Synergistic effect of oxygen vacancies and in-situ formed bismuth metal centers on BiVO as an enhanced bifunctional Li-O batteries electrocatalyst.

Bismuth Vanadate (BiVO) is a promising oxide-based photoanode for electrochemical applications, yet its practical use is constrained by poor charge transport properties, particularly under dark conditions. This study introduces a novel BiVO variant (Bi-BiVO-10) that incorporates abundant oxygen vacancies and in-situ formed Bi metal, significantly enhancing its electrical conductivity and catalytic performance. Bi-BiVO-10 demonstrates superior electrochemical performances compared to conventional BiVO (C-BiVO), demonstrated by its most positive half-wave potential with the highest diffusion-limiting current in the oxygen reduction reaction (ORR) and earliest onset potential in the oxygen evolution reaction (OER). Notably, Bi-BiVO-10 is explored for the first time as an electrocatalyst for lithium-oxygen (Li-O) cells, showing reduced overcharge (610 mV) in the first cycle and extended cycle life (1050 h), outperforming carbon (320 h) and C-BiVO (450 h) references. The enhancement is attributed to the synergy of oxygen vacancies, Bi metal formation, increased surface area, and improved electrical conductivity, which collectively facilitate LiO growth, enhance charge transport kinetics, and ensure stable cycling. Theoretical calculations reveal enhanced chemical interactions between intermediate molecules and the defect-rich surfaces of Bi-BiVO-10, promoting efficient discharge and charge processes in Li-O batteries. This research highlights the potential of unconventional BiVO-based materials as durable electrocatalysts and for broader electrochemical applications.