Tip and heterogeneous effects co-contribute to a boosted performance and stability in zinc air battery.

The zinc-air battery (ZAB) performance and stability strongly depend on the structure of bifunctional electrocatalyst for oxygen reduction/evolution reaction (ORR/OER). In this work, we combine the tip and heterogeneous effects to construct cobalt/cobalt oxide heterostructure nanoarrays (Co/CoO-NAs). Due to the formed heterostructure, more oxygen vacancies are found for Co/CoO-NAs resulting in a 1.4-fold higher ORR intrinsic activity than commercial carbon supported platinum electrocatalyst (Pt/C) at 0.8 V versus reversible hydrogen electrode (vs. RHE). Moreover, a fast surface reconstruction is observed for Co/CoO-NAs during OER catalysis evidenced by in-situ electrochemical impedance spectroscopy and Raman tests. In addition, the tip effect efficiently lowers the mass transfer resistance triggering a low overpotential of 347 mV at 200 mA cm-2 for Co/CoO-NAs. The strong electronic interplay between cobalt (Co) and cobalt oxide (CoO) contributes to a stable battery performance during 1200 h galvanostatic charge-discharge test at 5 mA cm-2. This work offers a new avenue to construct high-performance and stable oxygen electrocatalyst for rechargeable ZAB.