The Oxygen Electrode at Low Temperatures

The reduction of molecular oxygen that is supplied either directly from containers or in a diluted form as air constitutes the reaction at the cathode in fuel cells. The use of air is preferable for economic reasons. Platinum metals and alloys of platinum metals are electrocatalysts for acid and alkaline electrolytes. Silver, silver alloys, nickel, carbon, and intermetallic compounds represent less expensive electrocatalysts for the oxygen electrode in alkaline solutions. In contrast to the hydrogen electrode, the overvoltage of the oxygen electrode is large at temperatures below 100 °C when a reasonable current is drawn. 

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Kobayashi et conducted steam electrolysis experiments using SrZrg gYbo.iOj. 5 tubular electrolytes (2-mm walls) with platinum electrodes (cermet with the electrolyte powder) at low temperatures (460 to 600°C) and was successful in generating hydrogen and oxygen. They used the low temperatures in an attempt to avoid excessive electronic (hole) conductivity in the electrolyte. 

One factor contributing to the inefficiency of a fuel ceU is poor performance of the positive electrode. This accounts for overpotentials of 300—400 mV in low temperature fuel ceUs. An electrocatalyst that is capable of oxygen reduction at lower overpotentials would benefit the overall efficiency of the fuel ceU. Despite extensive efforts expended on electrocatalysis studies of oxygen reduction in fuel ceU electrolytes, platinum-based metals are stiU the best electrocatalysts for low temperature fuel ceUs. 

An example for a compound of the perovskite type is LaNiOj. In other com-ponnds of the perovskite type, nickel may be replaced by cobalt or iron, and lan-thannm in part by alkaline-earth metals, an example being Lag 8Sro2Co03. The activity of perovskites toward cathodic oxygen reduction is low at room temperature but rises drastically with increasing temperature (particularly so above 150°C). In certain cases the activity rises so much that the equilibrium potential of the oxygen electrode is established. 

Thermodynamic data have also been calculated for carbon—oxygen reactions in fused salts [7, 8], The oxidation of solid carbon principally yields carbon dioxide at low temperature and carbon monoxide at high temperature. In this case, at constant temperature, the CO/CO2 concentration ratio at solid carbon depends on pressure. The carbon—oxygen electrode is used as reference to investigate cryolite—alumina melts at c. 1000°C [9] and molten slags at higher temperatures. 

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