A facile and efficient method for preparing La-doped Co3O4 by electrodeposition as an efficient air cathode in rechargeable zinc-air batteries: Role of oxygen vacancies

A rechargeable zinc-air battery (ZAB) is a promising candidate for simple and low-cost energy storage systems. However, preparing the air cathode material using a binder-free method and a bifunctional catalyst is still the major challenge in the field. Herein, we demonstrate the effect of different La contents doped into the Co3O4 spinel structure in the presence of oxygen vacancies prepared by a facile and efficient electrodeposition technique on the oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and ZAB performance. Incorporating the La dopant into the Co3O4 improves the OER and ORR performances and thus enhances the specific capacity and energy density of ZAB. The optimal La-doping amount in the CoLa-1 catalyst demonstrates high feasibility for practical application with a capacity of 780 ± 24 mAh/g and an energy density of 901 ± 39 mW g−1, significantly outperforming the pristine Co3O4. The stability and cycling tests reveal good durability performance after 300 cycles and 100 h of testing without degradation, which is much more stable than the benchmark Pt/C + RuO2 electrode. The performance enhancement is attributed to the synergetic effect of high active surface area, low charge transfer resistance, and optimal oxygen vacancies. A kinetic micromechanism is proposed to illustrate the importance of the oxygen vacancy amount in trapping oxygen gas and maximizing the number of ORR and OER reactions.