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An inorganic–organic proton exchange membrane for fuel cells with a controlled nanoscale pore structure

Abstract

Proton exchange membrane fuel cells have the potential for applications in energy conversion and energy storage, but their development has been impeded by problems with the membrane electrode assembly. Here, we demonstrate that a silicon-based inorganic–organic membrane offers a number of advantages over Nafion—the membrane widely used as a proton exchange membrane in hydrogen fuel cells—including higher proton conductivity, a lack of volumetric size change, and membrane electrode assembly construction capabilities. Key to achieving these advantages is fabricating a silicon membrane with pores with diameters of 5–7 nm, adding a self-assembled molecular monolayer on the pore surface, and then capping the pores with a layer of porous silica. The silica layer reduces the diameter of the pores and ensures their hydration, resulting in a proton conductivity that is two to three orders of magnitude higher than that of Nafion at low humidity. A membrane electrode assembly constructed with this proton exchange membrane delivered an order of magnitude higher power density than that achieved previously with a dry hydrogen feed and an air-breathing cathode.

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Figure 1: Schematic of the membrane with functionalized pore wall and thin layers of porous silica on both sides of the membrane.
Figure 2: Fabrication process for the porous silicon membrane.
Figure 3: FTIR spectra of the membrane at different stages of pore surface modification.
Figure 4: Self-assembly of functional groups on the membrane wall of the pores.
Figure 5: Membrane pore size characterization and details of the MEA and its test package.
Figure 6: Performance of the PS–PEM membrane and MEA using a dry hydrogen feed and an air-breathing cathode.

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References

  1. Gold, S., Chu, K.-L., Lu, C., Shannon, M. A. & Masel, R. I. Acid loaded porous silicon as a proton exchange membrane for micro-fuel cells. J. Power Sources 135, 198–203 (2004).

    Article  CAS  Google Scholar 

  2. Pichonat, T. & Gauthier-Manuel, B. Realization of porous silicon based miniature fuel cells. J. Power Sources 154, 198–201 (2006).

    Article  CAS  Google Scholar 

  3. Devanathan, R. Recent developments in proton exchange membranes for fuel cells. Energy Environ. Sci. 1, 101–119 (2008).

    Article  CAS  Google Scholar 

  4. Athens, G. L., Ein-Eli, Y. & Chmelka, B. F. Acid-functionalized mesostructured aluminosilica for hydrophilic proton conduction membranes. Adv. Mater. 19, 2580–2587 (2007).

    Article  CAS  Google Scholar 

  5. Lehmann, V. Electrochemistry of Silicon: Instrumentation, Science, Materials and Applications (Wiley-VCH, 2002).

    Book  Google Scholar 

  6. Föll, H., Carstensen, J. & Frey, S. Porous and nanoporous semiconductors and emerging applications. J. Nanomater. 2006, 1–10 (2006).

    Article  Google Scholar 

  7. Glass, J. A., Wovchko, E. A. & Yates, J. T. Reaction of atomic hydrogen with hydrogenated porous silicon-detection of precursor to silane formation. Surf. Sci. 348, 325–334 (1996).

    Article  CAS  Google Scholar 

  8. Silberzan, P., Leger, L., Ausserre, D. & Benattar, J. J. Silanation of silica surfaces. A new method of constructing pure or mixed monolayers. Langmuir 7, 1647–1651 (1991).

    Article  CAS  Google Scholar 

  9. Tripp, C. P. & Hair, M. L. An infrared study of the reaction of octadecyltrichlorosilane with silica. Langmuir 8, 1120–1126 (1992).

    Article  CAS  Google Scholar 

  10. Le Grange, J. D., Markham, J. L. & Kurkjian, C. R. Effects of surface hydration on the deposition of silane monolayers on silica. Langmuir 9, 1749–1753 (1993).

    Article  CAS  Google Scholar 

  11. Tripp, C. P. & Hair, M. L. Direct observation of the surface bonds between self-assembled monolayers of octadecyltrichlorosilane and silica surfaces: a low-frequency IR study at the solid/liquid interface. Langmuir 11, 1215–1219 (1995).

    Article  CAS  Google Scholar 

  12. Onclin, S., Ravoo, B. J. & Reinhoudt, D. N. Engineering silicon oxide surfaces using self-assembled monolayers. Angew. Chem. Int. Ed. 44, 6282–6304 (2005).

    Article  CAS  Google Scholar 

  13. Gupta, P., Colvin, V. L. & George, S. M. Hydrogen desorption kinetics from monohydride and dihydride species on silicon surfaces. Phys. Rev. B 37, 8234–8243 (1988).

    Article  CAS  Google Scholar 

  14. Halimaoui, A., Campidelli, Y., Larre, A. & Bensahel, D. Thermally induced modifications in the porous silicon properties. Phys. Status Solidi 190, 35–40 (1995).

    Article  CAS  Google Scholar 

  15. Sugiyama, H. & Nittono, O. Microstructure and lattice distortion of anodized porous silicon layers. J. Crystal Growth 103, 156–163 (1990).

    Article  CAS  Google Scholar 

  16. Herino, R., Perio, A., Barla, K. & Bomchil, G. Microstructure of porous silicon and its evolution with temperature. Mater. Lett. 2, 519–523 (1984).

    Article  CAS  Google Scholar 

  17. Labunova, V., Bondarenkoa, V., Glinenkoa, I., Dorofeeva, A. & Tabulinaa, L. Heat treatment effect on porous silicon. Thin Solid Films 137, 123–134 (1986).

    Article  Google Scholar 

  18. Gupta, P., Dillon, A. C., Bracker, A. S. & George, S. M. FTIR studies of H2O and D2O decomposition on porous silicon surfaces. Surf. Sci. 245, 360–372 (1991).

    Article  CAS  Google Scholar 

  19. Ogata, Y., Niki, H., Sakka, T. & Iwasaki, M. Oxidation of porous silicon under water vapor environment. J. Electrochem. Soc. 142, 1595–1601 (1995).

    Article  CAS  Google Scholar 

  20. Gorbanyuk, T. I., Evtukh, A. A., Litovchenko, V. G., Solnsev, V. S. & Pakhlov, E. M. Porous silicon microstructure and composition characterization depending on the formation conditions. Thin Solid Films 495, 134–138 (2006).

    Article  CAS  Google Scholar 

  21. Iler, R. K. The Chemistry of Silica (Wiley, 1976).

    Google Scholar 

  22. Brinker, C. J. & Scherer, G. W. Sol–Gel Science: The Physics and Chemistry of Sol–Gel Processing (Academic Press, 1990).

    Google Scholar 

  23. Jiang, Y.-B. et al. Sub-10-nm-thick microporous membranes made by plasma-defined atomic layer deposition of a bridged silsesquioxane precursor. J. Am. Chem. Soc. 129, 15446–15447 (2007).

    Article  CAS  Google Scholar 

  24. Sone, Y., Ekdunge, P. & Simonsson, D. Proton conductivity of Nafion 117 as measured by a four-electrode AC impedance method. J. Electrochem. Soc. 143, 1254–1259 (1996).

    Article  CAS  Google Scholar 

  25. Zawodzinski, T. A. et al. A comparative study of water uptake by and transport through ionomeric fuel cell membranes. J. Electrochem. Soc. 140, 1981–1985 (1993).

    Article  CAS  Google Scholar 

  26. Sumner, J. J., Creager, S. E., Ma, J. J. & DesMarteau, D. D. Proton conductivity in Nafion 117 and in a novel bis[(perfluoroalkyl)sulfonyl]imide ionomer membrane. J. Electrochem. Soc. 145, 107–110 (1998).

    Article  CAS  Google Scholar 

  27. Lucovsky, G., Yang, J., Chao, S. S., Tyler, J. E. & Czubatyj, W. Oxygen-bonding environments in glow-discharge-deposited amorphous silicon–hydrogen alloy films. Phys. Rev. B 28, 3225–3233 (1983).

    Article  CAS  Google Scholar 

  28. Uchino, T., Sakka, T. & Iwasaki, M. Interpretation of hydrated states of sodium silicate glasses by infrared and Raman analysis. J. Am. Ceram. Soc. 74, 306–313 (1991).

    Article  CAS  Google Scholar 

  29. Hagymassy, J., Brunauer, S. & Mikhail, R. S. Pore structure analysis by water vapor adsorption. I. t-curves for water vapor. J. Colloid Interface Sci. 29, 485–491 (1969).

    Article  CAS  Google Scholar 

  30. Moghaddam, S., Pengwang, E., Lin, K. Y., Masel, R. I. & Shannon, M. A. Millimeter-scale fuel cell with onboard fuel and passive control system. J. MEMS 17, 1388–1395 (2008).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Financial support for the UIUC team was provided by the Defense Advanced Research Projects Agency (DARPA). C.J.B. was supported through the US Department of Energy, Office of Basic Energy Sciences (grant DE-FG02-02-ER15368) and, Division of Catalysis and Division of Materials Sciences and Engineering. Y.B.J. was supported through the Sandia National Laboratories LDRD program. This work was carried out in part in the Frederick Seitz Materials Research Laboratory Central Facilities, University of Illinois, which are partially supported by the US Department of Energy under grant nos DE-FG02-07ER46453 and DE-FG02-07ER46471. The authors would like to thank T. Spila, R. Haasch and V.V. Mainz for their assistance with the ToF–SIMS, XPS and NMR analysis, and G. Mensing for reviewing the paper. The help of R. Morgan and J. Jihyung in preparing catalysts is also appreciated.

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Contributions

S.M. conceived the asymmetric PEM and MEA designs and conceived and performed the self-terminating pore fabrication process as well as modification of the pore surface properties. S.M. performed characterization tests and data analysis. S.M. and M.A.S. discussed the results. E.P. KOH-etched the silicon membranes and deposited the chromium/gold layers. Y.B.J. and C.J.B. performed the PD–ALD work and wrote the corresponding section in the paper. A.R.G. and D.J.B. conducted water desorption tests on some of the membranes. S.M. wrote the paper. M.A.S., C.J.B. and R.I.M commented on the paper.

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Correspondence to Saeed Moghaddam or Mark A. Shannon.

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Moghaddam, S., Pengwang, E., Jiang, YB. et al. An inorganic–organic proton exchange membrane for fuel cells with a controlled nanoscale pore structure. Nature Nanotech 5, 230–236 (2010). https://doi.org/10.1038/nnano.2010.13

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