Covalent organic frameworks with Ni-Bis(dithiolene) and Co-porphyrin units as bifunctional catalysts for Li-O 2 batteries.

The rational design of efficient and stable catalysts for the oxygen reduction reaction and oxygen evolution reaction (ORR/OER) is the key to improving Li-O 2 battery performance. Here, we report the construction of ORR/OER bifunctional cathode catalysts in a covalent organic framework (COF) platform by simultaneously incorporating Ni-bis(dithiolene) and Co-porphyrin units. The resulting bimetallic Ni/Co-COF exhibits high surface area, fairly good electrical conductivity, and excellent chemical stability. Li-O 2 batteries with the Ni/Co-COF-based cathode show a low discharge/charge potential gap (1.0 V) and stable cycling (200 cycles) at a current density of 500 mA g -1 , rivaling that of PtAu nanocrystals. Density functional theory computations and control experiments using nonmetal or single metal-based isostructural COFs reveal the critical role of Ni and Co sites in reducing the discharge/charge overpotentials and regulating the Li 2 O 2 deposition. This work highlights the advantage of bimetallic COFs in the rational design of efficient and stable Li-O 2 batteries.