Preparation of High Geometric Filling Factor Perovskite Module and Feasibility Study on Electrocatalytic Hydrogen Production

Round 1

Reviewer 1 Report

The Research on Optimization of Preparation Process for Perovskite Solar Modules Used for Electrocatalytic Hydrogen Production by authors Lang Yu , Wenfeng Zhang, Hao Ge, Guangyuan Yan, Wei Yu, Yonghong Du, Leyi Zhou, Wei Long and Yuelong Huang shows an interesting research regarding development of an efficient perovskite module with high geometric fill factor (GFF) based on a two-step spin-coating method by optimizing the laser ablation step and optimization of the parameters and process for achieving an ultra-high GFF of over 99%.

Firstly, Perovskite Solar Modules and similar alternative and green energy power generation is not used only for Electrocatalytic Hydrogen Production. Hence the title should be changed. Especially as the paper deals only with optimization of the parameters and process for achieving an ultra-high GFF in PSMs. Maybe feasibility should be added.

The goal of the research is not emphasized enough. The Authors need to address the Goal and the Aim of the research.

Lines 68-71. This should be written as one sentence. Remove dot from line 69

The introduction should also include other examples of using PSMs, not only for hydrogen production, as this is just one of the examples.

Lines 125-132: In Materials and Methods, supplier city/state/country needs to be added.

Line 133: “…an ITO glass with a square resistance of 15 Ω/□” should be “an ITO glass with a square resistance of 15 Ω/cm²”

Figure 1b: In stead of squaring P1, P2 and P3 Authors should put in two sided arrows. It can confuse the readers, as P1 looks as input, not that it is ablated area.

Figure 2b: Micrograph of the ablated area with different P2 laser repetition frequency (KHz). – what P2 laser power is used with different repetition frequencies in the presented figure?

Lines 259-272: At what laser power were these experiments performed?

Lines 309-313: A part of sentence “…for the experimental setup we used…” or similar needs to be added.

Line 326: “there are two process routes for P3…” should be “There are two process routes for P3…”

Minor errors. English is satisfactory.

Author Response

Response Letter

May 24, 2023

Title: Optimization of Preparation Process for Perovskite Solar Modules Used for Electrocatalytic Hydrogen Production

Manuscript ID: catalysts-2385270

 

Dear Reviewer

We sincerely thank the editor and all reviewers for their valuable feedback that we have used to improve the quality of our manuscript. The reviewer comments are laid out below in italicized font and specific concerns have been numbered. Our response is given in normal font and changes/additions to the manuscript are given in the red text. All changes we made in the manuscript were made in Track changes mode, and you can open it to determine what changes we made.

 

1. Firstly, Perovskite Solar Modules and similar alternative and green energy power generation is not used only for Electrocatalytic Hydrogen Production. Hence the title should be changed. Especially as the paper deals only with optimization of the parameters and process for achieving an ultra-high GFF in PSMs. Maybe feasibility should be added.

We think this is a good suggestion. We have revised the title of the paper in the manuscript, and the revised title is “Preparation of High Geometric Filling Factor Perovskite Module and Feasibility Study on Electrocatalytic Hydrogen Production”.

2. The goal of the research is not emphasized enough. The Authors need to address the Goal and the Aim of the research.

We sincerely thank you for your valuable comments. We have carefully examined the literature and added an emphasis on the goals and objectives of our topic in the introduction section. (Lines 142-147).

3. Lines 68-71. This should be written as one sentence. Remove dot from line 69.

We have revised this section based on reviewer suggestions. (Lines 70-73).

4. The introduction should also include other examples of using PSMs, not only for hydrogen production, as this is just one of the examples.

We sincerely thank you for your valuable comments. I would like to explain this. Chalcogenide is an emerging photovoltaic cell that is still in a high development stage, and currently it does not have many applications in many directions. Its main application is photovoltaic power generation, which is widely known, and its application in electrolysis of water for hydrogen production is almost non-existent. Our main work is to make it possible to generate more electricity, and the electrolysis of hydrogen from water is our extension of its subsequent application area, and we have analyzed and verified its feasibility.

5. Lines 125-132: In Materials and Methods, supplier city/state/country needs to be added.

As suggested by the reviewer, we have added the supplier city/state/country in Materials and Methods. (Lines 174-180).

6. Line 133: “…an ITO glass with a square resistance of 15 Ω/□” should be “an ITO glass with a square resistance of 15 Ω/cm²”

We have re-written this part according to the Reviewer’s suggestion.

7. Figure 1b: Instead of squaring P1, P2 and P3 Authors should put in two sided arrows. It can confuse the readers, as P1 looks as input, not that it is ablated area.

We sincerely thank you for your valuable comments. After consideration, we have replaced Figure 1b to make it more visual to show the laser scribing process and the ablation area.

8. Figure 2b: Micrograph of the ablated area with different P2 laser repetition frequency (KHz). – what P2 laser power is used with different repetition frequencies in the presented figure?

Thank you for your reminder. The laser power used in Figure 2b is 0.5 W. We have indicated this in the article.

9. Lines 259-272: At what laser power were these experiments performed?

Thank you for your reminder. All these experiments were conducted at 0.5w laser power, which is the optimal power we compared. We have marked them in the text.

10. Lines 309-313: A part of sentence “…for the experimental setup we used…” or similar needs to be added.

Thanks for your suggestion. We have re-written this part according to the Reviewer’s suggestion.

11. Line 326: “there are two process routes for P3…” should be “There are two process routes for P3…”

We think this is an excellent suggestion. We have made changes here in the word.

We tried our best to improve the manuscript and made some changes marked in red in revised paper which will not influence the content and framework of the paper. We appreciate for Editors/Reviewers’ warm work earnestly and hope the correction will meet with approval. Once again, thank you very much for your comments and suggestions.

 

Yours sincerely,

 

Zhang Wenfeng

School of New Energy and Materials

Southwest Petroleum University

Chengdu 610500, China

E-mail: [email protected]

Author Response File: Author Response.docx

Reviewer 2 Report

Reviewing Report for the manuscript ID: catalysts-2385270

Here is my reviewing report for the manuscript under title “Optimization of Preparation Process for Perovskite Solar Modules Used for Electrocatalytic Hydrogen Production” with ID number: catalysts-2385270. Kindly find it.

 In this manuscript, the authors outlined a way to overcome the loss efficiency in the perovskite solar cells modules by constructing the entire device structure by picosecond green pulsed laser. Due to this treatment, the dead area significantly reduced, and the assembled PSC with an aperture area of 12.6 cm2 showed excellent (99%) geometric fill factor (GFF), and the maximum photoelectric conversion efficiency (PCE) was 22.79%.

Also, they reported the application of the assembled PSC modules showed an excellent performance for electrocatalytic hydrogen production.

Generally, the findings are interesting for readers, however, there are some revisions required before publication.

1-    The language of the manuscript needed to be revised. For example, there are many long sentences, also some time they use Fig. and Figure.

2-    It’s recommended to compare the findings in this manuscript with the others.

3-    In line 188 (page 2), use only GFF not geometric fill factor (GFF).

4-    From line 133 (page 3), make this section under sub-title; Fabrication of Perovskite solar module (PSM), or other suitable sub-title.

5-    In table 2 (page 7): can the authors explain the main aspersions for the irregular trend in R_S.

6-     In Figure 3, and line 267 (page 7), the authors mentioned that as the laser repetition frequency increases, the P2 ablation area becomes cleaner. Can they explain how this affects the total performance of the assembled devices?

7-    In line 375 (page 11), Figure 6b should be Figure 7b.

8-    In page 11, paragraph (375-384), needs to be rewritten and deleted the repeated words to be understandable.

9-    In page 11, line 403 needs to be deleted or introduced in the above sentence.

 

All regards,

Abdelaal Ahmed

The English of the manuscript needs to be carefully revised 

Author Response

Response Letter

May 24, 2023

Title: Optimization of Preparation Process for Perovskite Solar Modules Used for Electrocatalytic Hydrogen Production

Manuscript ID: catalysts-2385270

 

Dear Reviewer

We sincerely thank the editor and all reviewers for their valuable feedback that we have used to improve the quality of our manuscript. The reviewer comments are laid out below in italicized font and specific concerns have been numbered. Our response is given in normal font and changes/additions to the manuscript are given in the red text. All changes we made in the manuscript were made in Track changes mode, and you can open it to determine what changes we made.

 

1. The language of the manuscript needed to be revised. For example, there are many long sentences, also some time they use Fig. and Figure.

Thank you very much for your advice. We apologize for our carelessness. It has been revised in our resubmitted manuscript.

2. It’s recommended to compare the findings in this manuscript with the others.

As suggested by the reviewers, we added additional references to compare with our results. (References 17.39.40.41.42.43).

3. In line 188 (page 2), use only GFF not geometric fill factor (GFF).

Thank you very much for your advice. We have made changes in the resubmitted manuscript.

4. From line 133 (page 3), make this section under sub-title; Fabrication of Perovskite solar module (PSM), or other suitable sub-title.

We think this is an excellent suggestion. We have added subheadings in Chapter 2 to give the reader a better understanding of our experimental ideas.

5. In table 2 (page 7): can the authors explain the main aspersions for the irregular trend in RS.

Thank you for your question. I will explain this question next. The irregular trend of Rs in Table 2 is mainly due to the effective removal of non-conductive PbI2 inside the P2 trench, which increases the contact area between the top metal electrode and the TCO layer and improves the charge transfer efficiency. During the P2 laser scribing process, chalcocite will partially decompose to form PbI₂ due to its instability, and due to its autogenous and more stable nature, PbI₂ will not be removed as easily as chalcocite. Therefore, when the laser power is low, there will be more PbI₂ residue, which will affect the contact between the top and bottom electrodes, thus increasing the series resistance Rs. And when the laser power is high, the P2 laser will ablate through the TCO layer, resulting in the reduction of its contact area with the top electrode, which will also increase Rs.

6. In Figure 3, and line 267 (page 7), the authors mentioned that as the laser repetition frequency increases, the P2 ablation area becomes cleaner. Can they explain how this affects the total performance of the assembled devices?

Thank you for your question. I will explain this issue next. As I replied in the fifth question, the residual PbI₂ inside the P2 ablation area is a non-conductive insulator, and its presence will affect the contact between the top and bottom electrodes, which will increase the series resistance Rs of the device, thus decreasing the short-circuit current density J_SC and thus affecting the overall performance of the device.

7. In line 375 (page 11), Figure 6b should be Figure 7b.

Thank you for your suggestion, we apologize for our mistake and have made changes in the resubmitted manuscript.

8. In page 11, paragraph (375-384), needs to be rewritten and deleted the repeated words to be understandable.

We have re-written this part according to the Reviewer’s suggestion.

9. In page 11, line 403 needs to be deleted or introduced in the above sentence.

Thank you for your suggestion, we apologize for our mistake and have made changes in the new manuscript.

 

We tried our best to improve the manuscript and made some changes marked in red in revised paper which will not influence the content and framework of the paper. We appreciate for Editors/Reviewers’ warm work earnestly and hope the correction will meet with approval. Once again, thank you very much for your comments and suggestions.

 

Yours sincerely,

 

Zhang Wenfeng

School of New Energy and Materials

Southwest Petroleum University

Chengdu 610500, China

E-mail: [email protected]

 

References

(17)   Bu, T.; Li, J.; Li, H.; Tian, C.; Su, J.; Tong, G.; Ono, L. K.; Wang, C.; Lin, Z.; Chai, N.; Zhang, X.-L.; Chang, J.; Lu, J.; Zhong, J.; Huang, W.; Qi, Y.; Cheng, Y.-B.; Huang, F. Lead Halide–Templated Crystallization of Methylamine-Free Perovskite for Efficient Photovoltaic Modules. Science 2021, 372 (6548), 1327–1332. https://doi.org/10.1126/science.abh1035.

(39)   Moon, S.-J.; Yum, J.-H.; Löfgren, L.; Walter, A.; Sansonnens, L.; Benkhaira, M.; Nicolay, S.; Bailat, J.; Ballif, C. Laser-Scribing Patterning for the Production of Organometallic Halide Perovskite Solar Modules. IEEE Journal of Photovoltaics 2015, 5 (4), 1087–1092. https://doi.org/10.1109/JPHOTOV.2015.2416913.

(40)   Liu, C.; Yang, Y.; Rakstys, K.; Mahata, A.; Franckevicius, M.; Mosconi, E.; Skackauskaite, R.; Ding, B.; Brooks, K. G.; Usiobo, O. J.; Audinot, J.-N.; Kanda, H.; Driukas, S.; Kavaliauskaite, G.; Gulbinas, V.; Dessimoz, M.; Getautis, V.; De Angelis, F.; Ding, Y.; Dai, S.; Dyson, P. J.; Nazeeruddin, M. K. Tuning Structural Isomers of Phenylenediammonium to Afford Efficient and Stable Perovskite Solar Cells and Modules. Nat Commun 2021, 12 (1), 6394. https://doi.org/10.1038/s41467-021-26754-2.

(41)   Yoo, J. W.; Jang, J.; Kim, U.; Lee, Y.; Ji, S.-G.; Noh, E.; Hong, S.; Choi, M.; Seok, S. I. Efficient Perovskite Solar Mini-Modules Fabricated via Bar-Coating Using 2-Methoxyethanol-Based Formamidinium Lead Tri-Iodide Precursor Solution. Joule 2021, 5 (9), 2420–2436. https://doi.org/10.1016/j.joule.2021.08.005.

(42)   Abdollahi Nejand, B.; Ritzer, D. B.; Hu, H.; Schackmar, F.; Moghadamzadeh, S.; Feeney, T.; Singh, R.; Laufer, F.; Schmager, R.; Azmi, R.; Kaiser, M.; Abzieher, T.; Gharibzadeh, S.; Ahlswede, E.; Lemmer, U.; Richards, B. S.; Paetzold, U. W. Scalable Two-Terminal All-Perovskite Tandem Solar Modules with a 19.1% Efficiency. Nat Energy 2022, 7 (7), 620–630. https://doi.org/10.1038/s41560-022-01059-w.

(43)   Gao, Y.; Liu, C.; Xie, Y.; Guo, R.; Zhong, X.; Ju, H.; Qin, L.; Jia, P.; Wu, S.; Schropp, R. E. I.; Mai, Y. Can Nanosecond Laser Achieve High-Performance Perovskite Solar Modules with Aperture Area Efficiency Over 21%? Advanced Energy Materials 2022, 12 (41), 2202287. https://doi.org/10.1002/aenm.202202287.

 

Author Response File: Author Response.docx

Reviewer 3 Report

1.      At the bottom of the page 11, something is missing.

2.      In the introduction part, please clarify if there is similar work in open literature ?

3.      If similar work exists, please compare these work with your results

English is fine, minor editing can improve the manuscript

Author Response

Response Letter

May 24, 2023

Title: Optimization of Preparation Process for Perovskite Solar Modules Used for Electrocatalytic Hydrogen Production

Manuscript ID: catalysts-2385270

 

Dear Reviewer

We sincerely thank the editor and all reviewers for their valuable feedback that we have used to improve the quality of our manuscript. The reviewer comments are laid out below in italicized font and specific concerns have been numbered. Our response is given in normal font and changes/additions to the manuscript are given in the red text. All changes we made in the manuscript were made in Track changes mode, and you can open it to determine what changes we made.

 

1. At the bottom of the page 11, something is missing.

We have re-written this part according to the Reviewer’s suggestion.

2. In the introduction part, please clarify if there is similar work in open literature?

We sincerely appreciate the valuable comments. Similar work already exists. We have checked the literature carefully and added more references on the research history of GFF in PSMs and dead width optimization in recent years in the revised manuscript. (References 35.36.37.38.39.40.41.42.43)

3. If similar work exists, please compare these works with your results.

As suggested by the reviewers, we added additional references to compare with our results. (References 17.39.40.41.42.43)

 

We tried our best to improve the manuscript and made some changes marked in red in revised paper which will not influence the content and framework of the paper. We appreciate for Editors/Reviewers’ warm work earnestly and hope the correction will meet with approval. Once again, thank you very much for your comments and suggestions.

 

Yours sincerely,

 

Zhang Wenfeng

School of New Energy and Materials

Southwest Petroleum University

Chengdu 610500, China

E-mail: [email protected]

 

References

(17)   Bu, T.; Li, J.; Li, H.; Tian, C.; Su, J.; Tong, G.; Ono, L. K.; Wang, C.; Lin, Z.; Chai, N.; Zhang, X.-L.; Chang, J.; Lu, J.; Zhong, J.; Huang, W.; Qi, Y.; Cheng, Y.-B.; Huang, F. Lead Halide–Templated Crystallization of Methylamine-Free Perovskite for Efficient Photovoltaic Modules. Science 2021, 372 (6548), 1327–1332. https://doi.org/10.1126/science.abh1035.

(35)   Razza, S.; Di Giacomo, F.; Matteocci, F.; Cinà, L.; Palma, A. L.; Casaluci, S.; Cameron, P.; D’Epifanio, A.; Licoccia, S.; Reale, A.; Brown, T. M.; Di Carlo, A. Perovskite Solar Cells and Large Area Modules (100 Cm2) Based on an Air Flow-Assisted PbI2 Blade Coating Deposition Process. Journal of Power Sources 2015, 277, 286–291. https://doi.org/10.1016/j.jpowsour.2014.12.008.

(36)   Agresti, A.; Pescetelli, S.; Palma, A. L.; Del Rio Castillo, A. E.; Konios, D.; Kakavelakis, G.; Razza, S.; Cinà, L.; Kymakis, E.; Bonaccorso, F.; Di Carlo, A. Graphene Interface Engineering for Perovskite Solar Modules: 12.6% Power Conversion Efficiency over 50 Cm 2 Active Area. ACS Energy Lett. 2017, 2 (1), 279–287. https://doi.org/10.1021/acsenergylett.6b00672.

(37)   Du, M.; Zhu, X.; Wang, L.; Wang, H.; Feng, J.; Jiang, X.; Cao, Y.; Sun, Y.; Duan, L.; Jiao, Y.; Wang, K.; Ren, X.; Yan, Z.; Pang, S.; Liu, S. (Frank). High‐Pressure Nitrogen‐Extraction and Effective Passivation to Attain Highest Large‐Area Perovskite Solar Module Efficiency. Adv. Mater. 2020, 32 (47), 2004979. https://doi.org/10.1002/adma.202004979.

(38)   Green, M. A.; Dunlop, E. D.; Hohl‐Ebinger, J.; Yoshita, M.; Kopidakis, N.; Hao, X. Solar Cell Efficiency Tables (Version 58). Prog Photovolt Res Appl 2021, 29 (7), 657–667. https://doi.org/10.1002/pip.3444.

(39)   Moon, S.-J.; Yum, J.-H.; Löfgren, L.; Walter, A.; Sansonnens, L.; Benkhaira, M.; Nicolay, S.; Bailat, J.; Ballif, C. Laser-Scribing Patterning for the Production of Organometallic Halide Perovskite Solar Modules. IEEE Journal of Photovoltaics 2015, 5 (4), 1087–1092. https://doi.org/10.1109/JPHOTOV.2015.2416913.

(40)   Liu, C.; Yang, Y.; Rakstys, K.; Mahata, A.; Franckevicius, M.; Mosconi, E.; Skackauskaite, R.; Ding, B.; Brooks, K. G.; Usiobo, O. J.; Audinot, J.-N.; Kanda, H.; Driukas, S.; Kavaliauskaite, G.; Gulbinas, V.; Dessimoz, M.; Getautis, V.; De Angelis, F.; Ding, Y.; Dai, S.; Dyson, P. J.; Nazeeruddin, M. K. Tuning Structural Isomers of Phenylenediammonium to Afford Efficient and Stable Perovskite Solar Cells and Modules. Nat Commun 2021, 12 (1), 6394. https://doi.org/10.1038/s41467-021-26754-2.

(41)   Yoo, J. W.; Jang, J.; Kim, U.; Lee, Y.; Ji, S.-G.; Noh, E.; Hong, S.; Choi, M.; Seok, S. I. Efficient Perovskite Solar Mini-Modules Fabricated via Bar-Coating Using 2-Methoxyethanol-Based Formamidinium Lead Tri-Iodide Precursor Solution. Joule 2021, 5 (9), 2420–2436. https://doi.org/10.1016/j.joule.2021.08.005.

(42)   Abdollahi Nejand, B.; Ritzer, D. B.; Hu, H.; Schackmar, F.; Moghadamzadeh, S.; Feeney, T.; Singh, R.; Laufer, F.; Schmager, R.; Azmi, R.; Kaiser, M.; Abzieher, T.; Gharibzadeh, S.; Ahlswede, E.; Lemmer, U.; Richards, B. S.; Paetzold, U. W. Scalable Two-Terminal All-Perovskite Tandem Solar Modules with a 19.1% Efficiency. Nat Energy 2022, 7 (7), 620–630. https://doi.org/10.1038/s41560-022-01059-w.

(43)   Gao, Y.; Liu, C.; Xie, Y.; Guo, R.; Zhong, X.; Ju, H.; Qin, L.; Jia, P.; Wu, S.; Schropp, R. E. I.; Mai, Y. Can Nanosecond Laser Achieve High-Performance Perovskite Solar Modules with Aperture Area Efficiency Over 21%? Advanced Energy Materials 2022, 12 (41), 2202287. https://doi.org/10.1002/aenm.202202287.

Round 2

Reviewer 3 Report

the author revised the paper appropriately, it can be published

minor editing is needed