Defect-Engineered High-Entropy Spinel Oxide@Onion-Like Carbon Catalysts for High-Areal-Energy Rechargeable Zinc-Air Batteries.

Rechargeable zinc-air batteries (ReZAB) have emerged as the next-generation batteries with several advantages over the conventional lithium-ion battery. In this work, single nanocrystals of inverse-type high-entropy spinel oxides (HESOx, particle size of 10-12 nm) confined in highly curved defective onion-like carbons (HESOx/OLC) as efficient electrocatalysts for oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and ReZAB, have been synthesized. The HESOx materials were thoroughly characterized using several analytical techniques, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), Raman, and electron paramagnetic resonance (EPR). HESOx/OLC catalyst was tested for ReZAB using literature-recommended parameters that would allow for real technological application. These parameters include a current loading of 10 mA cm and a discharge areal energy density of 35 mWh cm , which maps a Li-ion battery pack-level specific energy of 120 Wh kg . HESOx/OLC electrocatalysts allowed for continuous discharging and charging at a current loading of 10 mA cm with discharge areal energy densities between 37 and 74 mWh cm , thus outperforming the recommended threshold of 35 mWh cm . Considering that most studies (>90%) hardly meet the recommended threshold for technological application of ReZAB, the present work represents one of the top-performing electrocatalysts for ReZAB. The excellent electrocatalytic properties of defect-rich HESOx/OLC toward ORR/OER and ReZAB are governed by the strong electronic modulation arising from d-π hybridization, the availability of multiple catalytic sites for intermediates, and weakened d-band centers of the rate-determining intermediates (i.e., *O adsorption for ORR and *OOH formation for OER) compared to the pristine HESOx. This work introduces an effective approach for the design and synthesis of single nanocrystals of high-entropy electrocatalysts for the development of low-cost, robust, and technologically relevant rechargeable zinc-air batteries.