Skip to main content
SpringerLink
Log in

Ultra-low loading Pt-sputtered gas diffusion electrodes for oxygen reduction reaction

  • Research Article
  • Published:
Journal of Applied Electrochemistry Aims and scope Submit manuscript

Abstract

Ultra-low Pt-loaded (3–54 µg cm− 2) gas diffusion electrodes were prepared by a direct current unbalanced magnetron sputtering process. Pt films were deposited directly onto the microporous layer of the gas diffusion electrode and tested in a half-cell and proton exchange membrane fuel cell. While the apparent activity towards oxygen reduction reaction under half-cell conditions is dependent on Pt loading, mass activity is Pt loading independent, indicating constant catalyst utilization. Assuming the validity of the porous electrode model, kinetic parameters are extracted from the experimental data. Unlike the results from the half-cell study, the U–I curves of the proton exchange membrane fuel cell at different loadings show a decrease of the catalyst utilization at higher Pt loadings. The Pt structure on the gas diffusion electrode was investigated by electron microscopy, atomic force microscopy and X-ray diffraction.

Graphical Abstract

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Barbir F (2005) PEM fuel cells: theory and practice. Elsevier, Amsterdam

    Google Scholar 

  2. Speder J, Altmann L, Roefzaad M et al (2013) Pt based PEMFC catalysts prepared from colloidal particle suspensions—a toolbox for model studies. Phys Chem Chem Phys 15:3602–3608. https://doi.org/10.1039/c3cp50195g

    Article  CAS  Google Scholar 

  3. Stephens IEL, Rossmeisl J, Chorkendorff I (2016) Toward sustainable fuel cells. Science 354:1378

    Article  CAS  Google Scholar 

  4. Debe MK (2012) Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486:43–51. https://doi.org/10.1038/nature11115

    Article  CAS  Google Scholar 

  5. Li M, Li M, Zhao Z et al (2016) Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction. Science 354:1414. https://doi.org/10.1126/science.aaf9050

    Article  CAS  Google Scholar 

  6. Nesselberger M, Roefzaad M, Fayçal Hamou R et al (2013) The effect of particle proximity on the oxygen reduction rate of size-selected platinum clusters. Nat Mater 12:1–6. https://doi.org/10.1038/nmat3712

    Article  Google Scholar 

  7. Eikerling M, Kornyshev AA, Kucernak AR (2006) Water in polymer electrolyte fuel cells: friend or foe?. Phys Today 59:38–44. https://doi.org/10.1063/1.2387087

    Article  CAS  Google Scholar 

  8. Zhang J (2008) PEM fuel cell electrocatalysts and catalyst layers, fundamentals and applications. Springer, Berlin

    Book  Google Scholar 

  9. Lazar F, Morin a, Pauc N et al (2012) Supported platinum nanotubes array as new fuel cell electrode architecture. Electrochim Acta 78:98–108. https://doi.org/10.1016/j.electacta.2012.05.114

    Article  CAS  Google Scholar 

  10. Debe MK (2013) Tutorial on the fundamental characteristics and practical properties of nanostructured thin film (NSTF) catalysts. J Electrochem Soc 160:F522–F534. https://doi.org/10.1149/2.049306jes

    Article  CAS  Google Scholar 

  11. Gruber D, Ponath N, Müller J, Lindstaedt F (2005) Sputter-deposited ultra-low catalyst loadings for PEM fuel cells. J Power Sources 150:67–72. https://doi.org/10.1016/j.jpowsour.2005.02.076

    Article  CAS  Google Scholar 

  12. Hirano S, Kim J, Srinivasan S (1997) High performance proton exchange membrane fuel cells with sputter-deposited Pt layer electrodes. Electrochim Acta 42:1587–1593

    Article  CAS  Google Scholar 

  13. Schwanitz B, Schulenburg H, Horisberger M et al (2011) Stability of ultra-low Pt anodes for polymer electrolyte fuel cells prepared by magnetron sputtering. Electrocatalysis 2:35

    Article  CAS  Google Scholar 

  14. Schwanitz B (2012) Reduzierung der Platinbeladung und Imaging von Alterungsphaenomenen in der Polymerelektrolyt-Brennstoffzelle

  15. Slavcheva E, Topalov G, Ganske G et al (2010) Influence of sputtering pressure on surface structure and oxygen reduction reaction catalytic activity of thin platinum films. Electrochim Acta 55:8992–8997. https://doi.org/10.1016/j.electacta.2010.08.047

    Article  CAS  Google Scholar 

  16. Yamada K, Miyazaki K, Koji S et al (2008) Catalytic performance of Pt film with dendritic structure for PEFC. J Power Sources 180:181–184. https://doi.org/10.1016/j.jpowsour.2008.02.059

    Article  CAS  Google Scholar 

  17. Dilonardo E, Milella A, Palumbo F et al (2010) One-step plasma deposition of platinum containing nanocomposite coatings. Plasma Process Polym 7:51–58. https://doi.org/10.1002/ppap.200900118

    Article  CAS  Google Scholar 

  18. Huang K, Lai Y, Tsai C (2006) Effects of sputtering parameters on the performance of electrodes fabricated for proton exchange membrane fuel cells. 156:pp 224–231

  19. Sievers G, Quade A, Kruth A, Brueser V (2016) Combined balanced magnetron sputtering and substrate-annealing synthesis for Pt and Pt/C oxygen reduction catalysts. J Electrochem Soc 163:F341–F346. https://doi.org/10.1149/2.0351605jes

    Article  CAS  Google Scholar 

  20. O’Hayre R, Lee S-J, Cha S-W, Prinz F (2002) A sharp peak in the performance of sputtered platinum fuel cells at ultra-low platinum loading. J Power Sources 109:483–493. https://doi.org/10.1016/S0378-7753(02)00238-0

    Article  Google Scholar 

  21. Transactions ECS, Society TE (2017) Oxygen reduction reaction activity of platinum thin films with different densities B. Ergul 80:847–852

    Google Scholar 

  22. Keijser T, Langford J, Mittemeijer E, Vogels A (1982) J Appl Crystallogr 15:308–314

    Article  Google Scholar 

  23. Sievers G, Mueller S, Quade A et al (2014) Mesoporous Pt–Co oxygen reduction reaction (ORR) catalysts for low temperature proton exchange membrane fuel cell synthesized by alternating sputtering. J Power Sources 268:255–260. https://doi.org/10.1016/j.jpowsour.2014.06.013

    Article  CAS  Google Scholar 

  24. Himanen O, Hottinen T, Tuurala S (2007) Operation of a planar free-breathing PEMFC in a dead-end mode. Electrochem commun 9:891–894. https://doi.org/10.1016/j.elecom.2006.12.002

    Article  CAS  Google Scholar 

  25. Zalitis CM, Kramer D, Kucernak AR (2013) Electrocatalytic performance of fuel cell reactions at low catalyst loading and high mass transport. Phys Chem Chem Phys PCCP 15:4329–4340. https://doi.org/10.1039/c3cp44431g

    Article  CAS  Google Scholar 

  26. Shinozaki K, Zack JW, Richards RM et al (2015) Oxygen reduction reaction measurements on platinum electrocatalysts utilizing rotating disk electrode technique: I. Impact of impurities, measurement protocols and applied corrections. J Electrochem Soc 162:F1144–F1158. https://doi.org/10.1149/2.1071509jes

    Article  CAS  Google Scholar 

  27. Zalitis CM, Kramer D, Kucernak AR (2013) Electrocatalytic performance of fuel cell reactions at low catalyst loading and high mass transport. Phys Chem Chem Phys 15:4329–4340. https://doi.org/10.1039/c3cp44431g

    Article  CAS  Google Scholar 

  28. Eikerling M, Ioselevich AS, Kornyshev AA (2004) How good are the electrodes we use in PEFC?. Fuel Cells 4:131–140. https://doi.org/10.1002/fuce.200400029

    Article  CAS  Google Scholar 

  29. Vidakovic-Koch T, Hanke-Rauschenbach R, Gonzalez-Martinez I, Sundmacher K (2016) Catalyst layer modeling. In: Breitkopf S-L (ed) Handbook of electrochemical energy, Springer, Berlin, pp 259–285

    Google Scholar 

  30. Takasu Y, Ohashi N, Zhang XG et al (1996) Size effects of platinum particles on the electroreduction of oxygen. Electrochim Acta 41:2595–2600. https://doi.org/10.1016/0013-4686(96)00081-3

    Article  CAS  Google Scholar 

  31. Topalov A, Katsounaros I, Auinger M et al (2012) Dissolution of platinum: limits for the deployment of electrochemical energy conversion?. Angew Chem 51:12613–12615. https://doi.org/10.1002/anie.201207256

    Article  CAS  Google Scholar 

  32. Antoine O, Bultel Y, Durand R (2001) Oxygen reduction reaction kinetics and mechanism on platinum nanoparticles inside Nafion®. J Electroanal Chem 499:85–94

    Article  CAS  Google Scholar 

  33. Kaskiala T (2002) Determination of oxygen solubility in aqueous sulphuric acid media. Miner Eng 15:853–857. https://doi.org/10.1016/S0892-6875(02)00089-4

    Article  CAS  Google Scholar 

  34. Sethuraman VA, Khan S, Jur JS et al (2009) Measuring oxygen, carbon monoxide and hydrogen sulfide diffusion coefficient and solubility in Nafion membranes. Electrochim Acta 54:6850–6860. https://doi.org/10.1016/j.electacta.2009.06.068

    Article  CAS  Google Scholar 

  35. Sambandam S, Parrondo J, Ramani V (2013) Estimation of electrode ionomer oxygen permeability and ionomer-phase oxygen transport resistance in polymer electrolyte fuel cells. Phys Chem Chem Phys 15:14994–15002. https://doi.org/10.1039/c3cp51450a

    Article  CAS  Google Scholar 

  36. Markovic NM, Schmidt TJ, Stamenkovic V, Ross PN (2001) Oxygen reduction reaction on Pt and Pt bimetallic surfaces: a selective review. Fuel Cells 1:105–116

    Article  CAS  Google Scholar 

  37. Gasda MD, Teki R, Lu T-M et al (2009) Sputter-deposited Pt PEM fuel cell electrodes: particles vs layers. J Electrochem Soc 156:B614–B619

    Article  CAS  Google Scholar 

  38. Brouzgou A, Song SQ, Tsiakaras P (2012) Low and non-platinum electrocatalysts for PEMFCs: current status, challenges and prospects. Appl Catal B 127:371–388. https://doi.org/10.1016/j.apcatb.2012.08.031

    Article  CAS  Google Scholar 

Download references

Acknowledgements

TVK gratefully acknowledges the financial support by German Research Foundation (Deutsche Forschungsgemeinschaft, DFG) within the framework of the project Grant VI 845/1-1. The authors would like to thank S. Wandenälis for proof-reading of the manuscript.

Author information

Authors and Affiliations

  1. Leibniz Institute for Plasma Technology and Science, Felix-Hausdorff-Str. 2, 17489, Greifswald, Germany

    Gustav Sievers, Christian Walter, Angela Kruth & Volker Brüser

  2. Max Planck Institute for Dynamics of Complex Technical Systems, Sandtorstr. 1, 39106, Magdeburg, Germany

    Tanja Vidakovic-Koch, Dana Hermsdorf & Kai Sundmacher

  3. EKPRO GmbH, Gardeschützenweg 7, 12203, Berlin, Germany

    Florian Steffen & Sven Jakubith

Authors
  1. Gustav Sievers
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Tanja Vidakovic-Koch
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Christian Walter
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Florian Steffen
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Sven Jakubith
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Angela Kruth
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Dana Hermsdorf
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Kai Sundmacher
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Volker Brüser
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Gustav Sievers or Tanja Vidakovic-Koch.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 3079 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sievers, G., Vidakovic-Koch, T., Walter, C. et al. Ultra-low loading Pt-sputtered gas diffusion electrodes for oxygen reduction reaction. J Appl Electrochem 48, 221–232 (2018). https://doi.org/10.1007/s10800-018-1149-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10800-018-1149-7

Keywords

Search

Navigation