CoNi Nanoparticles Supported on N-Doped Bifunctional Hollow Carbon Composites as High-Performance ORR/OER Catalysts for Rechargeable Zn–Air Batteries

Searching for high-quality air electrode catalysts is the long-term goal for the practical application of Zn-air batteries. Here, a series of coexistent composite materials (CoNi/NHCS-TUC-x) of cobalt-nickel supported on nitrogen-doped hollow spherical carbon and tubular carbon are obtained using a simple pyrolysis strategy. Co and Ni in the composites are mainly present in the form of alloy nanoparticles, M-N_x and M-C_x (M = Co or Ni) species, with high oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) electroactivity. The materials containing different proportions of spherical carbon and tubular carbon obtained by simply adjusting the raw materials for generating tubular carbon exhibit interesting bifunctional performance: samples with an abundant tubular content have the highest ORR onset potential (0.91 V vs reversible hydrogen electrode), while those with a rich spherical content have the highest ORR current density (5.13 mA·cm^-2). Furthermore, CoNi/NHCS-TUC-3 provides the lowest potential difference (ΔE = E_j=10 - E_1/2) of 0.806 V. We then test the potential possibility of CoNi/NHCS-TUC-3 as an air electrode for primary and rechargeable Zn-air batteries. The primary battery delivers an open-circuit potential of 1.59 V, a peak power density of 361.8 mA·cm^-2, and a specific capacity of 756.5 mA h·g_Zn^-1. The rechargeable battery could be cycled stably for more than 55 h at 10 mA·cm^-2. These characteristics make CoNi/NHCS-TUC-3 a superior electrocatalyst for both the ORR and OER, as well as a suitable bifunctional electrode applied to a rechargeable Zn-air battery.