Because of the remarkably high theoretical energy output, metal–air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal–air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal–air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic–organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal–air batteries (219 references).

Metal–air batteries: from oxygen reduction electrochemistry to cathode catalysts

Spinels with the formula of AB2O4 (where A and B are metal ions) and the properties of magnetism, optics, electricity, and catalysis have taken significant roles in applications of data storage, biotechnology, electronics, laser, sensor, conversion reaction, and energy storage/conversion, which largely depend on their precise structures and compositions. In this review, various spinels with controlled preparations and their applications in oxygen reduction/evolution reaction (ORR/OER) and beyond are summarized. First, the composition and structure of spinels are introduced. Then, recent advances in the preparation of spinels with solid-, solution-, and vapor-phase methods are summarized, and new methods are particularly highlighted. The physicochemical characteristics of spinels such as their compositions, structures, morphologies, defects, and substrates have been rationally regulated through various approaches. This regulation can yield spinels with improved ORR/OER catalytic activities, which can furth...

Spinels: Controlled Preparation, Oxygen Reduction/Evolution Reaction Application, and Beyond

Replacing the rare and precious platinum (Pt) electrocatalysts with earth-abundant materials for promoting the oxygen reduction reaction (ORR) at the cathode of fuel cells is of great interest in developing high-performance sustainable energy devices. However, the challenging issues associated with non-Pt materials are still their low intrinsic catalytic activity, limited active sites, and the poor mass transport properties. Recent advances in material sciences and nanotechnology enable rational design of new earth-abundant materials with optimized composition and fine nanostructure, providing new opportunities for enhancing ORR performance at the molecular level. This Review highlights recent breakthroughs in engineering nanocatalysts based on the earth-abundant materials for boosting ORR.

Earth-Abundant Nanomaterials for Oxygen Reduction.

Fuel cell reactions invariably involve an oxygen reduction reaction (ORR) at the cathode, which is one of the main rate-decreasing steps on platinum (Pt)-catalysts in the water formation reaction and energy conversion efficiency in polymer electrolyte membrane fuel cells (PEMFCs). The Pt scarcity and cost have led to the development of alternative catalyst materials for fuel cell applications. This paper reviews ORR catalysts with regard to their classification, mechanism, activity and performances. From conventional Pt-based catalysts to non-noble metal or bio-inspired catalysts, we show how significant progresses were made in ORR catalysis.

Low-platinum and platinum-free catalysts for the oxygen reduction reaction at fuel cell cathodes

This paper reports a systematical study on the electrochemical properties of MnO2-based nanostructures as low-cost catalysts for oxygen reduction reaction (ORR) in alkaline media The results show 

MnO2-Based Nanostructures as Catalysts for Electrochemical Oxygen Reduction in Alkaline Media†

The Mn3O4 nanoparticles (ca. 10 nm) were artificially loaded the on the outer surface of CMK-3, rather than forming within the pores of CMK-3, by utilizing the hydrophobic property of CMK-3 itself and its narrow pore size. The electrocatalytic performance for the oxygen reduction of the prepared Mn3O4/CMK-3 composite was extensively studied as an air diffusion electrode material in comparison with the composite catalysts based on the other carbons (carbon nanotubes, activated carbon, and graphite). The results of electrochemical tests indicate that the Mn3O4/CMK-3 composite can provide sufficient effective three-phase interface area due to the unique structures, which plays the important role in the complex three-phase interface electrocatalytic reaction. As a result, the composite electrode behaves with a much higher electrocatalytic performance for oxygen reduction than that of the composite catalysis based on the other carbons.

Feng Li

Papers

High Electrocatalytic Performance of Mn3O4/Mesoporous Carbon Composite for Oxygen Reduction in Alkaline Solutions