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Cited by 291Fuel Cells and Related MaterialsElectrocatalysts for Energy ConversionAdvancements in Solid Oxide Fuel Cells

The role of oxygen-permeable ionomer for polymer electrolyte fuel cells

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Jinnouchi, Ryosuke, Kudo, Kenji, Kodama, Kensaku, Kitano, Naoki, Suzuki, Takahisa, Minami, Saori, Shinozaki, Kazuma, Hasegawa, Naoki +1 more·2021·Nature Communications
DOI 10.1038/s41467-021-25301-3PMC PMC8368003
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Abstract

In recent years, considerable research and development efforts are devoted to improving the performance of polymer electrolyte fuel cells. However, the power density and catalytic activities of these energy conversion devices are still far from being satisfactory for large-scale operation. Here we report performance enhancement via incorporation, in the cathode catalyst layers, of a ring-structured backbone matrix into ionomers. Electrochemical characterizations of single cells and microelectrodes reveal that high power density is obtained using an ionomer with high oxygen solubility. The high solubility allows oxygen to permeate the ionomer/catalyst interface and react with protons and electrons on the catalyst surfaces. Furthermore, characterizations of single cells and single-crystal surfaces reveal that the oxygen reduction reaction activity is enhanced owing to the mitigation of catalyst poisoning by sulfonate anion groups. Molecular dynamics simulations indicate that both the high permeation and poisoning mitigation are due to the suppression of densely layered folding of polymer backbones near the catalyst surfaces by the incorporated ring-structured matrix. These experimental and theoretical observations demonstrate that ionomer’s tailored molecular design promotes local oxygen transport and catalytic reactions.

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  • The high oxygen solubility of HOPI allows high permeation and mitigates catalyst poisoning by one or two oxygen atom(s) of the terminal sulfonate group.

    “This occurs because the high oxygen solubility allows high permeation and mitigates catalyst poisoning by one or two oxygen atom(s) of the terminal sulfonate group [100,101].”

    From Recent Advances on PEM Fuel Cells: From Key Materials to Membrane Electrode Assembly (2023) · cites this paper as [100]

    The Introduction and Results and discussion state that HOPI’s high oxygen solubility increases permeation and that reduced sulfonate-anion adsorption mitigates catalyst poisoning. The paper does not specify poisoning by one or two oxygen atoms of the terminal sulfonate group; its discussion describes sulfonate-anion adsorption on Pt instead. No page numbers are available in our copy. (LLM, conf=0.87)

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  • Several research groups have reported significant improvements in fuel cell performance without any remarkable adverse effects by using highly oxygen-permeable ionomers (HOPIs) in the catalyst layer.

    “Several research groups have reported significant improvements in fuel cell performance without any remarkable adverse effects by using highly oxygen-permeable ionomers (HOPIs) in the catalyst layer (Fig. 8b).”

    From Recent Advances on PEM Fuel Cells: From Key Materials to Membrane Electrode Assembly (2023) · cites this paper as [100]

  • Jinnouchi et al. reported that a HOPI incorporating a ring-structured monomer significantly enhances both the interfacial oxygen permeation and ORR activity.

    “Jinnouchi et al. reported that a HOPI incorporating a ring-structured monomer significantly enhances both the interfacial oxygen permeation and ORR activity.”

    From Recent Advances on PEM Fuel Cells: From Key Materials to Membrane Electrode Assembly (2023) · cites this paper as [100]

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  1. [1]Borup R Scientific aspects of polymer electrolyte fuel cell durability and degradation Chem. Rev. 2007 107 3904 3951 10.1021/cr050182l 17850115 · DOI
  2. [2]Gasteiger HA Marković NM Just a dream—or future reality? Science 2009 324 48 10.1126/science.1172083 19342578 · DOI
  3. [4]Kongkanand A Mathias MF The priority and challenge of high-power performance of low-platinum proton-exchange membrane fuel cells J. Phys. Chem. Lett. 2016 7 1127 1137 10.1021/acs.jpclett.6b00216 26961326 · DOI · Paper page
  4. [6]Kulkarni A Siahrostami S Patel A Nørskov JK Understanding catalytic activity trends in the oxygen reduction reaction Chem. Rev. 2018 118 2302 2312 10.1021/acs.chemrev.7b00488 29405702 · DOI
  5. [7]Yoshida T Kojima K Toyota MIRAI fuel cell vehicle and progress toward a future hydrogen society Interface Mag. 2015 24 45 49 10.1149/2.F03152if · DOI
  6. [8]Pollet BG Kocha SS Staffell I Current status of automotive fuel cells for sustainable transport Curr. Opin. Electrochem 2019 16 90 95 10.1016/j.coelec.2019.04.021 · DOI
  7. [9]Gittleman CS Kongkanand A Masten D Gu W Materials research and development focus areas for low cost automotive proton-exchange membrane fuel cells Curr. Opin. Electrochem 2019 18 81 89 10.1016/j.coelec.2019.10.009 · DOI
  8. [11]Suzuki T Toward the future fuel cell -challenge for 2040 ECS Trans. 2019 92 3 7 10.1149/09208.0003ecst · DOI
  9. [14]Kodama K Nagai T Kuwaki A Jinnouchi R Morimoto Y Challenges in applying highly active Pt-based nanostructured catalysts for oxygen reduction reactions to fuel cell vehicles Nat. Nanotechnol. 2021 16 140 147 10.1038/s41565-020-00824-w 33479539 · DOI
  10. [15]Sepa DB Vojnovic MV Damjanovic A Reaction intermediates as a controlling factor in the kinetics and mechanism of oxygen reduction at platinum electrodes Electrochim. Acta 1981 26 781 793 10.1016/0013-4686(81)90037-2 · DOI
  11. [16]Gasteiger HA Kocha SS Sompalli B Wagner FT Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs Appl. Catal. B: Environ. 2005 56 9 35 10.1016/j.apcatb.2004.06.021 · DOI · Paper page
  12. [17]Kudo K Suzuki T Morimoto Y Analysis of oxygen dissolution rate from gas phase into Nafion surface and development of an agglomerate model ECS Trans. 2010 33 1495 1502 10.1149/1.3484642 · DOI
  13. [18]Ono Y The analysis of performance loss with low platinum loaded cathode catalyst layers ECS Trans. 2010 28 69 78 10.1149/1.3496614 · DOI
  14. [19]Greszler TA Caulk D Sinha P The impact of platinum loading on oxygen transport resistance J. Electrochem. Soc. 2012 159 F831 F840 10.1149/2.061212jes · DOI
  15. [20]Suzuki T Kudo K Morimoto Y Model for investigation of oxygen transport limitation in a polymer electrolyte fuel cell J. Power Sources 2013 222 379 389 10.1016/j.jpowsour.2012.08.068 · DOI
  16. [21]Kudo K Jinnouchi R Morimoto Y Humidity and temperature dependences of oxygen transport resistance of Nafion thin film on platinum electrode Electrochim. Acta 2016 209 682 690 10.1016/j.electacta.2016.04.023 · DOI
  17. [22]Kudo K Morimoto Y Analysis of oxygen transport resistance of Nafion thin film on Pt electrode ECS Trans. 2013 50 1487 1494 10.1149/05002.1487ecst · DOI
  18. [23]Liu H Epting WK Litster S Gas transport resistance in polymer electrolyte thin films on oxygen reduction reaction catalysts Langmuir 2015 31 9853 9858 10.1021/acs.langmuir.5b02487 26299282 · DOI
  19. [24]Jinnouchi R Kudo K Kitano N Morimoto Y Molecular dynamics simulations on O2 permeation through Nafion ionomer on platinum surface Electrochim. Acta 2016 188 767 776 10.1016/j.electacta.2015.12.031 · DOI
  20. [25]Kurihara Y Mabuchi T Tokumasu T Molecular dynamics study of oxygen transport resistance through ionomer thin film on Pt surface J. Power Sources 2019 414 263 271 10.1016/j.jpowsour.2019.01.011 · DOI
  21. [26]Schuler T Fuel-cell catalyst-layer resistance via hydrogen limiting-current measurements J. Electrochem. Soc. 2019 166 F3020 F3031 10.1149/2.0031907jes · DOI
  22. [27]Mu Y-T Weber AZ Gu Z-L Tao W-Q Mesoscopic modeling of transport resistances in a polymer-electrolyte fuel-cell catalyst layer: analysis of hydrogen limiting currents Appl. Energy 2019 255 113895 10.1016/j.apenergy.2019.113895 · DOI
  23. [28]Vanya P Sharman J Elliott JA Mesoscale simulations of confined Nafion thin films J. Chem. Phys. 2017 147 214904 10.1063/1.4996695 29221394 · DOI
  24. [29]Modestino MA Self-assembly and transport limitations in confined Nafion films Macromolecules 2013 46 867 873 10.1021/ma301999a · DOI
  25. [30]Ferreira PJ Instability of Pt∕C electrocatalysts in proton exchange membrane fuel cells J. Electrochem. Soc. 2005 152 A2256 A2271 10.1149/1.2050347 · DOI
  26. [31]Tang L Electrochemical stability of nanometer-scale Pt particles in acidic environments J. Am. Chem. Soc. 2010 132 596 600 10.1021/ja9071496 20017546 · DOI
  27. [32]Jinnouchi R Toyoda E Hatanaka T Morimoto Y First principles calculations on site-dependent dissolution potentials of supported and unsupported Pt particles J. Phys. Chem. C. 2010 114 17557 17568 10.1021/jp106593d · DOI
  28. [33]Shinozaki K Morimoto Y Pivovar BS Kocha SS Suppression of oxygen reduction reaction activity on Pt-based electrocatalysts from ionomer incorporation J. Power Sources 2016 325 745 751 10.1016/j.jpowsour.2016.06.062 · DOI
  29. [34]Iden H Ohma A An in situ technique for analyzing ionomer coverage in catalyst layers J. Electroanal. Chem. 2013 693 34 41 10.1016/j.jelechem.2013.01.026 · DOI
  30. [35]Kamitaka Y Takeshita T Morimoto Y MgO-templated mesoporous carbon as a catalyst support for polymer electrolyte fuel cells Catalysts 2018 8 230 10.3390/catal8060230 · DOI
  31. [36]Yarlagadda V Boosting fuel cell performance with accessible carbon mesopores ACS Energy Lett. 2018 3 618 621 10.1021/acsenergylett.8b00186 · DOI · Paper page
  32. [37]Takeshita T Kamitaka Y Shinozaki K Kodama K Morimoto Y Evaluation of ionomer coverage on Pt catalysts in polymer electrolyte membrane fuel cells by CO stripping voltammetry and its effect on oxygen reduction reaction activity J. Electroanal. Chem. 2020 871 114250 10.1016/j.jelechem.2020.114250 · DOI
  33. [38]Yamada K Hommura S Shimohira T Effect of high oxygen permeable ionomers on MEA performance for PEFC ECS Trans. 2013 50 1495 1501 10.1149/05002.1495ecst · DOI
  34. [39]Shimizu R Park Y-C Kakinuma K Iiyama A Uchida M Effects of both oxygen permeability and ion exchange capacity for cathode ionomers on the performance and durability of polymer electrolyte fuel cells J. Electrochem. Soc. 2018 165 F3063 F3071 10.1149/2.0071806jes · DOI
  35. [40]Rolfi A Oldani C Merlo L Facchi D Ruffo R New perfluorinated ionomer with improved oxygen permeability for application in cathode polymeric electrolyte membrane fuel cell J. Power Sources 2018 396 95 101 10.1016/j.jpowsour.2018.05.093 · DOI
  36. [41]Katzenberg A Highly permeable perfluorinated sulfonic acid ionomers for improved electrochemical devices: insights into structure–property relationships J. Am. Chem. Soc. 2020 142 3742 3752 10.1021/jacs.9b09170 31955580 · DOI
  37. [42]Ott S Ionomer distribution control in porous carbon-supported catalyst layers for high-power and low Pt-loaded proton exchange membrane fuel cells Nat. Mater. 2020 19 77 85 10.1038/s41563-019-0487-0 31570820 · DOI · Paper page
  38. [43]Kodama K Catalyst poisoning property of sulfonimide acid ionomer on Pt (111) surface J. Electrochem. Soc. 2014 161 F649 F652 10.1149/2.051405jes · DOI · Paper page
  39. [44]Kodama K Increase in adsorptivity of sulfonate anions on Pt (111) surface with drying of ionomer Electrochem. Commun. 2013 36 26 28 10.1016/j.elecom.2013.09.005 · DOI
  40. [45]Subbaraman R Strmcnik D Stamenkovic V Markovic NM Three phase interfaces at electrified metal−solid electrolyte systems 1. Study of the Pt(hkl)−Nafion interface J. Phys. Chem. C. 2010 114 8414 8422 10.1021/jp100814x · DOI
  41. [46]Kodama K Effect of the side-chain structure of perfluoro-sulfonic acid ionomers on the oxygen reduction reaction on the surface of Pt ACS Catal. 2018 8 694 700 10.1021/acscatal.7b03571 · DOI · Paper page
  42. [48]Chen Q Schmidt-Rohr K 19F and 13C NMR signal assignment and analysis in a perfluorinated ionomer (Nafion) by two-dimensional solid-state NMR Macromolecules 2004 37 5995 6003 10.1021/ma049759b · DOI
  43. [49]Robert, C. et al. Amorphous fluoropolymer: next generation optical coating candidate. in Proc. SPIE (1994).
  44. [50]Hung MH The chemistry of fluorinated dioxoles and dioxolanes. 5. Structure-property relationship of fluorinated dioxole polymers Macromolecules 1993 26 5829 5834 10.1021/ma00074a001 · DOI
  45. [51]Mauritz KA Moore RB State of understanding of nafion Chem. Rev. 2004 104 4535 4586 10.1021/cr0207123 15669162 · DOI · Paper page
  46. [52]Scheirs, J. Modern Fluoropolymers: High Performance Polymers for Diverse Applications (Wiley, 1997).
  47. [53]Mitsushima S Araki N Kamiya N Ota K-I Analysis of oxygen reduction on Pt microelectrode with polymer electrolytes of various exchange capacities J. Electrochem. Soc. 2002 149 A1370 A1375 10.1149/1.1506164 · DOI
  48. [54]Fuel Cell Commercialization Conference of Japan (FCCJ). http://fccj.jp/pdf/23_01_kt.pdf (2007).
  49. [56]Baker DR Caulk DA Neyerlin KC Murphy MW Measurement of oxygen transport resistance in PEM fuel cells by limiting current methods J. Electrochem. Soc. 2009 156 B991 B1003 10.1149/1.3152226 · DOI
  50. [57]Lefebvre MC Characterization of ionic conductivity profiles within proton exchange membrane fuel cell gas diffusion electrodes by impedance spectroscopy Electrochem. Solid-State Lett. 1999 2 259 261 10.1149/1.1390804 · DOI
  51. [58]Büchi FN Wakizoe M Srinivasan S Microelectrode investigation of oxygen permeation in perfluorinated proton exchange membranes with different equivalent weights J. Electrochem. Soc. 1996 143 927 932 10.1149/1.1836560 · DOI
  52. [59]Berendsen HJC Postma JPM van Gunsteren WF DiNola A Haak JR Molecular dynamics with coupling to an external bath J. Chem. Phys. 1984 81 3684 3690 10.1063/1.448118 · DOI
  53. [60]Momma K Izumi F VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data J. Appl. Crystallogr. 2011 44 1272 1276 10.1107/S0021889811038970 · DOI

Cited by

Sorted by citations

Authors
Jinnouchi, R., Kudo, K., Kodama, K., Kitano, N., Suzuki, T., Minami, S., Shinozaki, K., Hasegawa, N., & Shinohara, A.
Affiliations
Toyota Central Research and Development Laboratories (Japan) (JP)
Corresponding author
Jinnouchi, Ryosuke
ORCID
Venue
Nature Communications
Publisher
Springer Science and Business Media LLC
Published
2021-08-16
Volume
12
Issue
1
Pages
4956-4956
ISSN
2041-1723 (ISSN-L)
DOI
10.1038/s41467-021-25301-3
PMC
PMC8368003
OpenAlex
W3195792810
Cited by
291
References
3
Citations by year
2026: 53 · 2025: 91 · 2024: 68 · 2023: 51 · 2022: 27 · 2021: 1
FWCI
10.81
Type
journal article
Language
en
Update notices
correction (2023-09-01)
Open access
Licence
Locations
  • Nature Communications (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • RePEc: Research Papers in Economics (submittedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
Topics
  • Physical Sciences › Engineering › Electrical and Electronic Engineering › Fuel Cells and Related Materials
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
  • Physical Sciences › Materials Science › Materials Chemistry › Advancements in Solid Oxide Fuel Cells
Keywords
proton exchange membrane fuel cells, cathode catalyst layer, oxygen solubility, oxygen reduction reaction, catalyst poisoning, oxygen transport, molecular dynamics simulation, power density

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