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The growing demands for energy and the associated environmental pollution have sparked a great deal of interest in the development of clean energy technologies including fuel cells, metal-air batteries, supercapacitors, and hydrogen production. Among them, Zinc-air batteries (ZABs) are potential possibilities because of their low cost, high theoretical energy density, high-level safety, and environmental friendliness. In addition, zinc (Zn) is abundant in the environment and far less expensive than lithium metals. Thus, ZABs have been proposed as promising energy sources for grid-scale ener...
Zinc–Air Batteries Authoritative and comprehensive resource covering foundational knowledge of zinc–air batteries as well as their practical applications Zinc–Air Batteries provides a comprehensive understanding of the history and development of Zn–air batteries, with a systematic overview of components, design, and device innovation, along with recent advances in the field, especially with regards to the cathode catalyst design made by cutting-edge materials, engineering processes, and technologies. In particular, design principles regarding the key components of Zn–air batteries, ranging from air cathode, to zinc anode, and to electrolyte, are emphasized. Furthermore, industrial developments of Zn–air batteries are discussed and emerging new designs of Zn–air batteries are also introduced. The authors argue that designing advanced Zn–air battery technologies is important to the realization of efficient energy storage and conversion—and, going further, eventually holds the key to a sustainable energy future and a carbon-neutral goal. Edited and contributed to by leading professionals and researchers in the field, Zinc–Air Batteries also contains information regarding: Design of oxygen reduction catalysts in primary zinc–air batteries, including precious metals, single-atoms, carbons, and transition metal oxides Design of bifunctional oxygen catalysts in rechargeable zinc–air batteries, covering specific oxygen redox reactions and catalyst candidates Design of three-dimensional air cathode in zinc–air batteries, covering loading of carbon-based and transition metal catalysts, plus design of the three-phase interface Design of electrolyte for zinc–air batteries, including liquid electrolytes (e.g., alkaline) and gel polymer electrolytes (e.g., PVA hydrogel) For students, researchers, and instructors working in battery technologies, materials science, and electrochemistry, and for industry and government representatives for decision making associated with energy and transportation, Zinc–Air Batteries summarizes the research results on Zn–air batteries and thereby helps researchers and developers to implement the technology in practice.
Zinc-air batteries, whose advantages include relatively high energy density (1218 Wh kg-1), abundance of zinc in earth's crust, and very safe operational characteristics, are promising for applications in consumer electronics, electrified transportation, grid storage, and other fields. At the moment, primary zinc-air batteries are produced for low-drain electronic gadgets such as hearing aids. However, secondary (i.e., electrically rechargeable) zinc-air batteries have eluded widespread adoption due mainly to the slow reaction kinetics of oxygen evolution at the air electrode during recharge. A bifunctional oxygen electrocatalyst that can recharge the batteries more efficiently is required. Moreover, in the presence of aqueous alkaline electrolytes, zinc-air batteries suffer from low durability and performance loss due mainly to the formation of zinc dendrites during charging, the loss of aqueous electrolytes, the detachment of the catalyst layer and the precipitation of carbonates at the air electrode. These persistent issues have motivated a shift in electrolyte design towards efficient hydroxide ion-conductive polymeric electrolytes. A combination of efficient bifunctional oxygen electrocatalysts and polymeric electrolyte improvements may enable zinc-air batteries to be implemented in widespread applications in flexible/lightweight electronic devices and electric vehicles. In this work, I present a feasible strategy combining material innovations with engineering methods to develop a new type of zinc-air battery, i.e., a flexible, rechargeable polymer electrolyte membrane zinc-air battery (PEMZAB). In the first study, a proof of concept of a film-shaped, rechargeable PEMZAB was conducted by using a KOH-doped poly(vinyl alcohol) (PVA) gel electrolyte, porous zinc electrode and bifunctional air electrode comprising a commercial Co3O4 nanoparticles-loaded carbon cloth. Then, a novel hydroxide ion-conductive polymeric electrolyte membrane and an efficient bifunctional oxygen zinc-air battery performance. Specifically, highly quaternaized cellulose nanofibers were synthesized to produce a hydroxide ion-conductive electrolyte membrane (referred to as QAFC). The QAFC membrane shows advantages of a high ionic conductivity of 21.2 mS cm-1, good chemical stability, mechanical robustness and flexibility, and inhibition of zinc dendrites and carbonations. In addition to the QAFC electrolyte membrane development, a hybrid bifunctional oxygen electrocatalyst, consisting of cobalt oxysulfide nanoparticles and nitrogen-doped graphene nanomeshes (CoO0.87S0.13/GN), was prepared. The defect chemistries of both oxygen-vacancy-rich cobalt oxysulfides and edge-nitrogen-rich graphene nanomeshes lead to a remarkable improvement in electrocatalytic performance, where CoO0.87S0.13/GN exhibits strongly comparable catalytic activity and much better stability than the best-known benchmark noble metal catalysts. A simple, water-based filtration method for a direct assembly of the QAFC membrane and the CoO0.87S0.13/GN catalyst film was demonstrated with the PEMZAB. Such a fabrication approach enables intimate contact between the solid-solid catalyst-electrolyte interfaces for facile charge transfer. Moreover, benefiting from the performance improvement of the QAFC electrolyte membrane and the CoO0.87S0.13/GN bifunctional catalyst, the resulting battery possesses a higher energy density of 857.9 Wh kg-1 and a more stable cycling performance, over 300 hours of operation at 20 mA cm-2 under ambient conditions, than those of a battery using PVA-KOH gel electrolyte and commercial Co3O4 bifunctional catalysts. In the last study, the knowledge gained from the hybrid CoO0.87S0.13/GN bifunctional catalyst is transferred to the fabrication of a hybrid catalyst/current collector assembly for the bifunctional air electrode. In this assembly, a hair-like array of mesoporous cobalt oxide nanopetals in nitrogen-doped carbon nanotubes is grown directly on a stainless-steel mesh through chemical vapor deposition and electrodeposition methods. Such integrative design not only ensures a large number of catalytically active sites in a given electrode surface, but also increases the electron transfer between each individual catalyst and the conductive substrate. This advanced air electrode assembly further boosts the PEMZAB performance, with a high peak power density of 160.7 mW cm-2 at 250 mA cm-2 and a remarkable cycling durability: lasting over 600 hours of operation at 25 mA cm-2 under ambient conditions.
Solid State Batteries: Materials Design and Optimization treats the fundamental and experimental aspects of solid state batteries, including the basic requirements for optimum performance of electrodes and electrolytes. Coverage includes key issues in solid state batteries such as electrode/electrolyte interface problems, charge mechanism and mass transport in solid electrodes and electrolytes. The authors also discuss the physics and chemistry of insertion electrodes and glassy electrolytes and provide experimental approaches for determining the physical and chemical properties of battery materials. With an interdisciplinary approach to the solid state physics and chemistry, materials science and electrochemistry of battery materials, Solid State Batteries: Materials Design and Optimization is a valuable reference not only for specialists but also for chemists, physicists and materials scientists who wish to enter the field of battery technology.
Aqueous Zinc Ion Batteries Pioneering reference book providing the latest developments and experimental results of aqueous zinc ion batteries Aqueous Zinc Ion Batteries comprehensively reviews latest advances in aqueous zinc ion batteries and clarifies the relationships between issues and solutions for the emerging battery technology. Starting with the history, the text covers essentials of each component of aqueous zinc ion batteries, including cathodes, anodes, and electrolytes, helping readers quickly attain a foundational understanding of the subject. Written by three highly qualified authors with significant experience in the field, Aqueous Zinc Ion Batteries provides in-depth coverage of sample topics such as: History, main challenges, and zinc metal anodes for aqueous zinc ion batteries Electrochemical reaction mechanism of aqueous zinc ion batteries and interfacial plating and stripping on zinc anodes Cathode materials for aqueous zinc ion batteries, covering manganese-based materials, vanadium-based materials, Prussian blue analogs, and other cathode materials Development of electrolytes, issues, and corresponding solutions for aqueous zinc ion batteries Separators for aqueous zinc ion batteries, development of full zinc ion batteries, and future perspectives on the technology A detailed resource on a promising alternative to current lithium-ion battery systems, Aqueous Zinc Ion Batteries is an essential read for materials scientists, electrochemists, inorganic chemists, surface chemists, catalytic chemists, and surface physicists who want to be on the cutting edge of a promising new type of battery technology.
Electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are the critical cathodic and anodic reactions, respectively, in electrically rechargeable Zn-air battery. With a variety of advantages including relatively high energy density (1218 Wh kg-1), the abundance of zinc in the earth, and secure handling and safe operation, electrically rechargeable (secondary) Zn-air battery technology has been regarded as highly promising energy applications in consumer electronics, electric vehicles, and smart grid storage. Zn-air batteries consist of not only zinc anode, polymer separator, and an alkaline electrolyte that are typical battery components, but also air-breathing cathode that makes Zn-"air" battery unique technology. Unlike other general battery systems such as lithium-ion batteries, there is no active material stored in cathode, but gaseous oxygen molecules in the air are used as the fuel for energy-generating reaction in the air cathode of Zn-air technology. The reactions occurring during battery discharge and charge are ORR and OER, respectively, which are mostly dominating the overall energy efficiency of the Zn-air battery system due to their intrinsically sluggish kinetics. The high energy barrier attributed to conversions between oxygen molecules diffused from the air and hydroxide ions in the electrolyte at the thin layer of the electrode leads to low charge/discharge energy efficiency and insufficient cycle stability hindering the commercialization of rechargeable Zn-air batteries to the market. Therefore, it is necessarily required to facilitate the slow kinetics of oxygen electrocatalytic reactions by using bifunctionally active and durable oxygen electrocatalyst materials to progress the reactions at practically viable and stable rates. With the use of bifunctional oxygen catalysts, kinetics of ORR and OER can be improved, leading to enhancement of Zn-air battery performances such as higher operating voltage and longer battery cycling life. The current best-known catalysts for ORR and OER are noble metals, including platinum (Pt) and iridium (Ir), respectively. However, high cost and scarcity of the precious metal-based catalysts hinder their employment in large scale energy applications. Furthermore, the electrochemical stability of these materials is well known to be very insufficient for long term usage even under typical device operating conditions. Therefore, the development of non-precious transition metal-based electrocatalysts has significantly been a momentous research field. Along with this movement, the facile synthesis and inexpensive preparation of highly active and durable electrocatalysts will take the top priority for the fulfillment of practically available rechargeable Zn-air battery technology in a variety of energy applications from portable electronics to electric vehicles and smart grid storage systems. In this work, novel design strategies of bifunctionally active and durable electrocatalysts possessing robust three-dimensional framework with hierarchical porosity are presented. A porous structure with a large surface area is essential to improve the oxygen electrocatalysis since the oxygen reactions take place at the surface of materials, where active sites reside, and thereby the large surface indicating plenty of catalytically active sites enhances kinetics of the reactions. Additionally, the porous architecture facilitates diffusion of oxygen gas molecules during the oxygen electrocatalysis, leading to enhanced mass transport of reactants and reduced overpotentials for ORR and OER polarizations, eventually resulting in improved activities. In addition to the improvement of activities, electrochemical stability is an essential fundamental property for the rational design of electrocatalysts. Thus, the 3D porous structure must have robust framework which can endure the highly oxidative environment in OER potential range. Therefore, the work presented in this thesis is aiming for the design and engineering of hierarchically porous transition metal-based electrocatalysts involving high porosity as well as electrocatalytically robust frameworks to improve the oxygen electrocatalytic activities and durability and thereby put the rechargeable Zn-air battery technology at a commercially viable level. In the first study, a facile polymer template-derived method has been used to synthesize three-dimensionally ordered meso/macro-porous (3DOM) spinel cobalt oxide as a bifunctional oxygen electrocatalyst. Physicochemical characterizations have revealed the morphology of the designed electrocatalyst to be a hierarchically meso/macro-porous metal oxide framework. As investigated by electrochemical characterizations, 3DOM Co3O4 shows far enhanced ORR and OER activities with improved kinetics compared to the bulk material. The enhancement is majorly attributed to the five times higher specific surface area and significantly greater pore volume, leading to the increased number of catalytic active sites and facilitated diffusion of oxygen molecules into and out of the structure, respectively. Moreover, the robust frameworks of 3DOM Co3O4 helps to withstand harsh cycling environments by exhibiting significantly small performance reduction and retaining the original morphology. The improved oxygen electrocatalytic activity and durability have been well demonstrated in the rechargeable Zn-air battery system. 3DOM Co3O4 presents remarkably enhanced rechargeability over 200 cycles while retaining quite comparable operating voltage gap in comparison with the precious benchmark catalyst. In the second study, palladium (Pd) nanoparticle is deposited on the surface of 3DOM Co3O4 via a simple chemical reduction process. The morphological advantages of the 3DOM framework, as confirmed in the previous study, are expected to facilitate diffusion of oxygen molecules into and out of the structure leading to the decreased overpotentials during ORR and OER. However, using metal oxides as electrocatalysts restricts fast electron transfer leading to limited activity for oxygen catalysis due to their intrinsically low electrical conductivity. Therefore, Pd nanoparticles are introduced into 3DOM Co3O4 by expecting synergy from the combination of the morphological advantage of 3DOM architecture and the significant thermodynamic stability as well as the excellent ORR activity of palladium metal. Electrochemical characterizations have revealed that the combination demonstrates synergistically improved bifunctional electrocatalytic activity and durability. Moreover, computational simulation via density-functional-theory (DFT) verifies Pd@Co3O4(3DOM) is superior in two ways; (i) Activity-wise: the d-band center of Pd deposited on 3DOM Co3O4 was found to decrease significantly, resulting in increased electron abundance at the Fermi level, which in turn enhanced the overall electrical conductivity; (ii) Durability-wise: synergistic hybrid of Pd and 3DOM Co3O4 resulted in a significantly improved corrosion resistance, due to the much higher carbon oxidation potential and bulk-like dissolution potential of Pd nanoparticles on 3DOM Co3O4. The remarkable electrochemical activities and stabilities of Pd@3DOM-Co3O4 obtained from the half-cell testing resulted in excellent rechargeability of a prototype Zn-air battery, demonstrating the synergistic introduction of Pd into 3DOM Co3O4. In the last study, a type of metal-organic-framework (MOF) is selected as a template to synthesize MOF-based electrocatalyst possessing robust framework with multi-level porosity. Typically, MOF materials consist of metal centers linked by functional organic ligands, which gives them unique material characteristics such as high porosity and surface area, morphological and compositional flexibility, and high crystallinity. Especially, transition metal-based Prussian blue analogue (PBA) nanocubes with a chemical formula MxII[MyIII(CN)6]z▪H2O, where MII and MIII are divalent and trivalent transition metal cations, respectively, are employed as the MOF precursors due to a several material advantages such as simple precipitation synthesis, various possible compositions, and robust structure with high porosity
This book aims to discuss the cutting-edge materials and technologies for zinc-air batteries. From the perspective of basic research and engineering application, the principle innovation, research progress, and technical breakthrough of key materials such as positive and negative electrodes, electrolytes, and separators of zinc-air batteries are discussed systematically, which can be used to guide and promote the development of zinc-air battery technology. We do believe that our experiences and in-depth discussions would make this book useful for researchers at all levels in the energy area and provide them with a quick way of understanding the development of zinc-air batteries.
Electrochemical energy storage has played important roles in energy storage technologies for portable electronics and electric vehicle applications. During the past thirty years, great progress has been made in research and development of various batteries, in term of energy density increase and cost reduction. However, the energy density has to be further increased to achieve long endurance time. In this book, recent research and development in advanced electrode materials for electrochemical energy storage devices are presented, including lithium ion batteries, lithium-sulfur batteries and metal-air batteries, sodium ion batteries and supercapacitors. The materials involve transition metal oxides, sulfides, Si-based material as well as graphene and graphene composites.
Zinc air batteries have great promise as a new age energy storage device due to their environmental benignity, high energy density in terms of both mass and volume, and low cost Zinc air batteries get their high energy density by using oxygen from the air as the active material. This means that all the mass and volume that are normally required for active material in a battery are replaced by a thin gas diffusion electrode which allows for oxygen from the air to diffuse into the cell. Although this seems ideal, there are many technical challenges associated with the cell being open to the atmosphere. Some of these issues include electrolyte and electrode drying out, poor reaction kinetics involving sluggish reaction, the need for bifunctional catalysts to charge and discharge, and durability of the gas diffusion electrode itself. The bifuntional catalysts used in these systems are often platinum or other precious metals since these are commonly known to have the highest performance, however the inherent cost of these materials limits the feasibility of zinc air systems. Thus, there is a need to limit or remove the necessity for platinum carbon catalysts. There are many types of non precious metal catalysts which can be used in place of platinum, however their performance is often not as high, and the durability of these catalysts is also weak. Similar limitations on feasibility are invoked by the poor durability of the gas diffusion electrodes. Carbon corrosion occurs at the harsh caustic conditions present at the gas diffusion electrodes, and this corrosion causes catalyst dissolution. Moreover, many issues with zinc electrode fabrication limit durability and usable anode surface area within these systems. There is a need for a stable, porous, high surface area anode with good structural integrity. These issues are addressed in this work by three studies which each focuses on solving some of the issues pertaining to a crucial component of zinc air batteries, those being the gas diffusion electrode, the zinc electrode, and the bifunctional catalyst necessary for oxygen reduction reactions (ORR) and oxygen evolution reactions (OER).