Atomically Dispersed Transition Metal-Nitrogen-Carbon Bifunctional Oxygen Electrocatalysts for Zinc-Air Batteries: Recent Advances and Future Perspectives (original) (raw)
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Angewandte Chemie (International ed. in English), 2015
The lack of high-efficient, low-cost, and durable bifunctional electrocatalysts that act simultaneously for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is currently one of the major obstacles to commercializing the electrical rechargeability of zinc-air batteries. A nanocomposite CoO-NiO-NiCo bifunctional electrocatalyst supported by nitrogen-doped multiwall carbon nanotubes (NCNT/CoO-NiO-NiCo) exhibits excellent activity and stability for the ORR/OER in alkaline media. More importantly, real air cathodes made from the bifunctional NCNT/CoO-NiO-NiCo catalysts further demonstrated superior performance to state-of-the-art Pt/C or Pt/C+IrO2 catalysts in primary and rechargeable zinc-air batteries.
Energy Materials, 2023
The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) for dual-functional non-precious metal electrocatalysts are promising alternatives for Pt/Ru-based materials in rechargeable zinc-air batteries (ZABs). However, how to achieve dual-functional oxygen electrocatalytic activity on single-component catalysts and identify the sites responsible for ORR and OER still face many challenges. Herein, an efficient and stable dual-functional electrocatalyst is fabricated by a two-step hydrothermal method with iron phthalocyanine (FePc) π-π stacking on nickel-iron selenide layered hydroxide derivatives (Se/Ni3Se4/Fe3O4). The as-prepared multi-component catalyst (named as FePc/Se@NiFe) exhibits better oxygen electrocatalytic properties than Pt/Ru-based catalysts, with a half-wave potential (E1/2) of 0.90 V and an overpotential of 10 mA cm-2 (Ej10) of 320 mV. More importantly, chronoamperometry (I-T) and accelerated durability tests (ADT) show the unordinary stability of the catalyst. Both physical characterization and experimental results verify that the Fe-N4 moieties and Ni3Se4 crystalline phase are the main active sites for ORR and OER activities, respectively. The small potential gap (ΔE = Ej10 - E1/2 = 0.622 V) represents superior dual-functional activities of the FePc/Se@NiFe catalyst. Subsequently, the ZABs assembled using FePc/Se@NiFe exhibit excellent performances. This study offers a promising design concept for promoting further development of high-performance ORR and OER electrocatalysts and their application in ZAB.
ChemElectroChem, 2021
Rechargeable zinc-air batteries (RZABs) are one of the most promising next-generation energy-storage technologies for stationary applications (home and industry), wearable and portable electronics, and transportation (including electric vehicles) due to their high energy density, environmental friendliness, safety, and low cost. However, RZABs still face serious challenges (such as sluggish oxygen reactions, poor durability, inferior reversibility of the zinc anode, and low cell energy efficiency) that conspire against their widespread commercialization. The reactions that occur at the three key components of the RZAB (air cathode, zinc anode, and electrolyte) cooperatively conspire against its performance. Thus, this review focuses on the bifunctional electrocatalytic events at the cathode (i. e., oxygen reduction reaction (ORR) and oxygen evolution reaction (OER)). That is in addition to the recent developments aimed at mitigating the performance-limiting events at the anode and the electrolytes. This review directs the attention of researchers and users to the critical areas for the development of the next-generation RZABs.
ACS nano, 2016
Rational design of efficient and durable bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalysts is critical for rechargeable metal-air batteries. Here, we developed a facile strategy for fabricating three-dimensional phosphorus and sulfur codoped carbon nitride sponges sandwiched with carbon nanocrystals (P,S-CNS). These materials exhibited high surface area and superior ORR and OER bifunctional catalytic activities than those of Pt/C and RuO2, respectively, concerning its limiting current density and onset potential. Further, we tested the suitability and durability of P,S-CNS as the oxygen cathode for primary and rechargeable Zn-air batteries. The resulting primary Zn-air battery exhibited a high open-circuit voltage of 1.51 V, a high discharge peak power density of 198 mW cm(-2), a specific capacity of 830 mA h g(-1), and better durability for 210 h after mechanical recharging. An extraordinary small charge-discharge voltage polarization...
ChemElectroChem, 2021
Developing high performance nonprecious metal-based electrocatalysts has become a critical first step towards commercial applications of metal-air batteries. Herein, nanocomposites based on Co/Co 2 P nanoparticles encapsulated within hierarchically porous N, P, S co-doped carbon are prepared by controlled pyrolysis of zeolitic imidazolate frameworks (ZIF-67) and poly (cyclotriphosphazene-co-4,4'-sulfonyldiphenol) (PZS). The resulting Co/Co 2 P@NPSC nanocomposites exhibit apparent oxygen reduction reaction (ORR) and evolution reaction (OER) catalytic performance, and are used as the reversible oxygen catalyst for zinc-air batteries (ZABs). Density functional theory (DFT) calculations exhibit that Co 2 P could provide active sites for the ORR and promote the conversion between the adsorbed intermedi-ates, and porous N,P,S co-doped carbon with Co 2 P nanoparticles also improves the exposure of actives sites and endows charge transport. Liquid-state ZABs with Co/ Co 2 P@NPSC as the cathode catalysts demonstrate the greater power density of 198.1 mW cm À 2 and a long cycling life of 50 h at 10 mA cm À 2 , likely due to the encapsulation of Co/Co 2 P nanoparticles by the carbon shell. Solid-state ZABs also display a remarkable performance with a high peak power density of 74.3 mW cm À 2. Therefore, this study indicates the meaning of the design and engineering of hierarchical porous carbon nanomaterial as electrocatalyst for rechargeable metal-air batteries.
Molecular Catalysts for OER/ORR in Zn-Air Batteries
Catalysts, 2023
Zn–air batteries are becoming the promising power source for small electronic devices and electric vehicles. They provide a relatively high specific energy density at relatively low cost. This review presents exciting advances and challenges related to the development of molecular catalysts for cathode reactions in Zn–air batteries. Bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play the main role in improving performance of reversible fuel cell and metal–air batteries. The catalyst development strategies are reviewed, along with strategies to enhance catalyst performance by application of magnetic field. Proper design of bifunctional molecular ORR/OER catalysts allows the prolongment of the battery reversibility to a few thousand cycles and reach of energy efficiencies of over 70%.
Nano Energy, 2016
Development of efficient bifunctional electrocatalysts from earth abundant elements, simultaneously active for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), remains to be a grand challenge for electrocatalysis. Herein we firstly synthesized a new type of bifunctional catalyst (NCNT/Co x Mn 1-x O) consisting of non-spinel cobalt-manganese oxide supported on N-doped carbon nanotubes through a simple non-surfactant assistant hydrothermal method. This hybrid catalyst exhibits much higher OER activity than that of IrO 2 , and comparable ORR activity to Pt/C with identical onset potential (0.96 V) in alkaline media. Furthermore, the NCNT/Co x Mn 1-x O catalyst was studied as a cathode in both primary and rechargeable zinc-air batteries demonstrating similar performance to commercial Pt/C or (Pt/C+IrO 2), respectively. Primary zinc-air battery tests show a gravimetric energy density of 695 Wh kg zn-1 , and the rechargeable battery exhibits a high round-trip efficiency evidenced by a low discharge-charge voltage gap (0.57 V) at a current density of 7 mA cm-2 .
Nanoscale, 2014
A nickel-doped cobalt oxide spinel structure is a promising non-precious metal electrocatalyst for oxygen evolution and oxygen reduction in rechargeable metal-air batteries and water electrolyzers operating with alkaline electrolytes. One dimensional NiCo 2 O 4 (NCO) nanostructures were prepared by using a simple electrospinning technique with two different metal precursors (metal nitrate/PAN and metal acetylacetonate/PAN). The effect of precursor concentration on the morphologies was investigated.
Advanced Functional Materials, 2018
Here first a 2D dual-metal (Co/Zn) and leaf-like zeolitic imidazolate framework (ZIF-L)-pyrolysis approach is reported for the low-cost and facile preparation of Co nanoparticles encapsulated into nitrogen-doped carbon nanotubes (Co-N-CNTs). Importantly, the reasonable Co/Zn molar ratio in the ZIF-L is the key to the emergence of the encapsulated microstructure. Specifically, high-dispersed cobalt nanoparticles are fully encapsulated in the tips of N-CNTs, leading to the full formation of highly active CoN -C moie-ties for oxygen reduction and evolution reactions (ORR and OER). As a result, the obtained CoN -CNTs present superior electrocatalytic activity and stability toward ORR and OER over the commercial Pt/C and IrO 2 as well as most reported metal-organic-framework-derived catalysts, respectively. Remarkably, as bifunctional air electrodes of the Zn-air battery, it also shows extraordinary charge-discharge performance. The present concept will provide a guideline for screening novel 2D metal-organic frameworks as precursors to synthesize advanced multifunctional nanomaterials for cross-cutting applications.