Polymer electrolytes Nafion

Several devices based solely on the compound have been prepared [27], usually involving a solid phase sandwiched between two optically transparent electrodes. An example is an arrangement of two ITO electrodes with a membrane of a solid polymer electrolyte (Nafion) [112] in between on which Prussian blue has been chemically generated. 

The same authors also demonstrated the feasibility of synthesizing ozone and hydrogen peroxide simultaneously using pure water and oxygen as the reactants [71]. Commercially available yS lead dioxide and graphite powders were used as the anode and cathode, respectively. While the lead dioxide was deposited directly onto a solid polymer electrolyte (Nafion 117), the graphite powder was deposited onto a carbon fiber paper and pressed against the membrane. At an applied potential of 4.5 V, with a current density of 2 A/cm, a 4.5% current efficiency was obtained for ozone evolution while the current efficiency for peroxide production was 0.8%. 

Despite perfluorinated polymer electrolytes (Nafion, Flemion, Aciplex) having been used extensively in PEMFCs, their poor thermal mechanical stability (low Tg), high methanol permeability, and extremely high production costs have led to limitations of their large-scale application. Therefore, a variety of hydrocarbon polymer electrolytes have been developed during the past decade, with the greatest emphasis placed on the costs, conductivity, and durability of these materials. At the same time, the poor mechanical stability and inadequate durability of the hydrocarbon polymer membranes were identified as the main barriers to their practical application. 

Y. Fujita and I. Tanigawa, Addition of ion-exchange resin to oxygen cathode directly bonded to solid polymer electrolytes (Nafion) and electrochemical charac-... 

Maldonado, L., Perrin, J-C., IMlet, J., and Lottin, O. 2012. Characterization of polymer electrolyte Nafion membranes Influence of temperature, heat treatment and drying protocol on sorption and transport properties, 389, 43-56. 

Hammami, R., Ahamed, Z., Charradi, K., Beji, Z., Ben Assaker, I., Ben Naceur, J., Auvity, B., Squadrito, G., Chtourou, R., Elaboration and characterization of hybrid polymer electrolytes Nafion-TiOj for PEMFCs, Int. J. Hydrogen Energy, 2013, 38,11583. 

Solid Polymer E,kctroljte. The electrolyte in soHd polymer electrolyte (SPE) units is Nafion, a soHd polymer developed by Du Pont, which has sulfonic acid groups attached to the polymer backbone. Electrodes are deposited on each side of the polymer sheet. H" ions produced at the anode move across the polymer to the cathode, and produce hydrogen. The OH ions at the anode produce oxygen. These units have relatively low internal resistances and can operate at higher temperatures than conventional alkaline electrolysis units. SPE units are now offered commercially. 

D. Tsiplakides, S. Neophytides, O. Enea, M.M. Jaksic, and C.G. Vayenas, Non-faradaic Electrochemical Modification of Catalytic Activity (NEMCA) of Pt Black Electrodes Deposited on Nafion 117 Solid Polymer Electrolyte, /. Electrochem. Soc. 144(6), 2072-2088 (1997). 

The oxidation of H2 at room temperature on Pt black electrodes deposited on Nafion 117 was the first electrochemical promotion study utilizing a solid polymer electrolyte.35... 

The experimental setup is shown in Figure 9.23. The Pt-black catalyst film also served as the working electrode in a Nafion 117 solid polymer electrolyte cell. The Pt-covered side of the Nafion 117 membrane was exposed to the flowing H2-02 mixture and the other side was in contact with a 0.1 M KOH aqueous solution with an immersed Pt counterelectrode. The Pt catalyst-working electrode potential, Urhe (=Uwr)> was measured with respect to a reversible reference H2 electrode (RHE) via a Luggin capillary in contact with the Pt-free side of the Nafion membrane. 

To keep the consumption of the valuable platinum low, thin foils have been glued to a graphite support [34] or thin-layers of platinum have been sputtered on to a glass base [59]. Platinum can be used in a particle electrode by plating silica gel with platinum [60], or in a solid polymer electrolyte where platinum is incorporated into a nafion ion exchange membrane [61]. 

Significant advances have been made in this decade in electrochemical H2 separation, mostly through the use of solid polymer electrolytes. Since the overpotentials for H2 reduction and oxidation are extremely low at properly constructed gas diffusion electrodes, very high current densities are achievable at low total polarization. Sedlak [13] plated thin layer of Pt directly on Nafion proton conductors 0.1-0.2cm in thickness, and obtained nearly 1200 mA/cm2 at less than 0.3 V. The... 

PEM Proton-exchange-membrane fuel cell (Polymer-electrolyte-membrane fuel cell) Proton- conducting polymer membrane (e.g., Nafion ) H+ (proton) 50-80 mW (Laptop) 50 kW (Ballard) modular up to 200 kW 25-=45% Immediate Road vehicles, stationary electricity generation, heat and electricity co-generation, submarines, space travel... 

Platinum chemically deposited on a Nafion membrane was used as a platinum SPE (Solid Polymer Electrolyte) electrode. The electrochemical measurements were performed using the half cell shown in Fig. 2-2. The cell body is made from Teflon (PTFE). The cell is divided into two compartments one for backside gas supply one for the electrolyte. SPE electrodes are placed between them with the deposited side facing the gas compartment. A gold foil with a hole was placed behind the SPE electrode... 

Figure 2.15 shows a schematic representation of the CCM manufacturing process. The first step for CCM preparation comprises mixing the reactive layer materials (e.g., platinum-supported carbonblack) with different amounts of PTFE, polymer electrolyte powder (e.g., Nafion), and/or filler materials... 

Passalacqua, E., Lufrano, F., Squadrito, G., Patti, A., and Giorgi, L. Nafion content in the catalyst layer of polymer electrolyte fuel cells Effects on structure and performance. Electrochimica Acta 2001 46 799-805. 

Hietala, S., Maunu, S. L. and Sundholm, E. 2000. Sorption and diffusion of methanol and water in PVDE-y-PSSA and Nafion 117 polymer electrolyte membranes. Journal of Polymer Science Part B Polymer Physics 38 3277-3284. 

Bauer, F., Denneler, S. and Wilert-Porada, M. 2005. Influence of temperature and humidity on the mechanical properties of Nafion 117 polymer electrolyte membrane. Journal of Polymer Science Part B Polymer Physics 43 786-795. 

Schematic depiction of the structural evolution of polymer electrolyte membranes. The primary chemical structure of the Nafion-type ionomer on the left with hydrophobic backbone, side chains, and acid head groups evolves into polymeric aggregates with complex interfacial structure (middle). Randomly interconnected phases of these aggregates and water-filled voids between them form the heterogeneous membrane morphology at the macroscopic scale (right).

Later, Hinatsu et al. studied the uptake of water, from the liquid and vapor states at various temperatures, in acid form Nafion 117 and 125, and Aciplex and Flemion membranes, although the latter two similar products will not be discussed here. These studies were motivated by a concern over the deleterious effects, involving either overly dry or overly wet membranes, on electrical conductivity within the context of polymer electrolyte fuel cells and polymer electrolyte water electrolyzers. 

One of the most important parts of the fuel cell is the electrolyte. For polymer-electrolyte fuel cells this electrolyte is a single-ion-conducting membrane. Specifically, it is a proton-conducting membrane. Although various membranes have been examined experimentally, most models focus on Nafion. Furthermore. it is usually necessary only to modify property values and not governing equations if one desires to model other membranes. The models presented and the discussion below focus on Nafion. 

Nafion is a copolymer of poly(tetrafluoroethylene) and polysulfonyl fluoride vinyl ether. It has fixed anions, which are sulfonic acid sites, and consequently, by electroneutrality, the concentration of positive ions is fixed. Furthermore, the transference number of protons in this system is 1, which greatly simplifies the governing transport equations, as seen below. There can be different forms of Nafion in terms of the positive counterion (e.g., proton, sodium, etc.). Most models deal only with the proton or acid form of Nafion, which is the most common form used in polymer-electrolyte fuel cells due to its high proton conductivity. 

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