4.8 Article

Lewis Acid Site Assisted Bifunctional Activity of Tin Doped Gallium Oxide and Its Application in Rechargeable Zn-Air Batteries

Journal

SMALL
Volume 18, Issue 34, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/smll.202202648

Keywords

gallium oxide; Lewis acid sites; oxygen evolution reaction; oxygen reduction reaction; Zn-air batteries

Funding

  1. UTEP start-up grant
  2. UT STARs award
  3. National Science Foundation (NSF) through NSF-PREM grant [DMR-1827745]
  4. DOE [DE-FE0031908]
  5. Biological and Environmental Research program [DE-AC05-76RL01830]
  6. Washington State Department of Commerce's Clean EnergyFund

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The enhanced safety, superior energy, and power density of rechargeable metal-air batteries make them ideal for energy grids and electric vehicles. However, the lack of a cost-effective and stable bifunctional catalyst has hindered their widespread adoption. This study demonstrates that tin-doped beta-gallium oxide can efficiently catalyze oxygen reduction and evolution reactions, making it a promising cathode material for zinc-air batteries. Experimental and theoretical analysis reveal that the Lewis acid sites in beta-gallium oxide play a crucial role in enhancing the electrocatalytic activity of the tin-doped catalyst.
The enhanced safety, superior energy, and power density of rechargeable metal-air batteries make them ideal energy storage systems for application in energy grids and electric vehicles. However, the absence of a cost-effective and stable bifunctional catalyst that can replace expensive platinum (Pt)-based catalyst to promote oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at the air cathode hinders their broader adaptation. Here, it is demonstrated that Tin (Sn) doped beta-gallium oxide (beta-Ga2O3) in the bulk form can efficiently catalyze ORR and OER and, hence, be applied as the cathode in Zn-air batteries. The Sn-doped beta-Ga2O3 sample with 15% Sn (Sn-x(=0.15)-Ga2O3) displayed exceptional catalytic activity for a bulk, non-noble metal-based catalyst. When used as a cathode, the excellent electrocatalytic bifunctional activity of Sn-x(=0.15)-Ga2O3 leads to a prototype Zn-air battery with a high-power density of 138 mW cm(-2) and improved cycling stability compared to devices with benchmark Pt-based cathode. The combined experimental and theoretical exploration revealed that the Lewis acid sites in beta-Ga2O3 aid in regulating the electron density distribution on the Sn-doped sites, optimize the adsorption energies of reaction intermediates, and facilitate the formation of critical reaction intermediate (O*), leading to enhanced electrocatalytic activity.

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