Oxygen concentration cell electrode polarity

To facilitate the rapid attainment of equilibrium, a liquid gas-diffusion electrode was developed whereby concentration polarization could be minimized. The ohmic polarization (the RI drop between the electrodes, which gives rise to an internal resistance) is also minimized when the anode-to-cathode separation is reduced. The apparatus of the hydrogen-oxygen fuel cell developed by Bacon with gas-diffusion electrodes is shown in Fig. 9.12. The operating temperature of 240" C is attained with an electrolyte concentration of about 80% KOH solution, which with the high pressures of about 600 psi for H2 and O2, allows high current densities to be drawn with relatively low polarization losses. Units such as these with power of 15 kW have been built and used successfully for long periods. 

The improvement in cell performance at higher pressure and high current density can be attributed to a lower diffusion polarization at the cathode and an increase in the reversible cell potential. In addition, pressurization decreases activation polarization at the cathode because of the increased oxygen and water partial pressures. If the partial pressure of water is allowed to increase, a lower acid concentration will result. This will increase ionic conductivity and bring about a higher exchange current density. The net outcome is a reduction in ohmic losses. It was reported (33) that an increase in cell pressure (100% H3PO4, 169°C (336°F)) from 1 to 4.4 atm (14.7 to 64.7 psia) produces a reduction in acid concentration to 97%, and a decrease of about 0.001 ohm in the resistance of a small six cell stack (350 cm electrode area). 

This approach was coupled to a system of three NAD+-dependent enzymes comprised of alcohol dehydrogenase (EC 1.1.1.1), aldehyde dehydrogenase (EC 1.2.1.3), and formate dehydrogenase (EC 1.2.1.2) to create an electrode theoretically capable of complete oxidation of methanol to carbon dioxide, as shown in Eigure 5. The anode was, in turn, coupled to a platinum-catalyzed oxygen cathode to produce a complete fuel cell operating at pH 7.5. With no externally applied convection, the cell produced power densities of 0.67 mW/cm at 0.49 V for periods of less than 1 min, before the onset of concentration polarization. 

The most obvious advantages of the oxygen cathode are that it has low weight and infinite capacity. Consequently, prototype D-size cells based on the zinc-air system have been shown to have twice the overall practical capacity of zinc-mercuric oxide cells (and 10 times that of a standard Leclanchd cell) when subjected to a continuous current drain of 250 mA. In the larger industrial cells, energy densities of up to 200 Wh/kg and specific capacities of 150 Ah/dm3 may be obtained. On the other hand, a catalytic surface must be provided for efficient charge transfer at the oxygen cathode, and by its nature the electrode is susceptible to concentration polarization. 

A higher polarization curve when cell operating pressure is increased can be expected on the base of the Nernst equation (3.15), but the concomitant increase of / o, due to the higher concentration of reactant gases on electrodes, with the consequent improvement of the hydrogen/oxygen reaction rate, has to be also considered [34]. 

Fig. 3.3 Polarization curves of a DEGFC. Cell temperatiue 80 °C. Anode 20 % PtSn/C, cathode 20 % Pt/C. Catalyst loading in both electrodes 2 mg/cm. Membrane Nafion 117. EG concentration and flow rate 1 M and 2 mL/min. Oxygen flow rate 0.5 L/min without backpressure...

Figure 23.14. Impact of ruthenium on oxygen reduction performance (a) CO stripping scans for the cathode and anode, (b) steady-state anode polarization plots before and alter contamination of the eathode, (c) H2-air steady-state polarization curves, and (d) DMFC steady-state polarization curves. Methanol concentration 0.3 M, anode potential during contamination 1.3 V vs. hydrogen counter/quasi-reference electrode, cell temperature 75 °C [65]. (Reprinted by permission of ECS— The Electrochemical Society, from Piela P, Eickes C, Brosha E, Garzon F, Zelenaya P. Ruthenium crossover in direct methanol fuel cell with Pt-Ru black anode.)...

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