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Poly(aryl piperidinium) membranes and ionomers for hydroxide exchange membrane fuel cells

Nature Energy volume 4, pages 392–398 (2019)Cite this article

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Abstract

One promising approach to reduce the cost of fuel cell systems is to develop hydroxide exchange membrane fuel cells (HEMFCs), which open up the possibility of platinum-group-metal-free catalysts and low-cost bipolar plates. However, scalable alkaline polyelectrolytes (hydroxide exchange membranes and hydroxide exchange ionomers), a key component of HEMFCs, with desired properties are currently unavailable, which presents a major barrier to the development of HEMFCs. Here we show hydroxide exchange membranes and hydroxide exchange ionomers based on poly(aryl piperidinium) (PAP) that simultaneously possess adequate ionic conductivity, chemical stability, mechanical robustness, gas separation and selective solubility. These properties originate from the combination of the piperidinium cation and the rigid ether-bond-free aryl backbone. A low-Pt membrane electrode assembly with a Ag-based cathode using PAP materials showed an excellent peak power density of 920 mW cm−2 and operated stably at a constant current density of 500 mA cm−2 for 300 h with H2/CO2-free air at 95 °C.

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Fig. 1: Chemical structure of the PAP HEM family.
Fig. 2: Alkaline stability of PAP HEMs in 1 M KOH at 100 °C.
Fig. 3: Mechanical properties and durability of PAP-TP-85.
Fig. 4: Properties of PAP HEMs at different temperatures.
Fig. 5: The typical examples of membrane, ionomer, MEA and fuel cell performance based on PAP materials.

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Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

References

  1. Yoshida, T. & Kojima, K. Toyota MIRAI fuel cell vehicle and progress toward a future hydrogen society. Interface Magazine 24, 45–49 (2015).

    Article  Google Scholar 

  2. Setzler, B. P., Zhuang, Z. B., Wittkopf, J. A. & Yan, Y. S. Activity targets for nanostructured platinum group-metal-free catalysts in hydroxide exchange membrane fuel cells. Nat. Nanotechnol. 11, 1020–1025 (2016).

    Article  Google Scholar 

  3. Bashyam, R. & Zelenay, P. A class of non-precious metal composite catalysts for fuel cells. Nature 443, 63–66 (2006).

    Article  Google Scholar 

  4. Lefevre, M., Proietti, E., Jaouen, F. & Dodelet, J. P. Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science 324, 71–74 (2009).

    Article  Google Scholar 

  5. Wu, G., More, K. L., Johnston, C. M. & Zelenay, P. High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science 332, 443–447 (2011).

    Article  Google Scholar 

  6. Gasteiger, H. A. & Markovic, N. M. Just a dream-or future reality? Science 324, 48–49 (2009).

    Article  Google Scholar 

  7. Liang, Y. Y. et al. Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nat. Mater. 10, 780–786 (2011).

    Article  Google Scholar 

  8. Varcoe, J. R. & Slade, R. C. T. Prospects for alkaline anion-exchange membranes in low temperature fuel cells. Fuel Cells 5, 187–200 (2005).

    Article  Google Scholar 

  9. Wang, Y. J., Qiao, J. L., Baker, R. & Zhang, J. J. Alkaline polymer electrolyte membranes for fuel cell applications. Chem. Soc. Rev. 42, 5768–5787 (2013).

    Article  Google Scholar 

  10. Varcoe, J. R. et al. Anion-exchange membranes in electrochemical energy systems. Energ. Environ. Sci. 7, 3135–3191 (2014).

    Article  Google Scholar 

  11. Wang, J. H., Gu, S., Kaspar, R. B., Zhang, B. Z. & Yan, Y. S. Stabilizing the imidazolium cation in hydroxide-exchange membranes for fuel cells. ChemSusChem 6, 2079–2082 (2013).

    Article  Google Scholar 

  12. Pan, J. et al. High-performance alkaline polymer electrolyte for fuel cell applications. Adv. Funct. Mater. 20, 312–319 (2010).

    Article  Google Scholar 

  13. Gu, S. et al. A soluble and highly conductive ionomer for high-performance hydroxide exchange membrane fuel cells. Angew. Chem. Int. Ed. 48, 6499–6502 (2009).

    Article  Google Scholar 

  14. Wang, J. H., Li, S. H. & Zhang, S. B. Novel hydroxide-conducting polyelectrolyte composed of an poly(arylene ether sulfone) containing pendant quaternary guanidinium groups for alkaline fuel cell applications. Macromolecules 43, 3890–3896 (2010).

    Article  Google Scholar 

  15. Noonan, K. J. T. et al. Phosphonium-functionalized polyethylene: A new class of base-stable alkaline anion exchange membranes. J. Am. Chem. Soc. 134, 18161–18164 (2012).

    Article  Google Scholar 

  16. Zha, Y. P., Disabb-Miller, M. L., Johnson, Z. D., Hickner, M. A. & Tew, G. N. Metal-cation-based anion exchange membranes. J. Am. Chem. Soc. 134, 4493–4496 (2012).

    Article  Google Scholar 

  17. Gu, S. et al. Permethyl cobaltocenium (Cp*2Co+) as an ultra-stable cation for polymer hydroxide-exchange membranes. Sci. Rep. 5, 11668 (2015).

  18. Hugar, K. M., Kostalik, H. A. & Coates, G. W. Imidazolium cations with exceptional alkaline stability: A systematic study of structure–stability relationships. J. Am. Chem. Soc. 137, 8730–8737 (2015).

    Article  Google Scholar 

  19. Marino, M. G. & Kreuer, K. D. Alkaline stability of quaternary ammonium cations for alkaline fuel cell membranes and ionic liquids. ChemSusChem 8, 513–523 (2015).

    Article  Google Scholar 

  20. Olsson, J. S., Pham, T. H. & Jannasch, P. Poly(arylene piperidinium) hydroxide ion exchange membranes: Synthesis, alkaline stability, and conductivity. Adv. Funct. Mater. 28, 1702758 (2017).

  21. Peng, H. G. et al. Alkaline polymer electrolyte fuel cells stably working at 80 °C. J. Power Sources 390, 165–167 (2018).

    Article  Google Scholar 

  22. Dang, H. S. & Jannasch, P. Alkali-stable and highly anion conducting poly(phenylene oxide)s carrying quaternary piperidinium cations. J. Mater. Chem. A 4, 11924–11938 (2016).

    Article  Google Scholar 

  23. Pham, T. H. & Jannasch, P. Aromatic polymers incorporating bis-N-spirocyclic quaternary ammonium moieties for anion-exchange membranes. ACS Macro Lett. 4, 1370–1375 (2015).

    Article  Google Scholar 

  24. Pham, T. H., Olsson, J. S. & Jannasch, P. N-spirocyclic quaternary ammonium ionenes for anion-exchange membranes. J. Am. Chem. Soc. 139, 2888–2891 (2017).

    Article  Google Scholar 

  25. Strasser, D. J., Graziano, B. J. & Knauss, D. M. Base stable poly(diallylpiperidinium hydroxide) multiblock copolymers for anion exchange membranes. J. Mater. Chem. A 5, 9627–9640 (2017).

    Article  Google Scholar 

  26. Olsson, J. S., Pham, T. H. & Jannasch, P. Poly(N,N-diallylazacycloalkane)s for anion-exchange membranes functionalized with N-spirocyclic quaternary ammonium cations. Macromolecules 50, 2784–2793 (2017).

    Article  Google Scholar 

  27. Ponce-Gonzalez, J. et al. High performance aliphatic-heterocyclic benzyl-quaternary ammonium radiation-grafted anion-exchange membranes. Energy Environ. Sci. 9, 3724–3735 (2016).

    Article  Google Scholar 

  28. Arges, C. G. & Ramani, V. Two-dimensional NMR spectroscopy reveals cation-triggered backbone degradation in polysulfone-based anion exchange membranes. Proc. Natl Acad. Sci. USA 110, 2490–2495 (2013).

    Article  Google Scholar 

  29. Mohanty, A. D., Tignor, S. E., Krause, J. A., Choe, Y. K. & Bae, C. Systematic alkaline stability study of polymer backbones for anion exchange membrane applications. Macromolecules 49, 3361–3372 (2016).

    Article  Google Scholar 

  30. Hibbs, M. R., Fujimoto, C. H. & Cornelius, C. J. Synthesis and characterization of poly(phenylene)-based anion exchange membranes for alkaline fuel cells. Macromolecules 42, 8316–8321 (2009).

    Article  Google Scholar 

  31. Fujimoto, C., Kim, D. S., Hibbs, M., Wrobleski, D. & Kim, Y. S. Backbone stability of quaternized polyaromatics for alkaline membrane fuel cells. J. Membr. Sci. 423, 438–449 (2012).

    Article  Google Scholar 

  32. Fujimoto, C. H., Hickner, M. A., Cornelius, C. J. & Loy, D. A. Ionomeric poly(phenylene) prepared by Diels–Alder polymerization: Synthesis and physical properties of a novel polyelectrolyte. Macromolecules 38, 5010–5016 (2005).

    Article  Google Scholar 

  33. Lee, W. H., Mohanty, A. D. & Bae, C. Fluorene-based hydroxide ion conducting polymers for chemically stable anion exchange membrane fuel cells. ACS Macro Lett. 4, 453–457 (2015).

    Article  Google Scholar 

  34. Lee, W. H., Kim, Y. S. & Bae, C. Robust hydroxide ion conducting poly(biphenyl alkylene)s for alkaline fuel cell membranes. ACS Macro Lett. 4, 814–818 (2015).

    Article  Google Scholar 

  35. Pan, J. et al. Constructing ionic highway in alkaline polymer electrolytes. Energy Environ. Sci. 7, 354–360 (2014).

    Article  Google Scholar 

  36. Tanaka, M. et al. Anion conductive block poly(arylene ether)s: Synthesis, properties, and application in alkaline fuel cells. J. Am. Chem. Soc. 133, 10646–10654 (2011).

    Article  Google Scholar 

  37. Li, N. W., Yan, T. Z., Li, Z., Thurn-Albrecht, T. & Binder, W. H. Comb-shaped polymers to enhance hydroxide transport in anion exchange membranes. Energy Environ. Sci. 5, 7888–7892 (2012).

    Article  Google Scholar 

  38. Li, N. W., Leng, Y. J., Hickner, M. A. & Wang, C. Y. Highly stable, anion conductive, comb-shaped copolymers for alkaline fuel cells. J. Am. Chem. Soc. 135, 10124–10133 (2013).

    Article  Google Scholar 

  39. Wang, J. H. et al. Structure–property relationships in hydroxide-exchange membranes with cation strings and high ion-exchange capacity. ChemSusChem 8, 4229–4234 (2015).

    Article  Google Scholar 

  40. Li, Y. F. et al. Polyethylene-based block copolymers for anion exchange membranes. Macromolecules 48, 6523–6533 (2015).

    Article  Google Scholar 

  41. Cruz, A. R. et al. Precision synthesis of narrow polydispersity, ultrahigh molecular weight linear aromatic polymers by A2 + B2 nonstoichiometric step-selective polymerization. Macromolecules 45, 6774–6780 (2012).

    Article  Google Scholar 

  42. Diaz, A. M. et al. A novel, one-pot synthesis of novel 3F, 5F, and 8F aromatic polymers. Macromol. Rapid Comm. 28, 183–187 (2007).

    Article  Google Scholar 

  43. Pena, E. R., Zolotukhin, M. & Fomine, S. Factors enhancing the reactivity of carbonyl compounds for polycondensations with aromatic hydrocarbons. A computational study. Macromolecules 37, 6227–6235 (2004).

    Article  Google Scholar 

  44. Cruz, A. R. et al. Use of 4-piperidones in one-pot syntheses of novel, high-molecular-weight linear and virtually 100%-hyperbranched polymers. Chem. Commun. 0, 4408–4410 (2009).

  45. Wang, J. H., Zhao, Z., Gong, F. X., Li, S. H. & Zhang, S. B. Synthesis of soluble poly(arylene ether sulfone) ionomers with pendant quaternary ammonium groups for anion exchange membranes. Macromolecules 42, 8711–8717 (2009).

    Article  Google Scholar 

  46. Kaspar, R. B. et al. Manipulating water in high-performance hydroxide exchange membrane fuel cells through asymmetric humidification and wetproofing. J. Electrochem. Soc. 162, F483–F488 (2015).

    Article  Google Scholar 

  47. Dekel, D. R. Review of cell performance in anion exchange membrane fuel cells. J. Power Sources 375, 158–169 (2018).

    Article  Google Scholar 

  48. Wang, L. Q., Bellini, M., Miller, H. A. & Varcoe, J. R. A high conductivity ultrathin anion-exchange membrane with 500+ h alkali stability for use in alkaline membrane fuel cells that can achieve 2 W cm−2 at 80 °C. J. Mater. Chem. A 6, 15404–15412 (2018).

    Article  Google Scholar 

  49. Peng, X. et al. Nitrogen-doped carbon–CoOx nanohybrids: A precious metal free cathode that exceeds 1.0 W cm−2 peak power and 100 h life in anion-exchange membrane fuel cells. Angew. Chem. Int. Ed. 2019, 1046 (2018).

  50. Dekel, D. R. et al. Effect of water on the stability of quaternary ammonium groups for anion exchange membrane fuel cell applications. Chem. Mater. 29, 4425–4431 (2017).

    Article  Google Scholar 

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Acknowledgements

This material is based upon work supported by the by the US Department of Energy, Advanced Research Projects Agency-Energy under Award No. DE-AR0000771. We thank Z. Green and H. Xu at Giner for performing the gas crossover measurement. We also thank R. Ma, J. Nash, J. A. Wittkopf and M. D. Woodroof for their assistance in the durability test of H2/O2 HEMFCs.

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  1. These authors contributed equally: Junhua Wang and Yun Zhao.

Authors and Affiliations

  1. Centre for Catalytic Science and Technology, Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, USA

    Junhua Wang, Yun Zhao, Brian P. Setzler, Santiago Rojas-Carbonell, Lan Wang, Keda Hu, Lin Shi, Shimshon Gottesfeld, Bingjun Xu & Yushan Yan

  2. Elbit Systems Ltd, Caesarea Business and Industrial Park, Caesarea, Israel

    Chaya Ben Yehuda, Alina Amel & Miles Page

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Contributions

J.W. synthesized the polymers, fabricated the membranes, and performed the characterizations of polymers and membranes. Y.Z. prepared MEAs with Pt electrodes and tested their H2/O2 performance and durability. B.P.S. measured the electronic area specific resistance and stability of the membrane under RH cycling and pressure differential. S.R.-C. and L.S. developed the casting process for fabricating the large membranes. C.B.Y., A.A. and M.P. prepared MEAs with Ag cathodes and low-Pt anodes and tested their H2/CO2-free air performance and durability. L.W. performed the thermal analysis for the membranes. K.H. measured the polymer molecular weight. S.G. provided guidance in the development and testing of H2/CO2-free air MEAs. J.W., Y.Z., B.X. and Y.Y. conceived the ideas and wrote the manuscript with support from other coauthors.

Corresponding authors

Correspondence to Bingjun Xu or Yushan Yan.

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C.B.Y, A.A. and M.P. are employed by Elbit Systems Ltd, which is a company specializing in fuel cells.

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Wang, J., Zhao, Y., Setzler, B.P. et al. Poly(aryl piperidinium) membranes and ionomers for hydroxide exchange membrane fuel cells. Nat Energy 4, 392–398 (2019). https://doi.org/10.1038/s41560-019-0372-8

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