Pursuing sustainable and efficient energy storage technologies has led to advancements in iron-air batteries. Understanding the intricate relationship between the microstructural features of iron electrodes and their oxidation and reduction behaviour is crucial for optimizing battery performance and lifespan. This thesis aims to investigate the impact of microstructural characteristics, such as phases, grain size, and defect density, on the formation of stable iron oxide/hydroxide compounds and the evolution of hydrogen gas (HER), using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) experiments in 6M KOH. The influence of an electrolyte additive, sodium stannate trihydrate, and an iron foam functioning as alternative electrode material are also examined. Hot-rolled, pure iron samples were subjected to annealing heat treatments, resulting in different grain-sized specimens. A dual-phase steel, DP1000 steel composed of ferrite and martensite phases as well as hot-rolled and cold-rolled iron electrodes, completed the materials that formed this study’s basis. Initial surface identification via optical microscopy (OM), scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), atomic force microscopy (AFM) and X-ray diffraction (XRD) have been performed. Results indicate a relatively lower formation of FeOOH for a DP1000 steel anode compared to cold-rolled alpha iron over 12 cycles. A marginally larger decline in HER kinetics is observed for a hot-rolled small grained anode compared to a coarse grained anode, while a clear effect of grain size on the development of Fe3O4 and FeOOH could not be established. An iron foam electrode showcases greatly enhanced anodic and cathodic current densities in comparison to solid sheet iron electrodes, due to its cellular structure. The effect of 0.01M sodium stannate added to the electrolyte illustrates a significant reduction in HER intensity for both foam and solid iron samples.