Sn-Controlled Co-Doped Hematite for Efficient Solar-Assisted Chargeable Zn–Air Batteries

The photoelectrochemical performance of a co-doped hematite photoanode might be hindered due to the unintentionally diffused Sn from a fluorine-doped tin oxide (FTO) substrate during the high-temperature annealing process by providing an increased number of recombination centers and structural disorder. We employed a two-step annealing process to manipulate the Sn concentration in co-doped hematite. The Sn content [Sn/(Sn + Fe)] of a two-step annealing sample decreased to 1.8 from 6.9% of a one-step annealing sample. Si and Sn co-doped hematite with the reduced Sn content exhibited less structural disorder and improved charge transport ability to achieve a 3.0 mA cm–2 photocurrent density at 1.23 VRHE, which was 1.3-fold higher than that of the reference Si and Sn co-doped Fe2O3 (2.3 mA cm–2). By decorating with the efficient co-catalyst NiFe(OH)x, a maximum photocurrent density of 3.57 mA cm–2 was achieved. We further confirmed that the high charging potential and poor cyclability of the zinc–air battery could be dramatically improved by assembling the optimized, stable, and low-cost hematite photocatalyst with excellent OER performance as a substitute for expensive Ir/C in the solar-assisted chargeable battery. This study demonstrates the significance of manipulating the unintentionally diffused Sn content diffused from FTO to maximize the OER performance of the co-doped hematite.