Nafion/polytetrafluoroethylene membranes

In Table I are summarized the results obtained for different sample Nafion perfluoroethylene membrane (NAF), acrylic acid irradiation grafted polytetrafluoroethylene (PTFE), sulfonated styrene irradiation grafted fluorinated ethylene propylene copolymer (RAI), and sulfonated polysulfone (SPS). 

Xing, D., He, G., Hou, Z., Ming, P, and Song, S. (2013) Properties and morphology of Nafion/polytetrafluoroethylene composite membrane fabricated by a solution-spray process, Int. J. Hydrogen Energ., 38, 8400-8408. 

As shown in Figure 1.6, the optimized cathode and anode structures in PEMFCs include carbon paper or carbon cloth coated with a carbon-PTFE (polytetrafluoroethylene) sub-layer (or diffusion layer) and a catalyst layer containing carbon-supported catalyst and Nafion ionomer. The two electrodes are hot pressed with the Nafion membrane in between to form a membrane electrode assembly (MEA), which is the core of the PEMFC. Other methods, such as catalyst coated membranes, have also been used in the preparation of MEAs. 

The most diffused material for membranes is based on co-polymers of tetrafluoroethylene (TEE) with perfluorosulfonate monomers. The resulting co-polymer is constituted by polytetrafluoroethylene polymeric chain (PTFE, commercially known as Teflon) in which some fluorine atoms are substituted by sulfonated side chains. The monomer perfluoro-sulfonyfluoride ethyl-propyl-vinyl ether is used in membranes commercialized by Dupont with the registered trademark Nafion (Fig. 3.2), which is the most well-known material used as electrolyte in PEM fuel cells. 

Although there have been various membranes used, none is more researched or seen as the standard than the Nafion family by E. I. du Pont de Nemours and Company. Like the other membranes used, the general structure of Nafion is a copolymer between polytetrafluoroethylene and polysulfonyl fluoride vinyl ether. These perfluorinated sulfonic acid (PFSA) ionomers exhibit many interesting properties such as a high conductivity, prodigious water uptake, and high anion exclusion to name a few. Nafion is the main membrane studied in this chapter. 

Figure 10.3.18 illustrates the structure of the electrode/membrane system where the membrane (e.g., Nafion 900 Series) is reinforced by a nonconductive polytetrafluoroethylene (PTFE) fabric. Note that the current flux deforms around the PTFE reinforcement, leading to an increase in the voltage drop through the membrane. Therefore, the arrangement of the PTFE reinforcement must be optimized for mechanical strength and voltage drop. 

Nafion ionomer is not the only perfluorosulfonic membrane material to be considered for PEMFCs. There are many other commercial perfluorinated ionomers, such as Asahi Glass (Flemion ), Asahi Kasei (Aciplex ), 3M (3M polymer), and Solvay Solexis (Hyflon ), all of which share some structural similarities with the polytetrafluoroethylene-based Nafion but use different perfluorinated vinyl ethers, as shown in Table 4.1. 

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. 

---