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

ACS Appl Mater Interfaces. 2021 Nov 24;13(46):54906-54915. doi: 10.1021/acsami.1c13872. Epub 2021 Nov 9.

Abstract

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.

Keywords: Sn diffusion; doping; hematite; two-step annealing; water splitting.