Moon Gyu Park

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

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.

Recent progress and perspectives on bi-functional oxygen electrocatalysts for advanced rechargeable metal–air batteries

With continued dependence on carbon-based fuels and rising concerns of environmental issues, the development of rechargeable metal–air batteries has recently gained tremendous attention. However, due to the slow kinetics of electrochemical oxygen reactions, the charge and discharge processes of a rechargeable metal–air battery must be catalyzed by using bi-functional catalysts that are active towards both the oxygen reduction and oxygen evolution reactions. This review focuses on recent developments in bi-functional catalysts and their catalytic activity in relation to materials composition, morphology, and crystal structure obtained through various synthetic techniques. The discussion is divided into sections based on the main types of recent bi-functional catalysts such as transition metal- and carbon-based materials, and hybrids which consist of the two. The subsections are then divided based on the metal substituents, types of dopant, degree of doping, and defect densities, discussing the effects of composition. In parallel, morphological effects on the catalytic activity, such as unique nanostructured design, surface area enhancements, and porosity, are also discussed. Currently, bi-functional oxygen electrocatalyst research is heading in the direction of reducing the loading of precious metals, and developing cost-competitive non-precious metal- and carbon-based catalysts to enable commercialization of rechargeable metal–air batteries for various applications including electric-drive vehicles and smart-grid energy storage. To understand the origin of bi-functional catalytic activity, future catalyst research should be conducted in combination with in situ characterizations, and computational studies, which will allow exploitation of active sites to maximize the efficacy of bi-functional catalysts.

Pomegranate‐Inspired Design of Highly Active and Durable Bifunctional Electrocatalysts for Rechargeable Metal–Air Batteries

Rational design of highly active and durable electrocatalysts for oxygen reactions is critical for rechargeable metal-air batteries. Herein, we report the design and development of composite electrocatalysts based on transition metal oxide nanocrystals embedded in a nitrogen-doped, partially graphitized carbon framework. Benefiting from the unique pomegranate-like architecture, the composite catalysts possess abundant active sites, strong synergetic coupling, enhanced electron transfer, and high efficiencies in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The Co3O4-based composite electrocatalyst exhibited a high half-wave potential of 0.842 V for ORR, and a low overpotential of only 450 mV at the current density of 10 mA cm(-2) for OER. A single-cell zinc-air battery was also fabricated with superior durability, holding great promise in the practical implementation of rechargeable metal-air batteries.

Flexible High‐Energy Polymer‐Electrolyte‐Based Rechargeable Zinc–Air Batteries

A thin-film, flexible, and rechargeable zinc-air battery having high energy density is reported particularly for emerging portable and wearable electronic applications. This freeform battery design is the first demonstrated by sandwiching a porous-gelled polymer electrolyte with a freestanding zinc film and a bifunctional catalytic electrode film. The flexibility of both the electrode films and polymer electrolyte membrane gives great freedom in tailoring the battery geometry and performance.

Self-Assembled NiO/Ni(OH)2 Nanoflakes as Active Material for High-Power and High-Energy Hybrid Rechargeable Battery

Herein, a proof-of-concept of novel hybrid rechargeable battery based on electrochemical reactions of both nickel-zinc and zinc-air batteries is demonstrated using NiO/Ni(OH)2 nanoflakes self-assembled into mesoporous spheres as the active electrode material. The hybrid battery operates on two sets of fundamentally different battery reactions combined at the cell level, unlike in other hybrid systems where batteries of different reactions are simply connected through an external circuitry. As a result of combining nickel-zinc and zinc-air reactions, the hybrid battery demonstrates both remarkably high power density (volumetric, 14 000 W L(-1); gravimetric, 2700 W kg(-1)) and energy density of 980 W h kg(-1), significantly outperforming the performances of a conventional zinc-air battery. Furthermore, the hybrid battery demonstrates excellent charge rate capability up to 10 times faster than the rate of discharge without any capacity and voltage degradations, which makes it highly suited for large-scale applications such as electric vehicle propulsion and smart-grid energy storage.

Synergistic bifunctional catalyst design based on perovskite oxide nanoparticles and intertwined carbon nanotubes for rechargeable zinc-air battery applications.

Advanced morphology of intertwined core-corona structured bifunctional catalyst (IT-CCBC) is introduced where perovskite lanthanum nickel oxide nanoparticles (LaNiO3 NP) are encapsulated by high surface area network of nitrogen-doped carbon nanotubes (NCNT) to produce highly active and durable bifunctional catalyst for rechargeable metal-air battery applications. The unique composite morphology of IT-CCBC not only enhances the charge transport property by providing rapid electron-conduction pathway but also facilitates in diffusion of hydroxyl and oxygen reactants through the highly porous framework. Confirmed by electrochemical half-cell testing, IT-CCBC in fact exhibits very strong synergy between LaNiO3 NP and NCNT demonstrating bifunctionality with significantly improved catalytic activities of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Furthermore, when compared to the state-of-art catalysts, IT-CCBC outperforms Pt/C and Ir/C in terms of ORR and OER, respectively, and shows improved electrochemical stability compared to them after cycle degradation testing. The practicality of the catalyst is corroborated by testing in a realistic rechargeable zinc-air battery utilizing atmospheric air in ambient conditions, where IT-CCBC demonstrates superior charge and discharge voltages and long-term cycle stability with virtually no battery voltage fading. These improved electrochemical properties of the catalyst are attributed to the nanosized dimensions of LaNiO3 NP controlled by simple hydrothermal technique, which enables prolific growth of and encapsulation by highly porous NCNT network. The excellent electrochemical results presented in this study highlight IT-CCBC as highly efficient and commercially viable bifunctional catalyst for rechargeable metal-air battery applications.

Perovskite–Nitrogen-Doped Carbon Nanotube Composite as Bifunctional Catalysts for Rechargeable Lithium–Air Batteries

Developing an effective bifunctional catalyst is a significant issue, as rechargeable metal-air batteries are very attractive for future energy systems. In this study, a facile one-pot process is introduced to prepare an advanced bifunctional catalyst (op-LN) incorporating nitrogen-doped carbon nanotubes (NCNTs) into perovskite La0.5 Sr0.5 Co0.8 Fe0.2 O3 nanoparticles (LSCF-NPs). Confirmed by half-cell testing, op-LN exhibits synergistic effects of LSCF-NP and NCNT with excellent bifunctionality for both the oxygen reduction reaction and the oxygen evolution reaction. Furthermore, op-LN exhibits comparable performances in these reactions to Pt/C and Ir/C, respectively, which highlights its potential for use as a commercially viable bifunctional catalyst. Moreover, the results obtained by testing op-LN in a practical Li-air battery demonstrate improved and complementary charge/discharge performance compared to those of LSCF-NP and NCNT, and this confirms that simply prepared op-LN is a promising candidate as a highly effective bifunctional catalyst for rechargeable metal-air batteries.

3D Ordered Mesoporous Bifunctional Oxygen Catalyst for Electrically Rechargeable Zinc-Air Batteries.

To enhance energy efficiency and durability, a highly active and durable 3D ordered mesoporous cobalt oxide framework has been developed for rechargeable zinc-air batteries. The bifunctional air electrode consisting of 3DOM Co3 O4 having high active surface area and robust structure, results in superior charge and discharge battery voltages, and durable performance for electrically rechargeable zinc-air batteries.

Highly Active and Durable Nanocrystal-Decorated Bifunctional Electrocatalyst for Rechargeable Zinc-Air Batteries.

A highly active and durable bifunctional electrocatalyst that consists of cobalt oxide nanocrystals (Co3 O4 NC) decorated on the surface of N-doped carbon nanotubes (N-CNT) is introduced as effective electrode material for electrically rechargeable zinc-air batteries. This active hybrid catalyst is synthesized by a facile surfactant-assisted method to produce Co3 O4 NC that are then decorated on the surface of N-CNT through hydrophobic attraction. Confirmed by half-cell testing, Co3 O4 NC/N-CNT demonstrates superior oxygen reduction and oxygen evolution catalytic activities and has a superior electrochemical stability compared to Pt/C and Ir/C. Furthermore, rechargeable zinc-air battery testing of Co3 O4 NC/N-CNT reveals superior galvanodynamic charge and discharge voltages with a significantly extended cycle life of over 100 h, which suggests its potential as a replacement for precious-metal-based catalysts for electric vehicles and grid energy storage applications.

Hierarchical Core–Shell Nickel Cobaltite Chestnut-like Structures as Bifunctional Electrocatalyst for Rechargeable Metal–Air Batteries

Nano-engineered hierarchical core-shell nickel cobaltite chestnut-like structures were successfully synthesized as a bifunctionally active electrocatalyst for rechargeable metal-air battery applications. Both the morphology and composition of the catalyst were optimized by a facile hydrothermal reaction, resulting in a 10 h reacted sample demonstrating significantly enhanced activity toward both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in 0.1 m KOH. Specifically, the catalyst demonstrated -0.28 and 0.60 V versus SCE (saturated calomel electrode) at the ORR half-wave potential and an OER current density of 10 mA cm-2 , respectively. The resulting ORR/OER potential difference of 0.90 V was the smallest compared to the catalysts synthesized using 2, 6, and 12 h of hydrothermal reaction time. The excellent bifunctional activity of the catalyst is attributed to the nanoscale porous morphology and the spinel nickel cobaltite composition, which improved the active site exposure and transport of reactants and charges during the oxygen reactions.