarize how this electronic modulation and structural regulation should be performed to ensure excellent low temperature performance of LIBs.

Author Response

Response to Reviewer 2 Comments

 

The manuscript "Electronic modulation and structural engineering of carbon-based anodes for low-temperature lithium-ion batteries: a review" is aimed to review the low temperature performance of lithium-ion batteries with anodes from various carbon-based materials.

So far, several reviews are available on the trouble shooting of the low temperature performance of lithium-ion batteries, among them:

- Rodrigues, M.-T.F. et al. A materials perspective on Li-ion batteries at extreme temperatures (2017) Nature Energy, 2 (8), art. no. 17108

- Zhu, G. et al. Materials insights into low-temperature performances of lithium-ion batteries (2015) Journal of Power Sources, 300, pp. 29-40

- Zhang, N. et al. Critical Review on Low-Temperature Li-Ion/Metal Batteries (2022) Advanced Materials, 34 (15), art. no. 2107899

- Collins, G.A. et al. Alternative anodes for low temperature lithium-ion batteries (2021) Journal of Materials Chemistry A, 9 (25), pp. 14172-14213

- Selinis, P., Farmakis, F. Review - A Review on the Anode and Cathode Materials for Lithium-Ion Batteries with Improved Subzero Temperature Performance (2022) Journal of the Electrochemical Society, 169 (1), art. no. 010526

and several others.  Also, there is a number of reviews on anode carbon materials, among them:

- Roy, P. et al. Nanostructured anode materials for lithium ion batteries (2015) Journal of Materials Chemistry A, 3 (6), pp. 2454-2484

- Zhang, L. et al. Advanced nanostructured carbon-based materials for rechargeable lithium-sulfur batteries (2019) Carbon, 141, pp. 400-416

- Roselin, L.S. et al. Recent advances and perspectives of carbon-based nanostructures as anode materials for Li-ion batteries (2019) Materials, 12 (8), art. no. 1229

In view of this abundance of general literature reviews on the topic, a more detailed and critical review on the sub-topic of carbon materials as anodes in low-temperature batteries could justify a new review paper in the family. In my view, the present manuscript should be carefully revised to make such review interesting and useful for a reader. In particular, the following issues should be addressed by the authors:

Point 1:- please mention the previous relevant reviews in the introduction section and highlight the novelty of your work;

 

Response 1: We thank the reviewer for the constructive suggestions. According to the comment, the the previous relevant reviews have been included in the introduction part to enrich our innovation.

 

Point 2:- please quantify formulations like "excellent conductivity" etc. when you describe materials, so that it could be possible to compare between them;

 

Response 2: Thanks for your valuable comments. The conductivity value of some materials, like LTO, carbon black, graphene, and so on have been provided in the revised manuscript.

Point 3:- please check carefully the language use, there is a lot of mistakes and sometimes the mistakes make the passages incomprehensible; some examples:

lines 59-61: "Under low temperature conditions, high rate charging will cause lithium metal precipitation, so that lithium metal and electrolyte reaction,"

lines 80-85: "The low-temperature performance of LIBs will be impacted from the outside in by factors such the packaging of the LIBs, external temperature, and charging cut-off voltage."

line 247: "Activated carbon performance is good, environmental protection, cheap price."

and in other places;

 

Response 3: Thanks for your valuable comments. We have checked the whole manuscript, and make sure to avoid the mistakes you have mentioned above. In addition, We choose MDPI Language Editing Services to improve our language. Our order invoice ID is english-60713.

 

Point 4:- please carefully revise the sources to be included in the review; for example, Li1.2Ni0.13Co0.13Mn0.54O2 (line 207) seems to be outside the review scope;

 

Response 4: Thanks for your valuable comments. This chapter serves as a introduction to the importance of modified electrode materials to adapt to low temperature LIBs. Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ as a kind of typical LIBs electrode materials, the researchers are focused on the enhanced low temperature LIBs performance. We rewrite this paragraph.

 

Point 5:- please use only family names when you mention other researchers, without first names;

 

Response 5: Thanks for your valuable comments. The researchers mentioned in the review have been used by only family names.

 

Point 6:- please expand abbreviations when they first appear in the text (e.g., SOC in line 41);

 

Response 6: Thanks for your valuable comments. All the abbreviations in the revised manuscript are written out in full the first time.

 

Point 7:- In conclusion it is stated that "Excellent low temperature performance of LIBs can be obtained by electronic modulation and structural regulation". Please summarize how this electronic modulation and structural regulation should be performed to ensure excellent low temperature performance of LIBs.

 

Response 7: Thanks for your valuable comments. The specific ways of electronic modulation and structural regulation have been included in the conclusion. The specific changes are as below:

In detail: (1) Manipulating the configurations and positions of doping in carbon-based materials is both challenging and intriguing. The integration of dopants with topological defects, such as pentagon rings and micropore edges, offers a plethora of possibilities for exploring novel applications of carbon-based nanomaterials. New synthesis methods, including organic synthesis, are predicted to enable the exclusive attainment of particular target configurations. By finely regulating the components on the interior and exterior surfaces, the carbon shells can be transformed into a Janus surface, thus achieving synergistic functions that enhance surface redox reactions or enable spatial separation of coupled reactions in low temperature LIBs; (2) Efficient methods for regulating the porous structure of carbon materials must be further developed. In particular, more convenient and scalable approaches than the simple capillarity method are required to regulate the mesopores, which are essential for practical applications of high-volumetric energy-density LIBs. Additionally, the precise regulation of perforated micropores throughout the shells via appropriate reactions would be valuable, as this is closely linked to the molecular sieving/blocking effect in energy storage; (3) The use of carbon-based materials to encapsulate or support foreign active materials has shown significant benefits in energy applications. Therefore, it is strongly advised to create more composites of this type, given their potential for exceptional performance. Efficient and controllable methods are necessary for encapsulating these materials, as complete encapsulation within the carbon materials is not always straightforward and can be time-consuming. In many instances, the amount of material that can be loaded is still considerably below the theoretical limit.

 

Round 2

Reviewer 2 Report

The authors have mostly addressed my concerns. I believe, the manuscript "Electronic modulation and structural engineering of carbon-based anodes for low-temperature lithium-ion batteries: a review" might be published in Molecules.

The review contains several illustrations adapted from other sources, the necessary references are given by the authors. Please check the copyright policies of the source publications. A permission for reuse of the illustrations might be required.

Author Response

Thanks for your valuable comments. A permission for reuse the images has been applied and obtained. It is also reflected in the revised manuscript.