Double-Faced Atomic-Level Engineering of Hollow Carbon Nanofibers as Free-Standing Bifunctional Oxygen Electrocatalysts for Flexible Zn–Air Battery

Flexible solid-state zinc–air batteries (ZABs) with low cost, excellent safety, and high energy density has been considered as one of ideal power sources for portable and wearable electronic devices, while their practical applications are still hindered by the kinetically sluggish cathodic oxygen reduction and oxygen evolution reactions (ORR/OER). Herein, a Janus-structured flexible free-standing bifunctional oxygen electrocatalyst, with OER-active O, N co-coordinated Ni single atoms and ORR-active Co3O4@Co1–x S nanosheet arrays being separately integrated at the inner and outer walls of flexible hollow carbon nanofibers (Ni-SAs/HCNFs/Co-NAs), is reported. Benefiting from the sophisticated topological structure and atomic-level-designed chemical compositions, Ni-SAs/HCNFs/Co-NAs exhibits outstanding bifunctional catalytic activity with the ΔE index of 0.65 V, representing the current state-of-the-art flexible free-standing bifunctional ORR/OER electrocatalyst. Impressively, the Ni-SAs/HCNFs/Co-NAs-based liquid ZAB show a high open-circuit potential (1.45 V), high capacity (808 mAh g–1 Zn), and extremely long life (over 200 h at 10 mA cm–2), and the assembled flexible all-solid-state ZABs have excellent cycle stability (over 80 h). This work provides an efficient strategy for developing high-performance bifunctional ORR/OER electrocatalysts for commercial applications.