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Review
. 2017 Jun 22;10(7):687.
doi: 10.3390/ma10070687.

Polymer and Composite Membranes for Proton-Conducting, High-Temperature Fuel Cells: A Critical Review

Eliana Quartarone  1 , Simone Angioni  2 , Piercarlo Mustarelli  3
Affiliations
Review

Polymer and Composite Membranes for Proton-Conducting, High-Temperature Fuel Cells: A Critical Review

Eliana Quartarone et al. Materials (Basel). .

Abstract

Polymer fuel cells operating above 100 °C (High Temperature Polymer Electrolyte Membrane Fuel Cells, HT-PEMFCs) have gained large interest for their application to automobiles. The HT-PEMFC devices are typically made of membranes with poly(benzimidazoles), although other polymers, such as sulphonated poly(ether ether ketones) and pyridine-based materials have been reported. In this critical review, we address the state-of-the-art of membrane fabrication and their properties. A large number of papers of uneven quality has appeared in the literature during the last few years, so this review is limited to works that are judged as significant. Emphasis is put on proton transport and the physico-chemical mechanisms of proton conductivity.

Keywords: PBI; fuel cells; high temperature; membrane; polymer.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Chemical structure of poly[(2,2′-(m-phenylene)-5,5′-(bibenzimidazole)].
Scheme 2
Scheme 2
Non-covalent interactions in sulphonated PBI membranes (taken from Ref. [28]).
Scheme 3
Scheme 3
Structure of F6-oxyPBI (upper) and F6-oxyPBI-2SO3H (lower) (taken from Ref. [21]).
Figure 1
Figure 1
Polarization curves of MEAs based on fluoro- and sulfonated fluoro-oxyPBI membranes at 150 °C and without any external humidification. The data of PBI_5N are shown for comparison. DL: doping level (taken from Ref. [21]). DL is given by the relationship.
Figure 2
Figure 2
Acid-base polymer cross-linking (from Ref. [34]).
Figure 3
Figure 3
Fuel cell performances of commercial membranes compared with a blend one (taken from Ref. [34]).
Figure 4
Figure 4
Proton conductivity vs. the filler content at 120 °C and 50% relative humidity, both for the as-prepared membranes and after leaching. The inset shows the proton conductivity behaviour when a commercial nanometer-scale silica is used as the filler (taken from Ref. [42]).
Figure 5
Figure 5
The proton conductivity of Nafion-117, PA-doped PBI, PBI/MWCNT–PBI, and PBI/MWCNT–Nafion composite membranes at 80–160 °C without humidification. The data measured with the composite membrane made of non-functionalized MWCNT (0.2 wt %) and PBI are also shown for comparison (taken from Ref. [61]).
Figure 6
Figure 6
The role of Nafion™ as the coupling agent in PTFE-PBI composite membranes (taken from Ref. [67]).
Figure 7
Figure 7
Rigid aromatic polymer based on pyridine. Reaction schemes proposed in Ref. [68].
Figure 8
Figure 8
Chemical formulas of some sulphonated aromatic polymers.
Figure 9
Figure 9
(a) Total proton conductivity, σexp, of phosphoric acid as a function of λ and its contributions from proton structural diffusion, σstructural, and ionic transport associated with the hydrodynamic background σvehicle; (b) The corresponding structural transference numbers at different temperatures (taken from Ref. [82]).
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