Freestanding MOF-Derived Honeycomb-Shape Porous MnOC@CC as an Electrocatalyst for Reversible LiOH Chemistry in Li-O2 Batteries

In rechargeable Li-O2 batteries, the electrolyte and the electrode are prone to be attacked by aggressive intermediates (O2– and LiO2) and products (Li2O2), resulting in low energy efficiency. It has been reported that in the presence of water, the formation of low-activity LiOH is more stable for electrolyte and electrode, effectively reducing the production of parasitic products. However, the reversible formation and decomposition of LiOH catalyzed by solid catalysts is still a challenge. Here, a freestanding metal–organic framework (MOF)-derived honeycomb-shape porous MnOC@CC cathode was prepared for Li-O2 batteries by in situ growth of urchin-like Mn-MOFs on carbon cloth (CC) and carbonization. The battery with the MnOC@CC cathode exhibits an ultrahigh practical discharge specific capacity of 22,838 mAh g–1 at 200 mA g–1, high-rate capability, and more stable cycling, which is superior to the MnOC powder cathode. X-ray diffraction and Fourier transform infrared results identify that the discharge product of the batteries is LiOH rather than highly active Li2O2, and no parasitic products were found during operation. The MnOC@CC cathode can induce the formation of flower-like LiOH in the presence of water due to its unique porous structure and directional alignment of Mn–O centers. This work achieves the reversible formation and decomposition of LiOH in the presence of water, offering some insights into the practical application of semiopen Li-O2 batteries.