Perfluorosulfonic acid ionomer structure

An adequate structure of polymer molecules promotes the advantageous phase separation into hydrophobic and hydrophilic domains upon water uptake. The most notable class of membranes based on this principle are the perfluorosulfonic acid ionomers (PFSI), Nafion [26] and similar membranes [27]. In these membranes, perfluorosulfonate side chains, terminated with hydrophilic —SO3H groups, are attached to a hydrophobic fluorocarbon backbone. The tendency of ionic groups to aggregate into ion clusters due to the amphiphilic nature of the ionomer leads to the formation of basic aqueous units. At sufficient humidity these units first get connected by narrow channels and then may even fuse to provide continuous aqueous pathways [28]. 

Numerous polymers have been studied for their potential apphcation in PEMFCs. Based on their chemical structure, these polymers can be categorized into (a) vinylic polymers, (b) aromatic polymers, and (c) polymer blends and composite/hybrid polymers. Generally, vinylic polymers are synthesized by addition polymerization, while aromatic polymers are synthesized by step-growth polymerization. The most studied vinylic polymers for PEMFC applications are perfluorosulfonic acid ionomers (PFSls), in particular Nation , and styrene sulfonic acid-based polymers. Chemical structures of representative vinyhc PEMs are shown in Scheme 2. 

The advent of Du Pont s inert perfluorosulfonic acid membranes, Nafion, in the late 1960,s made chlor-alkali production in a membrane cell a realistic possibility. The basic structure of Du Pont s fluoro ionomer is shown... 

Excellent reviews on chemical structure, morphology and properties of acid-bearing polymers can be found in Mauritz and Moore (2004), Peckham and Holdcroft (2010) and Yang et al. (2008). The base polymer of the prototypical DuPont Nafion perfluorosulfonic acid (PFSA) ionomer, shown in Figure 1.13(left), consists of a tetrafluoroethylene (TFE) backbone with randomly attached pendant sidechains of perfluorinated vinyl ethers. Sulfonic acid groups are fixed at the sidechain heads (Kreuer et al., 2004 Tanimura and Matsuoka, 2004 Yang et al., 2008 Yoshitake and Watakabe, 2008). 

Fig. 11.1 General structure of perfluorosulfonic acid (PFSA) ionomers...

In perfluorinated ionomers, a PTFE-based polymeric backbone offers chemical stability from the radical species or acid-base, which causes hydrolytic degradation of the polymer chain. Ionic conductivity is provided by pendant acidic moiety in carboxylate or sulfonate form. There are some reports on perfluorinated carboxylic acid (PFCA) materials, most of which are derived from Nafion [26-29]. However, PFCA is not suitable for fuel cell application due to its low proton conductivity. Perfluorosulfonic acid (PFSA) is the most favored choice among not only perfluorinated membranes but all other ionomers in fuel cell applications. Sulfonic acid form of Nafion is a representative PFSA and thus has been intensively studied since 1960s. Reported chemical structure of Nafion membrane is given in Fig. 13.8. 

Polymer electrolyte fuel cells (PEFCs) are unique in that they are the only variety of low-temperature fuel cell to utilize a solid electrolyte. The most common polymer electrolyte used in PEFCs is Nafion , produced by DuPont, a perfluorosulfonic ionomer that is commercially available in films of thicknesses varying from 25 to 175 pm. This material has a fluorocarbon polytetrafluoroethylene (PTFE)-kbone with side chains ending in pendant sulfonic acid moieties. The presence of sulfonic acid promotes water uptake, enabling the membrane to be a good protonic conductor, and thereby facilitating proton transport through the cell. This chapter reviews PEFC development, structure, and properties and presents an overview of PEM technology to date. 

---