PEMFC proton conductivity

Proton exchange membrane fuel cell (PEMFC) Proton conductive polymer membrane H2 O2 (in air) 60-90 Transportation vehicles, stationary power plants, cogeneration plants, portable power supplies... 

Keywords Polyoxadiazole, molecular weight, mechanical properties, thermal stability, sulfonation, composites, coating, corrosion, fuel cell, PEMFC, proton conductivity, carbon nanotubes... 

For last few years, extensive studies have been carried out on proton conducting inorganic/organic hybrid membranes prepared by sol-gel process for PEMFC operating with either hydrogen or methanol as a fuel [23]. A major motivation for this intense interest on hybrid membranes is high cost, limitation in cell operation temperature, and methanol cross-... 

The PEMFCs require expensive polymer membrane (e.g., Nation ), and operate at a low temperature (e.g., 80°C). Although low temperature reduced the cost of material, the heat generated at low temperatures is more difficult to remove. Alternate proton conducting membranes (e.g., inorganic polymer composites) that will operate at a high temperature (e.g., 200°C) are required. The expensive platinum catalyst used for electrochemical reactions can be poisoned by even trace amounts of carbon monoxide in the hydrogen fuel stream. Hence, a more tolerant catalyst material needs to be developed. 

The strategy towards CO tolerance has therefore been changed, towards the development of proton conducting polymers suitable for high-temperature operation of the PEMFC, i.e., 120 °C and higher. It is already demonstrated [68] that at this temperature, 1000 ppm CO leads to only minor loss of performance. The high temperature operation will be further addressed in the final section of this chapter. 

From these examples, it can be seen that water content has a strong effect upon proton conductivity. Thus, it is clear that water management is an important factor for efficient PEMFC operation. It will be discussed in Section 3.2.3. 

Jeske, M., Soltmann, C., Ellenberg, C., Wilhelm, M., Koch, D. and Grathwohl, G. 2007. Proton conducting membranes for the high temperature-polymer electrolyte membrane-fuel cell (HT-PEMFC) based on functionalized polysiloxanes. 

The actually developed PEMFCs have a Nafion membrane, which partially fulfills these requirements, since its thermal stability is limited to 100 °C and its proton conductivity decreases strongly at higher temperatures because of its dehydration. On the other hand, it is not completely tight to liquid fuels (such as alcohols). This becomes more important as the membrane is thin (a few tens of micrometers). Furthermore, its actual cost is too high (more than 500 m ), so that its use in a PEMFC for an electric car is not cost competitive. 

Proper water management in proton exchange membrane fuel cells (PEMFCs) is critical to PEMFC performance and durability. PEMFC performance is impaired if the membrane has insufficient water for proton conduction or if the open pore space of the gas diffusion layer (GDL) and catalyst layer (CL) or the gas flow channels becomes saturated with liquid water, there is a reduction in reactant flow to the active catalyst sites. PEMFC durability is reduced if water is left in the CL during freeze/thaw cycling which can result in CL or GDL separation from the membrane,1 and excess water in contact with the membrane can result in accelerated membrane thinning.2... 

Until recently (i.e., till early 1990s), most of the efforts to develop DMFCs has been with sulfuric acid as the electrolyte. The recent success with a proton conducting membrane (perfluorosulfonic acid membrane) in PEMFCs has steered DMFC research toward the use of this electrolyte. The positive feature of a liquid feed to a DMFC is that it eliminates the humidification subsystem, as required for a PEMFC with gaseous reactants. Another positive point is that the DMFC does not require the heavy and bulky fuel processor. Two problems continue to be nerve-wracking in the projects to develop DMFCs (1) the exchange current density for methanol oxidation, even on the... 

As a base of proton conducting membrane polyvinyl alcohol (PVS) and phenolsulfonic acid (PSA) was synthesized [9]. Membrane is rendered on a surface of a catalytic layer and dries up at room temperature. As shown in [9], at ratio PVS PSA=4 1 the membrane surpasses widely used in PEMFC membranes on the Nafion basis. Besides, experimental data testily that the solution can successfully be used as a connecting element for the anode and the cathode bonding at FC assembly. 

The internal resistance of a fuel cell includes the electric contact resistance among the fuel cell components, and the proton resistance of the proton-conducting membrane. In PEMFCs, the proton resistance of the polymer electrolyte membrane contributes the most to the total ohmic resistance. 

Figure 6.11. Nyquist plots for MEAs containing different proton-conducting ionomers at 0.85 V without external humidification catalyst loading = 0.4, 0.7 mg Pt/cm2 for anode and cathode, respectively TceU = 25°C Pressure = 1 atm and H2/02 flow = 400 cmVmin [8]. (Reprinted from Electrochimica Acta, 50(2-3), Ahn SY, Lee YC, Ha HY, Hong SA, Oh IH. Effect of the ionomers in the electrode on the performance of PEMFC under non-humidifying conditions, 673-6, 2004, with permission from Elsevier.)...

The membrane and ionomer humidification requirements are of paramount importance for PEMFC operation since the proton conductivity is a fundamental necessity in the membrane as well as in the electrode for the fuel cell to function. The operating conditions of current PEMFCs are dictated by the properties of the membranes/ionomers. Now, the most important membrane type (e.g., Nafion membranes from DuPont) is based on PFSA ionomers that are used in the membrane... 

PEM fuel cells use a solid proton-conducting polymer as the electrolyte at 50-125 °C. The cathode catalysts are based on Pt alone, but because of the required tolerance to CO a combination of Pt and Ru is preferred for the anode [8]. For low-temperature (80 °C) polymer membrane fuel cells (PEMFC) colloidal Pt/Ru catalysts are currently under broad investigation. These have also been proposed for use in the direct methanol fuel cells (DMFC) or in PEMFC, which are fed with CO-contaminated hydrogen produced in on-board methanol reformers. The ultimate dispersion state of the metals is essential for CO-tolerant PEMFC, and truly alloyed Pt/Ru colloid particles of less than 2-nm size seem to fulfill these requirements [4a,b,d,8a,c,66j. Alternatively, bimetallic Pt/Ru PEM catalysts have been developed for the same purpose, where nonalloyed Pt nanoparticles <2nm and Ru particles <1 nm are dispersed on the carbon support [8c]. From the results it can be concluded that a Pt/Ru interface is essential for the CO tolerance of the catalyst regardless of whether the precious metals are alloyed. For the manufacture of DMFC catalysts, in... 

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