Spin-State Manipulation of Two-Dimensional Metal-Organic Framework with Enhanced Metal-Oxygen Covalency for...

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 (t_2g ⁶ e_g ² ) of conductive nickel catecholate framework (Ni^II -NCF) nanowire arrays to high-valence Ni³⁺ (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 Ni³⁺ sites with the intermediate LiO₂ promotes formation of nanosheet-like Li₂ O₂ in the void space among Ni^III -NCF nanowires. The Li-O₂ 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-O₂ batteries and beyond.