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It has recently been established that 1-octanethiol in the electrolyte can allow iron electrodes to be discharged at higher rates. However, the effect of thiol additives on the air electrode has not yet been studied. The effect of solvated thiols on the surface positive electrode reaction is of prime importance if these are to be used in an iron-air battery. This work shows that the air-electrode catalyst is poisoned by the presence of octanethiol, with the oxygen reduction overpotential at the air electrode increasing with time of exposure to the solution and increased 1-octanethiol concentration in the range 0–0.1 mol dm −3 .  Post-mortem  XPS analyses were performed over the used air electrodes suggesting the adsorption of sulphur species over the catalyst surface, reducing its performance. Therefore, although sulphur-based additives may be suitable for nickel-iron batteries, they are not recommended for iron-air batteries except in concentrations well below 10 × 10 −3  mol dm −3 .

Effect of 1-octanethiol as an electrolyte additive on the performance of the iron-air battery electrodes