Intrinsically Conducting Polymer Binders for Battery Electrodes
Round 1
Reviewer 1 Report
The authors present a short introduction to the development, problems and role concerning intrinsically conducting polymers (ICP) in the construction of batteries and supercapacitors. The article is written as an "entry" type of article and it is well organized, short and clear. I do not know what is requirements for the Entry type of Manuscript but I found that some schemes or figures can contribute to the clearness of the Manuscript.
However, before publishing, some corrections should be made.
- Firstly the title of the article must be more precise. "Electrode" is a broad term. As the Entry depict the role of ICP in energy storage devices, mainly battery, I found that title needs to be corrected according to above mentioned.
- In Definition (line 18-19) the author claims that the increase in the storage capacity of the battery can be attributed to the redox activity of ICP. However, ICP has two forms, depending on the oxidation state, which one is insulating. The contribution of redox activity in total storage capacity owing to pseudocapacitance (redox activity) is the properties of the conducting redox polymers (CRPs).
- Section 2.2 (line 97): macromolecular polyanions are polyelectrolytes. Which charge of polyelectrolytes can be used related to the type of doping of ICPs?
- Line 116-117: poly(acrylic acid) is also polyelectrolyte. In this section, some terms must be more clearly described such as "binders". What is binder: ICP or polyelectrolytes? Polyelectrolytes have the role of suspending agent for ICP. However, the term "binder" is used with a different meaning.
- Section 2.3 As ICP has a "protection" role in this type of modification, what is the influence of polyelectrolytes on ions' mobility between electrodes, depending on doping type?
- Section 2.5 ( i) and ii)) reference should be given for these claims.
- Section 3: Which are traditional binder materials?
Author Response
The authors present a short introduction to the development, problems and role concerning intrinsically conducting polymers (ICP) in the construction of batteries and supercapacitors. The article is written as an "entry" type of article and it is well organized, short and clear. I do not know what is requirements for the Entry type of Manuscript but I found that some schemes or figures can contribute to the clearness of the Manuscript.
However, before publishing, some corrections should be made.
- Firstly the title of the article must be more precise. "Electrode" is a broad term. As the Entry depict the role of ICP in energy storage devices, mainly battery, I found that title needs to be corrected according to above mentioned.
Response and action: The term “Electrode” in electrochemistry is generally defined as a system, consisting of an electronically conducting material in contact with an ionically conducting second phase. In the simplest case it is a metal in contact with an electrolyte solution. Both phases may be more compex, e.g. porous electrodes, 3D-electrodes etc. The title should indeed reflkect that this entry is about electrodes for batteries. We have mdofied the title accordingly. Unfortunately the numerous requirements of the publisher regarding even minor details of submissions linmiting the length of the title to five words limit the extension, more complete would be "... battery and supercapacitor electrodes"
- In Definition (line 18-19) the author claims that the increase in the storage capacity of the battery can be attributed to the redox activity of ICP. However, ICP has two forms, depending on the oxidation state, which one is insulating. The contribution of redox activity in total storage capacity owing to pseudocapacitance (redox activity) is the properties of the conducting redox polymers (CRPs).
Response and action: The added charge storage pertains exactly to this redox transition. In the neutral state ICPs are not insulkators but poorly conducting. This is not welcome, but it does not prevent this contribution. We have amended the text.
- Section 2.2 (line 97): macromolecular polyanions are polyelectrolytes. Which charge of polyelectrolytes can be used related to the type of doping of ICPs?
Response and action: Macromolecular polyanions like PSS are only used as counteranions for the ICP, they support their solubility or dispersion-forming capability. To illustrate this detail we have added Figure 1.
- Line 116-117: poly(acrylic acid) is also polyelectrolyte. In this section, some terms must be more clearly described such as "binders". What is binder: ICP or polyelectrolytes? Polyelectrolytes have the role of suspending agent for ICP. However, the term "binder" is used with a different meaning.
Response and action: ICPs are the binders as clearly stated. In case the ICP can also be called with some other names or if the show properties which are also found with other materials like e.g. polyelectrolytes this is mentioned only when the authors believe it is needed to avoid confusion. We have amended the text.
- Section 2.3 ICP has a "protection" role in this type of modification, what is the influence of polyelectrolytes on ions' mobility between electrodes, depending on doping type?
Response and action: ICPs coating diminish side reactions including dissolution of the active material and support conductivity near surface of active grains and between them. We have amended the text.
- Section 2.5 ( i) and ii)) reference should be given for these claims.
Response and action: We have added references as suggested
- Section 3: Which are traditional binder materials?
Response and action: Traditional binder types fall into two major categories: one contains binder soluble in organic solvents represented by polyvinylidene fluoride (PVDF), the other is water-soluble binders represented by carboxymethylcellulose (CMC), mixture like carboxymethylcellulose/styrene butadiene rubber (SBR) and many others proposed recently. PVDF is the most widely used binders in lithium batteries application.
Reviewer 2 Report
This manuscript by the V. Kondratiev group describes the importance of intrinsically conducting polymer binders for electrodes. I will recommend the manuscript for publication in the Encyclopedia after major revision. Here are some comments from the authors.
1. The standard of English in the manuscript is extremely poor to meet the requirement of any standard journal. The numerous typos, grammatical errors, and instances of badly constructed sentences should be corrected in the entire manuscript. I strongly recommend the authors take the aid of a native English speaker/English editor before the new submission.
2. In the introduction section, the literature survey is limited. Therefore, the authors should provide more information on the recent development of ICP binders.
3. The authors are suggested to add references in the first part of the introduction.
4. The major drawback of the manuscript is the absence of schematics, no pictorial representation, no structural presentation for the binders, and no figures from the literature to show the advantage of the ICP binders. The authors should add molecular structures of the ICP binders, and schematics showing the mechanism of binding with electrode active material.
5. The author should provide proper references when stating some important information about the binder in the entire manuscript.
6. Author should explain- what is important for the binder’s ionic conductivity or electronic conductivity. These will strengthen the manuscript.
7. Solid electrolyte interphase (SEI) is one of the important aspects of battery chemistry and is known to be influenced by binders. There is no information about the SEI in the manuscript, the authors should explain how the ICP binders can influence SEI.
8. The authors should shed light on the cost-effectiveness of the ICP binders compared to PVDF, CMC-SBR, PAA, and Na-Alginate.
9. There is not a single reference in the method of preparation of composite electrodes with ICP. This is very important for the reader.
10. The authors should expand the contents of the manuscript more with more explanation and good references. Some part of the manuscript fails to connect with the story. The authors should pay more attention.
11. Finally, how is the viability of the ICP binders in the industrial scale?
Author Response
This manuscript by the V. Kondratiev group describes the importance of intrinsically conducting polymer binders for electrodes. I will recommend the manuscript for publication in the Encyclopedia after major revision. Here are some comments from the authors.
- The standard of English in the manuscript is extremely poor to meet the requirement of any standard journal. The numerous typos, grammatical errors, and instances of badly constructed sentences should be corrected in the entire manuscript. I strongly recommend the authors take the aid of a native English speaker/English editor before the new submission.
Response and action: The text has been carefully revised and has been checked by a native speaker familiar with the subject.
- In the introduction section, the literature survey is limited. Therefore, the authors should provide more information on the recent development of ICP binders.
Response and action: We have included all recent research reports and overviews which we think are relevant and helpful for a potential reader. We did not attempt to provide a comprehensive and all-inclusive review on the subject, this would certainly be beyond an encyclopedia entry.
- The authors are suggested to add references in the first part of the introduction.
Response and action: see # 2
- The major drawback of the manuscript is the absence of schematics, no pictorial representation, no structural presentation for the binders, and no figures from the literature to show the advantage of the ICP binders. The authors should add molecular structures of the ICP binders, and schematics showing the mechanism of binding with electrode active material.
Response and action: The authors use any kind of illustration only when needed and helpful. We have added figures where we feel they are really needed.
- The author should provide proper references when stating some important information about the binder in the entire manuscript.
Response and action: References have been added.
- Author should explain- what is important for the binder’s ionic conductivity or electronic conductivity. These will strengthen the manuscript.
Response and action: Both binder’s ionic conductivity and electronic conductivity are turned out very important for improvement of battery functional properties. The discussion of these issues will be done in article.
- Solid electrolyte interphase (SEI) is one of the important aspects of battery chemistry and is known to be influenced by binders. There is no information about the SEI in the manuscript, the authors should explain how the ICP binders can influence SEI.
Response and action: All types of binders are influenced on the properties of interface active grains-electrolyte. An engineering of interface is important and is considered as the constructing of artificial passivation layer, which prevent or brakes some side reactions. These issues will be considered in article. .
- The authors should shed light on the cost-effectiveness of the ICP binders compared to PVDF, CMC-SBR, PAA, and Na-Alginate.
Response and action: The cost-effectiveness of the ICP binders as well other will depends on the mass scale application in batteries. At the moment, the cost of polyelectrolytes like CMC, CMC-SBR, PAA, and Na-Alginate is not high in comparison with even traditional binder PVDF. However, the cost of industrial production of polyvinylidene fluoride (PVDF) and ICPs containing binder are comparable and will be probably equal in the case of wide application of ICPs.
- There is not a single reference in the method of preparation of composite electrodes with ICP. This is very important for the reader.
Response and action: Numerous references containing (except for some reviews) contain specific instructions for composite preparation.
- The authors should expand the contents of the manuscript more with more explanation and good references. Some part of the manuscript fails to connect with the story. The authors should pay more attention.
Response and action: The authors unfortunately failed to understand this criticism.
- Finally, how is the viability of the ICP binders in the industrial scale?
Response and action: The authors are not aware of any relevant statement on this question from a relevant source; they do not feel qualified to offer a personal opinion on this point.
Reviewer 3 Report
The manuscript entitled "Intrinsically conducting polymer binders for electrodes". This work is well written and it brings important information/discussion on electrochemistry related to conducting polymer binders for electrodes.
Before I recommend its acceptance, some points must be clarified and a moderate revision is needed.
Some other issues that need to be addressed are:
1. It is not clear the contribution of the manuscript to the empirical literature.
2. The authors should mention on the concept of this work with the progress against the most recent state-of-the-art similar studies.
3. Some images should enhance the quality of the paper.
4. The limitation of this study needs to be provided as well.
5. Conclusions and Prospects are very weak. All conclusions must be convincing statements on what was found to be impactful based on the strong support of the discussion.
Author Response
The manuscript entitled "Intrinsically conducting polymer binders for electrodes". This work is well written and it brings important information/discussion on electrochemistry related to conducting polymer binders for electrodes.
Before I recommend its acceptance, some points must be clarified and a moderate revision is needed.
Some other issues that need to be addressed are:
- It is not clear the contribution of the manuscript to the empirical literature.
Response and action: This is an entry for an open-access online work: Encyclopedia of Electrochemical Energy Storage and Conversion. Accordingly it is not an exhaustive review or a critical examination of all published literature but foremost an attempt to provide an introduction and overview for the interested reader.
- The authors should mention on the concept of this work with the progress against the most recent state-of-the-art similar studies.
Response and action: We have added a respective remark
- Some images should enhance the quality of the paper.
Response and action: The authors prefer to inbsert figures and illustrations only wehn needed and justified. We have added some figures.
- The limitation of this study needs to be provided as well.
Response and action: As this is no study (see # 1) the added remark should take into account this concern.
- Conclusions and Prospects are very weak. All conclusions must be convincing statements on what was found to be impactful based on the strong support of the discussion.
Response and action: We have amended the text.
Round 2
Reviewer 1 Report
The authors made amendments to the manuscript.
Reviewer 2 Report
Accept in present form
Reviewer 3 Report
The authors have addressed most of the comments; they have also tried to make changes according to the reviewers' suggestions. After revisions, the quality of the manuscript has been adequately enhanced. Therefore, the manuscript could be considered for publication in the Journal.
