Invited: Development of Highly Phosphonated Polymers for Fuel Cell Membranes

Phosphonated polymers may show high intrinsic proton conductivities at low water contents provided that the local concentration of phosphonic acid groups is very high [1,2]. Moreover, the lower acidity of aryl- and alkylphosphonic acids in relation to sulfonic acids requires higher acid contents to reach high conductivities also at higher water contents. In this context, poly(vinylphosphonic acid) (PVPA) has emerged as an interesting component for fuel cell membranes because of its extremely high concentration of phosphonic acid, corresponding to 9.25 mmol –PO₃H₂ per g dry material. However, the high ionic content leads to complete water solubility as well as poor mechanical properties in the solid state. Consequently, it is necessary to develop synthetic strategies to efficiently immobilize the PVPA in the membranes before practical use.

            We have previously immobilized PVPA by preparing various block and graft copolymers with PVPA segments [3]. These copolymers where found to self-assemble and form robust membranes with nanostructured morphologies and high proton conductivities. Very recently we have pursued a number of novel synthetic strategies towards different highly phosphonated membranes. These approaches include phosphonated norbornene copolymers prepared via ring opening metathesis polymerization (ROMP) [4], multiblock copolymers selectively grafted with PVPA via anionic polymerization [5], as well as block and graft copolymers containing the more acidic poly(tetrafluorostyrenephosphonic acid) via atom transfer radical polymerization (ATRP) [6]. Challenges and selected results on the synthesis and properties of these copolymers and membranes will be presented and discussed along with future prospects.

Acknowledgement

We gratefully acknowledge the financial support from the Danish Council for Strategic Research through contract no.09-065198, as well as the funding from the European Community’s Seventh Framework Programme (FP7/2010–2013) under the call ENERGY-2010-10.2-1: Future Emerging Technologies for Energy Applications (FET) under contract 256821 QuasiDry.

References

[1] Steininger, H. Schuster, M., Kreuer, K. D., Kaltbeitzel, A., Bingol, B., Meyer, W. H., Schauff, S.,Brunklaus, G., Maier, J.,Spiess, H. W., Phys. Chem. Phys., 2007, 9, 1764.

[2] Bingöl, B., Jannasch, P., Proton Conducting Phosphonated Polymers and Membranes for Fuel Cells, in Phosphorus-Based Polymers - From Synthesis to Applications, ed. S. Monge and G. David, 2014, Royal Society of Chemistry, in press.

[3] a) Perrin, R., Elomaa, M., Jannasch, P., Macromolecules, 2009, 42, 5146, b) Parvole, J., Jannasch, P. Macromolecules 2008, 41, 3893, c) Ingratta, M., Elomaa, M., Jannasch, P. Polym. Chem., 2010, 1, 739.

[4] Bingol, B., Kroeger, A., Jannasch, P., Polymer, 2013, 54, 6676.

[5] Sannigrahi, A., Takamuku, S., Jannasch, P., Polym. Chem., 2013, 4, 4207.

[6] Dimitrov, I., Takamuku, S., Jankova, K.,  Jannasch, P., Hvilsted, S., J. Membr. Sci., 2014, 450, 362.