Construction of 3D Hierarchical Co3O4@CoFe-LDH Heterostructures with Effective Interfacial Charge Redistribution for Rechargeable Liquid/Solid Zn-Air Batteries.

Abstract

Constructing three-dimensional (3D) hierarchical heterostructures is an appealing but challenging strategy to improve the performance of catalysts for electrical energy devices. Here, an efficient and robust flexible self-supporting catalyst, interface coupling of ultrathin CoFe-LDH nanosheets and Co3O4 nanowire arrays on the carbon cloth (CC/Co3O4@CoFe-LDH), was proposed for boosting oxygen evolution reaction (OER) in rechargeable liquid/solid Zn-air batteries (ZABs). The strong interfacial interaction between the CoFe-LDH and Co3O4 heterostructures stimulated the charge redistribution in their coupling regions, which improved the electron conductivity and optimized the adsorption free energy of OER intermediates, ultimately boosting the intrinsic OER performance. Besides, the 3D hierarchical nanoarray structure facilitated the exposure of catalytically active centers and rapid electron/mass transfer during the OER process. As such, the CC/Co3O4@CoFe-LDH catalyst achieved excellent OER catalytic activity in alkaline medium, with a small overpotential of 237 mV at 10 mA cm-2, a low Tafel slope of 35.43 mV dec-1, and long-term durability of up to 48 h, significantly outperforming the commercial RuO2 catalyst. More impressively, the liquid and flexible solid-state ZABs assembled by the CC/Co3O4@CoFe-LDH hybrid catalyst as the OER catalyst presented a stable open circuit voltage, large power density, superb cycling life, and satisfactory flexibility, indicating great potential applications in energy technology. This work provides a good guidance for the development of advanced electrocatalysts with heterostructures and an in-depth understanding of electronic modulation at the heterogeneous interface.