Spin‐State Manipulation of Two‐Dimensional Metal–Organic Framework with Enhanced Metal–Oxygen Covalency for Lithium‐Oxygen Batteries

Abstract Aprotic Li−O 2 batteries have attracted extensive attention in the past decade owing to their high theoretical energy density; however, they are obstructed by the sluggish reaction kinetics at the cathode and large voltage hysteresis. We regulate the spin state of partial Ni 2+ metal centers ( t 2g 6 e g 2 ) of conductive nickel catecholate framework (Ni II ‐NCF) nanowire arrays to high‐valence Ni 3+ ( t 2g 6 e g 1 ) for Ni III ‐NCF. The spin‐state modulation enables enhanced nickel–oxygen covalency in Ni III ‐NCF, which facilitates electron exchange between the Ni sites and oxygen adsorbates and accelerates the oxygen redox kinetics. Upon discharging, the high affinity of Ni 3+ sites with the intermediate LiO 2 promotes formation of nanosheet‐like Li 2 O 2 in the void space among Ni III ‐NCF nanowires. The Li−O 2 battery based on Ni III ‐NCF offers remarkably reduced discharge/charge voltage gaps, superior rate capability, and a long cycling stability of over 200 cycles. This work highlights the importance of electron spin state on the redox kinetics and will provide insight into electronic structure regulation of electrocatalysts for Li−O 2 batteries and beyond.