Porous electrocatalytic electrodes for the polysulfide redox system, containing one of various metallic sulfides (especially of Co, Cu, Pb) are described. Emphasis is placed on their use as counterelectrodes in photoelectrochemical cells employing polysulfide electrolytes. Their activity is measured as a function of electrolyte temperature and composition. The ratio of S to S 2-, and through it the local redox potential of the solution, is shown to be an important factor controlling electrode activity. The short and long term stability of the electrodes, as cathodes, is discussed, and it is shown that, when used in conjunction with photoanodes, Cu2S and CoS may poison the photoelectrode surface, thereby reducing total cell efficiency.

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