Phosphoric acid fuel cells operation

Figure 11.21. Nyquist plot of a H2/air phosphoric acid fuel cell operated at 0.2 A cm T ...

The use of H2 mixed with CO2 occurs particularly in phosphoric acid fuel cells, operating at about 200°C. Substituting the values for R, T, and F gives... 

Phosphoric Acid Fuel Cell. Concentrated phosphoric acid is used for the electrolyte ia PAFC, which operates at 150 to 220°C. At lower temperatures, phosphoric acid is a poor ionic conductor (see Phosphoric acid and the phosphates), and CO poisoning of the Pt electrocatalyst ia the anode becomes more severe when steam-reformed hydrocarbons (qv) are used as the hydrogen-rich fuel. The relative stabiUty of concentrated phosphoric acid is high compared to other common inorganic acids consequentiy, the PAFC is capable of operating at elevated temperatures. In addition, the use of concentrated (- 100%) acid minimizes the water-vapor pressure so water management ia the cell is not difficult. The porous matrix used to retain the acid is usually sihcon carbide SiC, and the electrocatalyst ia both the anode and cathode is mainly Pt. 

Because of this extreme sensitivity, attention shifted to an acidic system, the phosphoric acid fuel cell (PAFC), for other applications. Although it is tolerant to CO, the need for liquid water to be present to facilitate proton migration adds complexity to the system. It is now a relatively mature technology, having been developed extensively for stationary power usage, and 200 kW units (designed for co-generation) are currently for sale and have demonstrated 40,000 hours of operation. An 11 MW model has also been tested. 

One of the critical issues with regard to low temperamre fuel cells is the gradual loss of performance due to the degradation of the cathode catalyst layer under the harsh operating conditions, which mainly consist of two aspects electrochemical surface area (ECA) loss of the carbon-supported Pt nanoparticles and corrosion of the carbon support itself. Extensive studies of cathode catalyst layer degradation in phosphoric acid fuel cells (PAECs) have shown that ECA loss is mainly caused by three mechanisms ... 

There are six different types of fuel cells (Table 1.6) (1) alkaline fuel cell (AFC), (2) direct methanol fuel cell (DMFC), (3) molten carbonate fuel cell (MCFC), (4) phosphoric acid fuel cell (PAFC), (5) proton exchange membrane fuel cell (PEMFC), and (6) the solid oxide fuel cell (SOFC). They all differ in applications, operating temperatures, cost, and efficiency. 

This survey focuses on recent developments in catalysts for phosphoric acid fuel cells (PAFC), proton-exchange membrane fuel cells (PEMFC), and the direct methanol fuel cell (DMFC). In PAFC, operating at 160-220°C, orthophosphoric acid is used as the electrolyte, the anode catalyst is Pt and the cathode can be a bimetallic system like Pt/Cr/Co. For this purpose, a bimetallic colloidal precursor of the composition Pt50Co30Cr20 (size 3.8 nm) was prepared by the co-reduction of the corresponding metal salts [184-186], From XRD analysis, the bimetallic particles were found alloyed in an ordered fct-structure. The elecbocatalytic performance in a standard half-cell was compared with an industrial standard catalyst (bimetallic crystallites of 5.7 nm size) manufactured by co-precipitation and subsequent annealing to 900°C. The advantage of the bimetallic colloid catalysts lies in its improved durability, which is essential for PAFC applicabons. After 22 h it was found that the potential had decayed by less than 10 mV [187],... 

Progress continues in fuel cell technology since the previous edition of the Fuel Cell Handbook was published in November 1998. Uppermost, polymer electrolyte fuel cells, molten carbonate fuel cells, and solid oxide fuel cells have been demonstrated at commercial size in power plants. The previously demonstrated phosphoric acid fuel cells have entered the marketplace with more than 220 power plants delivered. Highlighting this commercial entry, the phosphoric acid power plant fleet has demonstrated 95+% availability and several units have passed 40,000 hours of operation. One unit has operated over 49,000 hours. 

Fuel cells can be broadly classified into two types high temperature fuel cells such as molten carbonate fuel cells (MCFCs) and solid oxide polymer fuel cells (SOFCs), which operate at temperatures above 923 K and low temperature fuel cells such as proton exchange membrane fuel cells (PEMs), alkaline fuel cells (AFCs) and phosphoric acid fuel cells (PAFCs), which operate at temperatures lower than 523 K. Because of their higher operating temperatures, MCFCs and SOFCs have a high tolerance for commonly encountered impurities such as CO and CO2 (CO c)- However, the high temperatures also impose problems in their maintenance and operation and thus, increase the difficulty in their effective utilization in vehicular and small-scale applications. Hence, a major part of the research has been directed towards low temperature fuel cells. The low temperature fuel cells unfortunately, have a very low tolerance for impurities such as CO , PAFCs can tolerate up to 2% CO, PEMs only a few ppm, whereas the AFCs have a stringent (ppm level) CO2 tolerance. 

With a Pt/metal ratio from 1 1 to 5 1, V, Hf, Zr, Nb, and Ta had been tried. All these metals are nonnoble and are expected to be dissolved in phosphoric acid in the fuel cell under operation conditions. The initially used binary alloys are indeed not stable enough, and the catalyst loses its enhanced catalytic activity during several thousand hours of operation. Recently it was detected and claimed that tertiary and quarternary alloys that contain chromium are remarkably much more stable than the binary alloys, so that the aim of 40,000 hr of operation, which is the usually assumed lifetime for phosphoric acid fuel cells, can be achieved. 

Operators of the Tokyo demonstration plant have concluded that phosphoric acid fuel cell technology is ready for commercialization. The project demonstrated that (I) fuel cells can be sited in urban areas which are regulated by strict environmental constraints (2) performance and operational characteristics were very close to design goals and (3) utility personnel can efficiently operate and maintain fuel cell plant equipment with minimal additional training. As a consequence of the demonstration plant success, a new 11 -MW power plant will be developed and marketed. A comparison of the new 1 C 23 Unit with the 4,5 MW demonstration plant is given in Table 4. 

Phosphoric acid fuel cell (PAFC)—Phosphoric acid electrolyte with platinum catalyst. It can use hydrocarbon fuel and is suited for stationary applications. It can generate both electricity and steam. As many as 200 units in sizes ranging from 200 kW to 1 mW are in operation. 

Figure 8.5 shows a schematic illustration of a phosphoric acid fuel cell (PAFC). This cell type is another fuel cell operating in acidic media, and the oxidation reaction in the anode is given by... 

Phosphoric-acid fuel cell (PAFC) — In PAFCs the -> electrolyte consists of concentrated phosphoric acid (85-100%) retained in a silicon carbide matrix while the -> porous electrodes contain a mixture of Pt electrocatalyst (or its alloys) (-> electrocatalysis) supported on -> carbon black and a polymeric binder forming an integral structure. A porous carbon paper substrate serves as a structural support for the electrocatalyst layer and as the current collector. The operating temperature is maintained between 150 to 220 °C. At lower temperatures, phosphoric acid tends to be a poor ionic conductor and poisoning of the electrocatalyst at the anode by CO becomes severe. 

The 200 kW phosphoric acid fuel cell (PAFC) was introduced into the market in 1991 by International Fuel Cells/ ONSI, now called UTC Fuel Cells. It is the only commercialized fuel cell technology. PAFC units have been installed in various applications—commercial, small industrial, landfill, and military—and some are used for cooling, heating, and power. To date there have been 250 units sold, at roughly 4500/kW. The U.S. Department of Defense (DOD) has cost-shared the purchase of three-quarters of the units sold to date. The units have performed well they have operated at 95 to 98 percent availability and 99.99 to 99.9999 percent reliability and have served 4 million customers and accumulated 4 million hours of operation. The cost of PAFC units has not decreased and in fact has increased from 3500/... 

Several types of fuel cells have been developed and are classified according to the electrolytes used alkaline fuel cells, molten carbonate fuel cells, phosphoric acid fuel cells (PAFCs), PEMFCs, and solid oxide fuel cells (SOFCs). As shown in Figure 1.3, the optimum operation temperatures of these fuel cells are different, and each type has different advantages and disadvantages. 

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