Transforming the Electrochemical Behaviors of Cobalt Oxide from “Supercapacitator” to “Battery” by Atomic‐Level Structure Engineering for Inspiring the Advance of Co‐Based Batteries

Cobalt-based electrodes receive emerging attention for their high theoretical capacity and rich valence variation ability, but state-of-the-art cobalt-based electrodes present performance far below the theoretical value. Herein, the in-depth reaction mechanisms in the alkaline electrolyte are challenged and proven to be prone to the surface-redox pseudocapacitor behavior due to the low adsorption energy to OH. Using the atomic-level structure engineering strategy after substitution metal searching, the adsorption energy is effectively enhanced, and the peak of CoOOH can be observed from in situ characterization for the first time, leading to the successful transition of charge storage behavior from "supercapacitor" to "battery". When used in a Zn-Co battery as a proof of concept, it shows comprehensive electrochemical performance with a flat discharge voltage plateau of ≈1.7 V, an optimal energy density of 506 Wh kg-1 , and a capacity retention ratio of 85.1% after 2000 cycles, shining among the reported batteries. As a practical demonstration, this battery also shows excellent self-discharge performance with the capacity retention of 90% after a 10 h delay. This work subtly tunes the intrinsic electrochemical properties of the cobalt-based material through atomic-level structure engineering, opening a new opportunity for the advance of energy storage systems.