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

Aprotic Li−O2 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 Ni2+ metal centers (t2g6eg2) of conductive nickel catecholate framework (NiII‐NCF) nanowire arrays to high‐valence Ni3+ (t2g6eg1) for NiIII‐NCF. The spin‐state modulation enables enhanced nickel–oxygen covalency in NiIII‐NCF, which facilitates electron exchange between the Ni sites and oxygen adsorbates and accelerates the oxygen redox kinetics. Upon discharging, the high affinity of Ni3+ sites with the intermediate LiO2 promotes formation of nanosheet‐like Li2O2 in the void space among NiIII‐NCF nanowires. The Li−O2 battery based on NiIII‐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−O2 batteries and beyond. NiIII‐NCF with enhanced nickel–oxygen covalency is obtained by manipulating the spin state of Ni2+ in NiII‐NCF, which facilitates formation of nanosheet‐like Li2O2 among NiIII‐NCF nanowire arrays upon discharging. This enables small charge/discharge overvoltages, superior rate capability, and long cycling stability.