Skip to main content
SpringerLink
Log in

Tunable nitrogen crafted 2D-graphene nano-hybrid from industrial expansive and ecological approach as robust cathode microporous layer to improve performance of a direct methanol fuel cell

  • Article
  • Published:
Science China Technological Sciences Aims and scope Submit manuscript

Abstract

In this work, the excess water-stagnation issue in the high current region in direct methanol fuel cells (DMFCs) is resolved by using atomic precision modulated nitrogen-crafted graphene (NG) in the cathode microporous layer by utilizing simplistic, industrial-expansive and ecological strategy. Few-layer 2D-graphene (∼2–5 nm thickness) is prepared by bath sonication approach from abundant feedstock-graphite and is treated with nitric acid to yield 1.8 wt.% uniformly dispersed nitrogen containing NG. Specifically, 1:4 weight ratio NG:carbon-black (CB) hybrid architecture, displays 0.252 V in 370 mA cm−2 with the peak power density of 93.4 mW cm−2, improving cell power density by 45.6% compared with standard one at 60°C and 1 mol/L methanol/oxygen conditions at ultra-low catalyst loadings and displaying exceptional stability. Atomic insights into NG reveal that interplay between bonding configurations, altered hydrophobic/hydrophilic porosity of graphene (10.6% less wettability from contact angle and 13.1% high electrode porosity measurements) contribute to the better mass-transport-porogenic effect (16.3% high oxygen-permeability), mildly affecting the electron pathway (6.5% reduced in-plane electrical conductivity), overall significantly improving cell performance. Altogether, this work delivers multiple advantages, i.e., the usage of material from facile, sustainable and cost-effective routes, while improving DMFC performance with potential industrial promise.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Dicks A, Rand D. Fuel Cell Systems Explained. Hoboken: Wiley, 2018

    Google Scholar 

  2. O’Hayre R. Fuel Cell Fundamentals. Hoboken: John Wiley & Sons, 2005

    Google Scholar 

  3. Lin C, Wang T, Ye F, et al. Effects of microporous layer preparation on the performance of a direct methanol fuel cell. Electrochem Commun, 2008, 10: 255–258

    Google Scholar 

  4. Weber A Z, Newman J. Effects of microporous layers in polymer electrolyte fuel cells. J Electrochem Soc, 2005, 152: A677

    Google Scholar 

  5. Rho Y W, Srinivasan S, Kho Y T. Mass transport phenomena in proton exchange membrane fuel cells using O2/He, O2/Ar, and O2/N2 mixtures: II. theoretical analysis. J Electrochem Soc, 1994, 141: 2089–2096

    Google Scholar 

  6. Lin J H, Chen W H, Su Y J, et al. Effect of gas diffusion layer compression on the performance in a proton exchange membrane fuel cell. Fuel, 2008, 87: 2420–2424

    Google Scholar 

  7. Antolini E, Passos R R, Ticianelli E A. Effects of the carbon powder characteristics in the cathode gas diffusion layer on the performance of polymer electrolyte fuel cells. J Power Sources, 2002, 109: 477–482

    Google Scholar 

  8. Hiramitsu Y, Sato H, Hori M. Prevention of the water flooding by micronizing the pore structure of gas diffusion layer for polymer electrolyte fuel cell. J Power Sources, 2010, 195: 5543–5549

    Google Scholar 

  9. Hwang C M, Ishida M, Ito H, et al. Influence of properties of gas diffusion layers on the performance of polymer electrolyte-based unitized reversible fuel cells. Int J Hydrogen Energy, 2011, 36: 1740–1753

    Google Scholar 

  10. Velayutham G, Kaushik J, Rajalakshmi N, et al. Effect of PTFE content in gas diffusion media and microlayer on the performance of PEMFC tested under ambient pressure. Fuel Cells, 2007, 7: 314–318

    Google Scholar 

  11. Liu S, Wippermann K, Lehnert W. Mechanism of action of polytetrafluoroethylene binder on the performance and durability of high-temperature polymer electrolyte fuel cells. Int J Hydrogen Energy, 2021, 46: 14687–14698

    Google Scholar 

  12. Gharibi H, Javaheri M, Mirzaie R A. The synergy between multi-wall carbon nanotubes and Vulcan XC72R in microporous layers. Int J Hydrogen Energy, 2010, 35: 9241–9251

    Google Scholar 

  13. Gallo Stampino P, Omati L, Cristiani C, et al. Characterisation of nanocarbon-based gas diffusion media by electrochemical impedance spectroscopy. Fuel Cells, 2010, 10: 270–277

    Google Scholar 

  14. Bottino A, Capannelli G, Comite A, et al. Microporous layers based on poly(vinylidene fluoride) and sulfonated poly(vinylidene fluoride). Int J Hydrogen Energy, 2015, 40: 14690–14698

    Google Scholar 

  15. Wang X L, Zhang H M, Zhang J L, et al. Micro-porous layer with composite carbon black for PEM fuel cells. Electrochim Acta, 2006, 51: 4909–49 15

    Google Scholar 

  16. Cindrella L, Kannan A M, Ahmad R, et al. Surface modification of gas diffusion layers by inorganic nanomaterials for performance enhancement of proton exchange membrane fuel cells at low RH conditions. Int J Hydrogen Energy, 2009, 34: 6377–6383

    Google Scholar 

  17. Wang Y, Al Shakhshir S, Li X. Development and impact of sandwich wettability structure for gas distribution media on PEM fuel cell performance. Appl Energy, 2011, 88: 2168–2175

    Google Scholar 

  18. Kitahara T, Nakajima H, Mori K. Hydrophilic and hydrophobic double microporous layer coated gas diffusion layer for enhancing performance of polymer electrolyte fuel cells under no-humidification at the cathode. J Power Sources, 2012, 199: 29–36

    Google Scholar 

  19. Geim A K. The rise and rise of graphene. Nature Nanotech, 2010, 5: 755

    Google Scholar 

  20. Balakrishnan P, Holmes S. 2D materials graphene and hBN boost DMFC performance. Fuel Cells Bull, 2017, 2017(4): 14

    Google Scholar 

  21. Han T, Luo Y, Wang C. Effects of SI, N and B doping on the mechanical properties of graphene sheets. Acta Mech Solid Sin, 2015, 28: 618–625

    Google Scholar 

  22. Yuan T, Yang J, Wang Y, et al. Anodic diffusion layer with graphene-carbon nanotubes composite material for passive direct methanol fuel cell. Electrochim Acta, 2014, 147: 265–270

    Google Scholar 

  23. Leeuwner M J, Wilkinson D P, Gyenge E L. Novel graphene foam microporous layers for PEM fuel cells: Interfacial characteristics and comparative performance. Fuel Cells, 2015, 15: 790–801

    Google Scholar 

  24. Najafabadi A T, Leeuwner M J, Wilkinson D P, et al. Electrochemically produced graphene for microporous layers in fuel cells. ChemSusChem, 2016, 9: 1689–1697

    Google Scholar 

  25. Ozden A, Shahgaldi S, Li X, et al. A graphene-based microporous layer for proton exchange membrane fuel cells: Characterization and performance comparison. Renew Energy, 2018, 126: 485–494

    Google Scholar 

  26. Leeuwner M J, Patra A, Wilkinson D P, et al. Graphene and reduced graphene oxide based microporous layers for high-performance proton-exchange membrane fuel cells under varied humidity operation. J Power Sources, 2019, 423: 192–202

    Google Scholar 

  27. Shavelkina M B, Kleimenov B V, Zhuk A Z, et al. Gas diffusion layers based on graphene flakes doped with nitrogen. J Phys-Conf Ser, 2019, 1281: 012072

    Google Scholar 

  28. Gallo Stampino P, Latorrata S, Molina D, et al. Investigation of hydrophobic treatments with perfluoropolyether derivatives of gas diffusion layers by electrochemical impedance spectroscopy in PEM-FC. Solid State Ion, 2012, 216: 100–104

    Google Scholar 

  29. Yu J, Islam M N, Matsuura T, et al. Improving the performance of a PEMFC with ketjenblack EC-600JD carbon black as the material of the microporous layer. Electrochem Solid-State Lett, 2005, 8: A320

    Google Scholar 

  30. Yong V, Hahn H T. Graphene growth with giant domains using chemical vapor deposition. CrystEngComm, 2011, 13: 6933

    Google Scholar 

  31. Bautista-Flores C, Sato-Berrú R Y, Mendoza D. Doping graphene by chemical treatments using acid and basic substances. J Mater Sci Chem Eng, 2015, 03: 17–21

    Google Scholar 

  32. Breitwieser M, Bayer T, Büchler A, et al. A fully spray-coated fuel cell membrane electrode assembly using Aquivion ionomer with a graphene oxide/cerium oxide interlayer. J Power Sources, 2017, 351: 145–150

    Google Scholar 

  33. Durge R, Kshirsagar R V, Tambe P. Effect of sonication energy on the yield of graphene nanosheets by liquid-phase exfoliation of graphite. Procedia Eng, 2014, 97: 1457–1465

    Google Scholar 

  34. Amiri A, Naraghi M, Ahmadi G, et al. A review on liquid-phase exfoliation for scalable production of pure graphene, wrinkled, crumpled and functionalized graphene and challenges. FlatChem, 2018, 8: 40–71

    Google Scholar 

  35. Balakrishnan P, Sanij F D, Chang Z, et al. Nano-graphene layer from facile, scalable and eco-friendly liquid phase exfoliation strategy as effective barrier layer for high-performance and durable direct liquid alcohol fuel cells. Molecules, 2022, 27: 3044

    Google Scholar 

  36. Compton O C, Nguyen S B T. Graphene oxide, highly reduced graphene oxide, and graphene: Versatile building blocks for carbon-based materials. Small, 2010, 6: 711–723

    Google Scholar 

  37. Wang X, Sun G, Routh P, et al. Heteroatom-doped graphene materials: Syntheses, properties and applications. Chem Soc Rev, 2014, 43: 7067–7098

    Google Scholar 

  38. Wang P, Zhang C. Doped ways of boron and nitrogen doped carbon nanotubes: A theoretical investigation. J Mol Structure-THEOCHEM, 2010, 955: 84–90

    Google Scholar 

  39. Ferraro J, Nakamoto K. Introductory Raman Spectroscopy. Amsterdam: Elsevier Science, 2012

    Google Scholar 

  40. Casiraghi C, Pisana S, Novoselov K S, et al. Raman fingerprint of charged impurities in graphene. Appl Phys Lett, 2007, 91: 233108

    Google Scholar 

  41. D’Arsié L, Esconjauregui S, Weatherup R S, et al. Stable, efficient P-type doping of graphene by nitric acid. RSC Adv, 2016, 6: 113185–113192

    Google Scholar 

  42. Tien H N, Kocabas C, Hur S H. One-step codoping of reduced graphene oxide using Boric and nitric acid mixture and its use in metalfree electrocatalyst. Mater Lett, 2015, 143: 205–208

    Google Scholar 

  43. Lee H J, Kim E, Park J, et al. Radio-frequency characteristics of graphene monolayer via nitric acid doping. Carbon, 2014, 78: 532–539

    Google Scholar 

  44. Coleman J N. Liquid exfoliation of defect-free graphene. Acc Chem Res, 2013, 46: 14–22

    Google Scholar 

  45. Balakrishnan P. Engineering the membrane electrode assembly of direct methanol fuel cells using novel graphene architecture. Dissertation for Doctoral Degree. Manchester: University of Manchester, 2018

    Google Scholar 

  46. Yang C, Hu M, Wang C, et al. A three-step activation method for proton exchange membrane fuel cells. J Power Sources, 2012, 197: 180–185

    Google Scholar 

  47. Awada H, Castelein G, Brogly M. Quantitative determination of surface energy using atomic force microscopy: The case of hydrophobic/hydrophobic contact and hydrophilic/hydrophilic contact. Surf Interface Anal, 2005, 37: 755–764

    Google Scholar 

  48. Yan X H, Zhao T S, An L, et al. A crack-free and super-hydrophobic cathode micro-porous layer for direct methanol fuel cells. Appl Energy, 2015, 138: 331–336

    Google Scholar 

  49. Bhaskar A, Banerjee R, Kharul U. ZIF-8@PBI-BuI composite membranes: Elegant effects of PBI structural variations on gas permeation performance. J Mater Chem A, 2014, 2: 12962

    Google Scholar 

  50. Bevers D, Rogers R, von Bradke M. Examination of the influence of PTFE coating on the properties of carbon paper in polymer electrolyte fuel cells. J Power Sources, 1996, 63: 193–201

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute for Energy Research, Jiangsu University, Zhenjiang, 212013, China

    Prabhuraj Balakrishnan, Li Guan, HuiYuan Liu, HuaNeng Su & Qian Xu

  2. School of Energy and Power Engineering, Chongqing University, Chongqing, 400030, China

    PuiKi Leung & Akeel Shah

  3. Department of Chemical Process Engineering, University of Surrey, Guildford, GU2 7XH, UK

    Lei Xing

Authors
  1. Prabhuraj Balakrishnan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Li Guan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. HuiYuan Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. PuiKi Leung
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Akeel Shah
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Lei Xing
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. HuaNeng Su
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Qian Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Lei Xing or Qian Xu.

Additional information

This work was supported by China Postdoctoral Science Foundation (Grant No. 2019M661749), Six-Talent-Peaks Project in Jiangsu Province (Grant No. 2016-XNY-015), the High-Tech Key Laboratory of Zhenjiang City (Grant No. SS2018002), and Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Balakrishnan, P., Guan, L., Liu, H. et al. Tunable nitrogen crafted 2D-graphene nano-hybrid from industrial expansive and ecological approach as robust cathode microporous layer to improve performance of a direct methanol fuel cell. Sci. China Technol. Sci. 66, 2669–2680 (2023). https://doi.org/10.1007/s11431-022-2355-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11431-022-2355-9

Keywords

Search

Navigation