Iron–air systems
are a very promising technology with the
potential to become one of the cheapest and safest energy storage
solutions of the future. However, iron anodes still face some challenges
like passivation, resulting in loss of capacity, due to the formation
of nonconductive species during cycling as well as the hydrogen evolution
reaction, a parasitic reaction interfering with the charging of the
electrode. In the present work these two issues are addressed: Sulfur-modified
mesoporous iron oxides are obtained and used as hot-pressed negative
electrodes for alkaline iron–air batteries. Iron electrodes
present average capacity values between 400 and 500 mA h g Fe
–1 for ∼100 h of operation, the S-modified
iron oxides being the most stable ones. An exponential deactivation
model fitting the discharge capacity of the different electrodes compared
to the number of cycles was proposed. According to the model, the
best of the electrodes loses less than 0.5% of its capacity per cycle.
Furthermore, doubling the charge and discharge rates allows increasing
both the discharge capacity and the Coulumbic efficiency, though at
the expense of stability. This manuscript proves that the proper distribution
of sulfur on the surface of the iron oxide is fundamental to suppress
the HER and passivation, enhancing the stability of the electrode.
These properties were further corroborated in long test-runs which
comprised more than 400 h of charging and discharging.