Air Electrode Property of Doped NiCo2O4 Based Oxide for Rechargeable Zn-Air Battery
Authors: Ishihara Tatsumi , Inoishi Yuiko 
Published: December 2020

There is a strong demand for rechargeable battery with large energy density and capacity because of increase in performance of mobile equipment such as mobile phone, laptop personal computer (PC) and also electric vehicle. At present, Li ion battery (LIB) have been widely used for such purpose. However, there are several issues such as the insufficient capacity and safety required to solve. Zinc-air batteries have been used commercially as a non rechargeable battery at present, however, recently, there is strong interest for development of rechargeable Zn-air battery because of its theoretical large capacity, low cost, and safety. However zinc-air rechargeable battery still has limits in cycle file and energy efficiency. In particular, increase in air electrode performance is strongly required. In this study, nickel cobalt spinel oxide, NiCo2O4, was studied as reversible air electrode for Zn-air battery. In addition, effects of dopant on oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) were studied. NiCo2O4 based spinel oxide is active to ORR and OER, however, surface area is still insufficient by the preparation of conventional hydrothermal method. Therefore, application of splay pyrolysis method for preparation of NiCo2O4 oxide is also studied for increasing ORR/OER activity and stability.
NiCo2O4 based oxide was prepared by hydrothermal synthesis method and partial substitution was performed by using Mn, Fe, and Cu. On spray pyrolysis method, precursor solvent turned into nano-sized droplet by ultrasonic wave vaporizer, and the droplets are transferred to the tubular electric furnaces by air as carrier gas. The solvent evaporates from the droplets resulting in the formation of mesopore and after calcination, the fine powder is gathered in filters. Air electrode performance was measured by using gas diffusion layer, and PTFE and graphitic carbon were mixed with NiCo2O4 spinel for electrode. 8MKOH aqueous solution at 313K was used for electrolyte and a constant current of 20 mA/cm2 was applied by battery charge discharge equipment.
Various spinel oxides were successfully prepared by hydrothermal synthesis method from XRD measurement. It was found that ORR and OER activity of MnCo2O4 and NiCo2O4 was reasonably high among the spinel oxides prepared. ORR activity is slightly higher on MnCo2O4, however, NiCo2O4 shows much longer cycle stability of ORR/OER. In addition, elution of Mn was observed in case of MnCo2O4, in contrast, almost no change in composition was observed for NiCo2O4 after cycle measurement. Therefore, NiCo2O4 shows reasonable activity to ORR and OER and high chemical stability. Effects of dopant on NiCo2O4 on ORR and OER activity and doping Cu and Fe is effective for increasing ORR potential and decreasing OER potential. Although the most superior performance of air electrode was observed on Cu doped one, elution of Cu is obviously observed. Therefore, from chemical stability, Fe doped NiCo2O4 is the most active to air electrode catalyst. The optimization of Fe amount in Ni site was also studied and it was found that Ni0.65Fe0.35Co2O4 is the most active and stable air electrode catalyst. On this electrode, overpotential for ORR reaction is around 0.25V at 20mA/cm2, 313 K and almost 500 cycles of ORR/OER which is 1 h ORR and OER each. In addition, introduction of mesoporous structure was achieved by splay pyrolysis method and increase in surface area is also effective for increasing stability to ORR/OER activity.
This work is based on results obtained from a project, "Research and Development Initiative for Scientific Innovation of New Generation Batteries (RISING2)", JPNP16001, commissioned by the New Energy and Industrial Technology Development Organization (NEDO).