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A rechargeable ZAB was assembled using a NiCo2O4 3DOM spinel displaying an open circuit potential of 1.44 V, a power density of 101 mW cm−2, and a high durability during charge/discharge cycling (being operated for 21 h).

In this work, atomically substituted three-dimensionally ordered macroporous (3DOM) spinels based on Co and Mn (MnCo2O4 and CoMn2O4) were synthetized and used as cathodic electrocatalysts in a primary Zn–air battery. Scanning/transmission electron microscopy images show a 3DOM structure for both materials. Skeleton sizes of 114.4 and 140.8 nm and surface areas of 65.3 and 74.6 m2 g–1 were found for MnCo2O4 and CoMn2O4, respectively. The increase in surface area and higher presence of Mn3+ and Mn4+ species in the CoMn2O4 3DOM material improved battery performance with a maximum power density of 101.6 mW cm–2 and a specific capacity of 1440 mA h g–1, which shows the highest battery performance reported to date using similar spinel materials. The stability performance of the electrocatalyst was evaluated in half-cell and battery cell systems, showing the higher durability of CoMn2O4, which was related to its better capability to perform the electrocatalytic process as adsorption, electron transfer, and desorption. It was found through density functional theory calculations that the CoMn2O4 spinel has a higher density of states in the Fermi level vicinity and better conductivity. Finally, the unique shape of 3DOM spinels promoted a high interaction between electroactive species and catalytic sites, making them suitable for oxygen reduction reaction applications.

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In this work, the proof of concept of a functional membraneless microfluidic Zn–air cell (μZAC) that operates with a flow-through arrangement is presented for the first time, where the activity and durability can be modulated by electrodepositing Zn on porous carbon electrodes. For this purpose, Zn electrodes were obtained using chronoamperometry and varying the electrodeposition times (20, 40, and 60 min), resulting in porous electrodes with Zn thicknesses of 3.3 ± 0.3, 11.6 ± 2.4, and 34.8 ± 5.1 μm, respectively. Pt/C was initially used as the cathode to analyze variables, such as KOH concentration and flow rate, and then, two manganese-based materials were evaluated (α-MnO2 and MnMn2O4 spinel, labeled as Mn3O4) to determine the effect of inexpensive materials on the cell performance. According to the transmission electron microscopy (TEM) results, α-MnO2 has a nanorod-like shape with a diameter of 11 ± 1.5 nm, while Mn3O4 presented a hemispherical shape with an average particle size of 22 ± 1.8 nm. The use of α-MnO2 and Mn3O4 cathodic materials resulted in cell voltages of 1.39 and 1.35 V and maximum power densities of 308 and 317 mW cm–2, respectively. The activities of both materials were analyzed through density of state calculations; all manganese species in the α-material MnO2 presented an equivalent density of states with a reduced orbital occupation to the left of the Fermi energy, which allowed for better global performance above Mn3O4/C and Pt/C.