Exploring Cu-Doped Co 3 O 4 Bifunctional Oxygen Electrocatalysts for Aqueous Zn-Air Batteries.

The efficiency of oxygen electrocatalysis is a key factor in diverse energy domain applications, including the performance of metal-air batteries, such as aqueous Zinc (Zn)-air batteries. We demonstrate here that the doping of cobalt oxide with optimal amounts of copper (abbreviated as Cu-doped Co 3 O 4 ) results in a stable and efficient bifunctional electrocatalyst for oxygen reduction (ORR) and evolution (OER) reactions in aqueous Zn-air batteries. At high Cu-doping concentrations (≥5%), phase segregation occurs with the simultaneous presence of Co 3 O 4 and copper oxide (CuO). At Cu-doping concentrations ≤5%, the Cu ion resides in the octahedral (O h ) site of Co 3 O 4 , as revealed by X-ray diffraction (XRD)/Raman spectroscopy investigations and molecular dynamics (MD) calculations. The residence of Cu@O h sites leads to an increased concentration of surface Co 3+ -ions (at catalytically active planes) and oxygen vacancies, which is beneficial for the OER. Temperature-dependent magnetization measurements reveal favorable d -orbital configuration (high e g occupancy ≈ 1) and a low → high spin-state transition of the Co 3+ -ions, which are beneficial for the ORR in the alkaline medium. The influence of Cu-doping on the ORR activity of Co 3 O 4 is additionally accounted in DFT calculations via interactions between solvent water molecules and oxygen vacancies. The application of the bifunctional Cu-doped (≤5%) Co 3 O 4 electrocatalyst resulted in an aqueous Zn-air battery with promising power density (=84 mW/cm 2 ), stable cyclability (over 210 cycles), and low charge/discharge overpotential (=0.92 V).