Unraveling the Role of the Stoichiometry of Atomic Layer Deposited Nickel Cobalt Oxides on the Oxygen Evolution Reaction

Nickel cobalt oxides (NCOs) are promising, non-precious oxygen evolution reaction (OER) electrocatalysts. However, the stoichiometry-dependent electrochemical behavior makes it crucial to understand the structure-OER relationship. In this work, NCO thin film model systems are prepared using atomic layer deposition. In-depth film characterization shows the phase transition from Ni-rich rock-salt films to Co-rich spinel films. Electrochemical analysis in 1 m KOH reveals a synergistic effect between Co and Ni with optimal performance for the 30 at.% Co film after 500 CV cycles. Electrochemical activation correlates with film composition, specifically increasing activation is observed for more Ni-rich films as its bulk transitions to the active (oxy)hydroxide phase. In parallel to this transition, the electrochemical surface area (ECSA) increases up to a factor 8. Using an original approach, the changes in ECSA are decoupled from intrinsic OER activity, leading to the conclusion that 70 at.% Co spinel phase NCO films are intrinsically the most active. The studies point to a chemical composition dependent OER mechanism: Co-rich spinel films show instantly high activities, while the more sustainable Ni-rich rock-salt films require extended activation to increase the ECSA and OER performance. The results highlight the added value of working with model systems to disclose structure-performance mechanisms. Atomic layer deposition offers control over the chemical composition of nickel cobalt oxide thin films, thereby enabling the investigation of their structure-oxygen evolution reaction (OER) performance relationship. The continuous hydroxide phase formation in nickel-rich rock-salt films proceed in parallel with the increase in their electrochemical surface area and OER performance, whereas cobalt-rich spinel films show a constant OER activity. image