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

In the past decade, there have been exciting developments in the field of lithium ion batteries as energy storage devices, resulting in the application of lithium ion batteries in areas ranging from small portable electric devices to large power systems such as hybrid electric vehicles. However, the maximum energy density of current lithium ion batteries having topatactic chemistry is not sufficient to meet the demands of new markets in such areas as electric vehicles. Therefore, new electrochemical systems with higher energy densities are being sought, and metal-air batteries with conversion chemistry are considered a promising candidate. More recently, promising electrochemical performance has driven much research interest in Li-air and Zn-air batteries. This review provides an overview of the fundamentals and recent progress in the area of Li-air and Zn-air batteries, with the aim of providing a better understanding of the new electrochemical systems.

https://www.onlinelibrary.wiley.com/doi/epdf/10.1002/aenm.201000010

Metal–Air Batteries with High Energy Density: Li–Air versus Zn–Air

Zinc–air is a century-old battery technology but has attracted revived interest recently. With larger storage capacity at a fraction of the cost compared to lithium-ion, zinc–air batteries clearly represent one of the most viable future options to powering electric vehicles. However, some technical problems associated with them have yet to be resolved. In this review, we present the fundamentals, challenges and latest exciting advances related to zinc–air research. Detailed discussion will be organized around the individual components of the system – from zinc electrodes, electrolytes, and separators to air electrodes and oxygen electrocatalysts in sequential order for both primary and electrically/mechanically rechargeable types. The detrimental effect of CO2 on battery performance is also emphasized, and possible solutions summarized. Finally, other metal–air batteries are briefly overviewed and compared in favor of zinc–air.

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Recent advances in zinc–air batteries

With the development of renewable energy and electrified transportation, electrochemical energy storage will be more important in the future than it has ever been in the past. Although lithium-ion batteries (LIBs) are traditionally considered to be the most likeliest candidate thanks to their relatively long cycle life and high energy efficiency, their limited energy density as well as cost are still causing a bottleneck for their long-term application. Alternatively, metal–air batteries have been proposed as a very promising large-scale electricity storage technology with the replacement of the intercalation reaction mechanism by the catalytic redox reaction of a light weight metal–oxygen couple. Generally, based on the electrolyte, these metal–air batteries can be divided into aqueous and nonaqueous systems, corresponding to two typical batteries of Zn–air and Li–air, respectively. The prominent feature of both batteries are their extremely high theoretical energy density, especially for nonaqueous Li–air batteries, which far exceeds the best that can be achieved with LIBs. In this review, we focus on the major obstacle of sluggish kinetics of the cathode in both batteries, and summarize the fundamentals and recent advances related to the oxygen catalyst materials. According to the electrolyte, the aqueous and nonaqueous electrocatalytic mechanisms of the oxygen reduction and evolution reactions are discussed. Subsequently, seven groups of oxygen catalysts, which have played catalytic roles in both systems, are selectively reviewed, including transition metal oxides (single-metal oxides and mixed-metal oxides), functional carbon materials (nanostructured carbons and doped carbons), metal oxide–nanocarbon hybrid materials, metal–nitrogen complexes (non-pyrolyzed and pyrolyzed), transition metal nitrides, conductive polymers, and precious metals (alloys). Nonaqueous systems have the advantages of energy density and rechargeability over aqueous systems and have gradually become the research focus of metal–air batteries. However, there are considerable challenges beyond catalysts from aqueous to nonaqueous electrolytes, which are also discussed in this review. Finally, several future research directions are proposed based on the results achieved in this field, with emphasis on nonaqueous Li–air batteries.

Oxygen electrocatalysts in metal–air batteries: from aqueous to nonaqueous electrolytes

Zinc-air batteries have attracted much attention and received revived research efforts recently due to their high energy density, which makes them a promising candidate for emerging mobile and electronic applications. Besides their high energy density, they also demonstrate other desirable characteristics, such as abundant raw materials, environmental friendliness, safety, and low cost. Here, the reaction mechanism of electrically rechargeable zinc-air batteries is discussed, different battery configurations are compared, and an in depth discussion is offered of the major issues that affect individual cellular components, along with respective strategies to alleviate these issues to enhance battery performance. Additionally, a section dedicated to battery-testing techniques and corresponding recommendations for best practices are included. Finally, a general perspective on the current limitations, recent application-targeted developments, and recommended future research directions to prolong the lifespan of electrically rechargeable zinc-air batteries is provided.

Electrically Rechargeable Zinc–Air Batteries: Progress, Challenges, and Perspectives

For the development of a long-lived, electrically rechargeable zinc–air battery the structure and wettability of pasted zinc electrodes were optimized. Pasted zinc electrodes containing 1 to 10% cellulose but having almost the same nominal capacities were prepared and tested in zinc/oxygen cells. The effect of discharge rate on cell voltage and delivered capacity, as well as the maximum power, were measured. Furthermore, cell charge–discharge behaviour and cycle life were examined. After different times of operation, the porosity and the pore size distribution of the pasted zinc electrodes were measured by means of mercury porosimetry. The cycle life and peak power drain capability of the Zn/oxygen battery could be substantially improved by the addition of 10wt% cellulose to the pasted zinc electrode.

Optimized zinc electrode for the rechargeable zinc–air battery

La0.6Ca0.4CoO3: a stable and powerful catalyst for bifunctional air electrodes

Mechanistic studies of oxygen reduction at La0.6Ca0.4CoO3-activated carbon electrodes in a channel flow cell

X-ray absorption and diffraction studies of La0.6Ca0.4CoO3 perovskite, a catalyst for bifunctional oxygen electrodes

Anodic oxidation of various aluminium alloys was investigated by means of rotating disc electrodes in 3 M H2SO4 as a function of Cl−, F−, Zn2+ and In3+ concentration. Al-In, Al-Zn/In and Al-Zn/Sn alloys yielded current-potential curves at the lowest overpotentials and faradaic efficiencies for anodic oxidation of up to 98% at currents ⩾ 50 mA cm−2. While these alloys were electrochemically active in the presence of chloride as the only additive in sulphuric acid, binary aluminium alloys with Ce, Ga, La, Nd, Sn, Ta, Te, Ti or Tl were only active when Cl−, Zn2+ and In3+ species were added to the electrolyte. With the exception of Al-Ga, binary alloys displayed high faradaic efficiencies of up to 95%. Fluoride additives resulted in current-potential curves at even more negative potentials than those with chlorides. In contrast to Cl−, fluoride ions are consumed during the aluminium oxidation process due to complexation with Al(III).

S. Müller

Papers

Optimized zinc electrode for the rechargeable zinc–air battery

La0.6Ca0.4CoO3: a stable and powerful catalyst for bifunctional air electrodes

Mechanistic studies of oxygen reduction at La0.6Ca0.4CoO3-activated carbon electrodes in a channel flow cell

X-ray absorption and diffraction studies of La0.6Ca0.4CoO3 perovskite, a catalyst for bifunctional oxygen electrodes

Aluminium alloys in sulphuric acid Part I: Electrochemical behaviour of rotating and stationary disc electrodes