RESUMEN
Catalysts for zinc-air batteries (ZABs) must be stable over long-term charging-discharging cycles and exhibit bifunctional catalytic activity. In this study, by doping nitrogen-doped carbon (NC) materials with three metal atoms (Fe, Ni, and Cu), a single-atom-distributed FeNiCu-NC bifunctional catalyst is prepared. The catalyst includes Fe(Ni-doped)-N4 for the oxygen evolution reaction (OER), Fe(Cu-doped)-N4 for the oxygen reduction reaction (ORR), and the NiCu-NC catalytic structure for the oxygen reduction reaction (ORR) in the nitrogen-doped carbon nanoparticles. This single-atom distribution catalyst structure enhances the bifunctional catalytic activity. If a trimetallic single-atom catalyst is designed, it will surpass the typical bimetallic single-atom catcalyst. FeNiCu-NC exhibits outstanding performance as an electrocatalyst, with a half-wave potential (E1/2) of 0.876 V versus RHE, overpotential (Ej = 10) of 253 mV versus RHE at 10 mA cm-2, and a small potential gap (ΔE = 0.61 V). As the anode in a ZAB, FeNiCu-NC can undergo continuous charge-discharged cycles for 575 h without significant attenuation. This study presents a new method for achieving high-performance, low-cost ZABs via trimetallic single-atom doping.
RESUMEN
The distinctive characteristics of alloy catalysts, encompassing composition, structure, and modifiable adsorption sites, present significant potential for the development of highly efficient electrocatalysts for oxygen evolution/reduction reactions [oxygen evolution reactions (OERs)/oxygen reduction reactions (ORRs)]. Machine learning (ML) methods can quickly establish the relationship between material features and catalytic activity, thus accelerating the development of alloy electrocatalysts. However, the current abundance of features presents a crucial challenge in selecting the most pertinent ones. In this study, we explored seven intrinsic features directly derived from the material's structure, with a specific focus on the chemical environment of active sites and their nearest neighbors. An accurate and efficient ML model to predict potential bifunctional oxygen electrocatalysts based on the intrinsic features of AB-type alloy active sites and intermediate free energies in the OERs/ORRs was established. These features possess clear physical and chemical meanings, closely linked to the electronic and geometric structures of active sites and neighboring atoms, thereby providing indispensable insights for the discovery of high-performance electrocatalysts. The ML model achieved R2 scores of 0.827, 0.913, and 0.711 for the predicted values of the three intermediate (OH, O, OOH) free energies, with corresponding mean absolute errors of 0.175, 0.242, and 0.200 eV, respectively. These results indicate that the ML model exhibits high accuracy in predicting the intermediate free energies. Furthermore, the ML model exhibited a prediction efficiency 150,000 times faster than traditional density functional theory calculations. This work will offer valuable insights and a framework for facilitating the rapid design of potential catalysts by ML methods.
RESUMEN
The electrochemical conversion of oxygen holds great promise in the development of sustainable energy for various applications, such as water electrolysis, regenerative fuel cells, and rechargeable metal-air batteries. Oxygen electrocatalysts are needed that are both highly efficient and affordable, since they can serve as alternatives to costly precious-metal-based catalysts. This aspect is particularly significant for their practical implementation on a large scale in the future. Herein, highly porous polyhedron-entrapped metal-organic framework (MOF)-assisted CoTe2/MnTe2 heterostructure one-dimensional nanorods were initially synthesized using a simple hydrothermal strategy and then transformed into ZIF-67 followed by tellurization which was used as a bifunctional electrocatalyst for both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). The designed MOF CoTe2/MnTe2 nanorod electrocatalyst exhibited superior activity for both OER (η = 220 mV@ 10 mA cm-2) and ORR (E1/2 = 0.81 V vs RHE) and outstanding stability. The exceptional achievement could be primarily credited to the porous structure, interconnected designs, and deliberately created deficiencies that enhanced the electrocatalytic activity for the OER/ORR. This improvement was predominantly due to the enhanced electrochemical surface area and charge transfer inherent in the materials. Therefore, this simple and cost-effective method can be used to produce highly active bifunctional oxygen electrocatalysts.
RESUMEN
Rational design and facile preparation of high-performance carbon-based eletrocatalysts for both oxygen reduction and evolution reactions (ORR and OER) is crucial for practical applications of rechargeable zinc-air batteries. Inspired by the fact that the metallic Co catalysis on the formation of carbon nanotubes (CNTs), this work develops a facial compression-pyrolysis route to synthesize a mesoporous waffle-like N-doped carbon framework with embedded Co nanoparticles (Co@pNC) using a Co metal-organic framework and melamine as precursors. The unique porous waffle-like carbon framework is built up of interwoven N-doped CNTs and graphene nanosheets, which offers abundant catalytic-active sites and rapid diffusion channels for intermediates and electrolyte. The optimized Co@pNC shows excellent bifunctional ORR/OER electrocatalytic activity in alkaline media with a half-wave potential (E1/2) of 0.85 V for ORR and a small potential gap of 0.70 V between ORR E1/2 and OER potential at 10 mA cm-2. Its assembled battery exhibits a peak power density up to 150.3 mW cm-2, an energy density of 928 Wh kgZn-1 and superb rate capability. It highlights a facile component and architecture strategy to design high-performance carbon-based eletrocatalysts.
RESUMEN
Rechargeable zinc-air batteries (ZABs) require bifunctional electrocatalysts presenting high activity in oxygen reduction/evolution reactions (ORR/OER), but the single-site metal-N-C catalysts suffer from their low OER activity. Herein, we designed a series of single-site Fe-N-C catalysts, which present high surface area and good conductivity by incorporating into mesoporous carbon supported on carbon nanotubes, to study the doping effect of N and P on the bifunctional activity. The additional P-doping dramatically increased the content of active pyridine-N and introduced P-N/C/O sites, which not only act as extra active sites but also regulate the electron density of Fe centers to optimize the absorption of oxygenated intermediates, thereby ultimately improving the bifunctional activity of Fe-N-C sites. The optimized catalyst displayed a half-wave potential of 0.882 V for ORR and a low overpotential of 365 mV at 10 mA cm-2 for OER, which significantly outperforms the counterpart without P, as well as noble-metal-based catalysts. The ZABs with air cathodes containing the N,P-co-doped catalysts exhibited a high peak power density of 201 mW cm-2 and a long cycling stability beyond 600 h. Doping has shown to be an effective way to optimize the performance of single-site catalysts in bifunctional oxygen electrocatalysis, which can be extended to other catalyst systems.
RESUMEN
Developing high-performance non-noble metal bifunctional oxygen reduction and evolution reaction electrocatalysts is a critical factor for the commercialization of rechargeable Zn-air batteries. Herein, Co/Co-N/Co-O rooted on reduced graphene oxide (rGO) hybrid boron and nitrogen codoped carbon (BCN) nanotube arrays (BCN/rGO-Co) is prepared by facile low-temperature precross-linking and high-temperature pyrolysis treatment. Benefit from the synergistic effect of its B/N codoping, Co/Co-N/Co-O bifunctional active sites, 3D hybrid porous structure of BCN nanotubes, and highly conductive rGO sheets. The obtained BCN/rGO-Co exhibits superior bifunctional oxygen catalytic activity with a positive ORR half-wave potential (0.85 V) and a low OER potential (1.61 V) at 10 mA cm-2. Additionally, the BCN/rGO-Co-based liquid Zn-air batteries displays a large peak power density of 157 mW cm-2, and a long charge/discharge cycle stability of 200 h, outdoing the commercial Pt/C+Ru/C catalyst.
RESUMEN
Currently, it is critical but a tricky point to develop economical, high-efficiency, and durable non-precious metal electrocatalysts towards oxygen reduction and oxygen evolution reaction (ORR/OER) in rechargeable Zn-air batteries. Herein, N, Mn-codoped three-dimensional (3D) fluffy porous carbon nanostructures encapsulating FeCo/FeCoP alloyed nanoparticles (FeCo/FeCoP@NMn-CNS) are prepared by one-step pyrolysis of the metal precursors and polyinosinic acid. The optimized hybrid nanocomposite (obtained at 800 °C, named as FeCo/FeCoP@NMn-CNS-800) exhibits outstanding catalytic performance in the alkaline electrolyte with a half-wave potential (E1/2) of 0.84 V for the ORR and an overpotential of 325 mV towards the OER at 10 mA cm-2. Impressively, the FeCo/FeCoP@NMn-CNS-800-assembled rechargeable Zn-air battery presents an open-circuit voltage of 1.522 V (vs. RHE), a peak power density of 135.0 mW cm-2, and long-term durability by charge-discharge cycling for 200 h, surpassing commercial Pt/C + RuO2 based counterpart. This work affords valuable guidelines for exploring advanced bifunctional ORR and OER catalysts in rational construction of high-quality Zn-air batteries.
RESUMEN
It is today advanced that the development of a free-standing (binderless) air cathode via direct growth of nonprecious metal electrocatalysts onto the surface of the conductive collector would be a cutting-edge strategy to reduce the interfacial resistance, improve the mechanical stability, and reduce the final weight and the cost of manufacturing. Here, for Zn-air batteries (ZABs), we propose an innovative binderless noble-metal-free hierarchical nanostructured bifunctional air cathode in which high-density MnOx nanorods (NRs) are directly grown on carbon nanotubes (CNTs) themselves synthesized on a microfibrous carbon paper (CP) substrate. All carbon/MnOx air cathodes achieved specific capacities very close to the theoretical value of 820 mAh gZn-1. A very stable voltage gap between the charge and discharge processes along hundred cycles was obtained, demonstrating the stability and good bifunctional electrocatalytic activities of these cathodes toward the oxygen reduction reaction/oxygen evolution reaction in a real ZAB device. As a proof-of-concept for handheld electronic applications, a ZAB assembled with CP/MnOx NRs as the air electrode and a Zn plate anode operated a timer for 14 days successfully, whereas two ZAB-based CNTs/MnOx cathodes connected in series powered a 2 V light-emitting diode (LED) bulb and a 3 V multimeter. The proposed strategy and results may pave the way for the rational design of hierarchical free-standing bifunctional electrocatalysts for ZABs, other metal-air batteries, and fuel cells.
RESUMEN
The rechargeable Zn-air batteries as an environmentally friendly sustainable energy technology have been extensively studied. However, it is still a challenge to develop non-noble metal bifunctional catalysts with high oxygen reduction as well as oxygen evolution reaction (ORR and OER) activity and superior durability, which limit the large-scale application of rechargeable Zn-air batteries. Herein, we synthesized an ultrastable FeCo bifunctional oxygen electrocatalyst on Se-doped CNTs (FeCo/Se-CNT) via a gravity guided chemical vapor deposition (CVD) strategy. The catalyst exhibits excellent ORR (E1/2 = 0.9 V) and OER (overpotential at 10 mA cm-2 = 340 mV) properties simultaneously, surpassing commercial Pt/C and RuO2/C catalysts. More importantly, the catalyst shows an unordinary stability, that is, is no obvious decrease after 30K cycles accelerated durability test for ORR and OER processes. The small potential gap (0.75 V) represents superior bifunctional ORR and OER activities of the FeCo/Se-CNT catalyst. The FeCo/Se-CNT catalyst possesses outstanding electrochemical performance for the rechargeable liquid and flexible all-solid-state Zn-air batteries, for example, a high open circuit voltage (OCV) and peak power density of 1.543 and 1.405 V and 173.4 and 37.5 mW cm-2, respectively.
RESUMEN
The inferior stability of bifunctional oxygen electrocatalysts in the air cathode is one of the main obstacles that impedes the commercialization of zinc-air batteries (ZABs). This work describes a self-assembly technique combined with subsequent calcination to prepare a bifunctional oxygen electrocatalyst of graphite nanoarrays-confined Fe and Co single-atoms within graphene sponges (FeCo-NGS). Specifically, graphene sponges overspread with graphite nanoarrays as a structure regulation, which can prevent the metal single-atoms from aggregating and accelerate the mass/electron transfer, provides a guarantee for the long-term operation. Furthermore, M-N4 (M = Fe/Co) as the intrinsic activity regulation can effectively drive the heterogeneous oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalytic processes. Thanks to the rationally designed regulations, FeCo-NGS shows both extraordinary electrocatalytic activity for ORR and OER, even outperforming commercial Pt/C and IrO2. Remarkably, ZABs with FeCo-NGS air cathode demonstrate a record-breaking cycle lifetime of more than 1500 h (over 9000 cycles) at 10 mA cm-2 with a small charge-discharge gap.
RESUMEN
LaMnO3 perovskite is one of the most promising catalysts for oxygen reduction reaction (ORR) in metal-air batteries and can be compared to Pt/C. However, the low catalytic activity toward oxygen evolution reaction (OER) limits its practical application in rechargeable metal-air batteries. In this work, the MnO2/La0.7Sr0.3MnO3 hierarchical core-shell composite materials with a special interface structure have been designed via the selective dissolution method. The core of La0.7Sr0.3MnO3 particles is wrapped by the porous and loose MnO2 nanoparticles. The as-prepared MnO2/La0.7Sr0.3MnO3 materials have excellent catalytic activity toward ORR/OER and are used as bifunctional oxygen electrocatalysts for metal-air batteries. Based on results of transmission electron microscopy, X-ray photoelectron spectroscopy, valence-band spectroscopy, and O2 temperature-programmed desorption analysis, we conclude that the bifunctional catalytic activity of the MnO2/La0.7Sr0.3MnO3 materials can be effectively promoted due to the specific interface structure between the La1-xSrxMnO3 core and the MnO2 shell. This can be attributed to three aspects: (a) the electronic conductivity, which is beneficial for providing the faster charge-transfer paths and kinetics at the oxide/solution interface than that of the MnO2 sample; (b) the enhancement of oxygen adsorption capacity due to surface defects (oxygen vacancies) and chemical adsorption, which is helpful to improve the reaction kinetics during the process of oxygen catalysis; and (c) the tuning of oxygen adsorption ability via the moderate Mn-O bond strength, which may be conducive to getting for obtain an enhanced Mn-O bond strength on the surfaces for ORR and a weakened Mn-O bond in the lattice for OER.
RESUMEN
The future of electrochemical energy storage spotlights on the designed formation of highly efficient and robust bifunctional oxygen electrocatalysts that facilitate advanced rechargeable metal-air batteries. We introduce a scalable facile strategy for the construction of a hierarchical three-dimensional sulfur-modulated holey C2N aerogels (S-C2NA) as bifunctional catalysts for Zn-air and Li-O2 batteries. The S-C2NA exhibited ultrahigh surface area (â¼1943 m2 g-1) and superb electrocatalytic activities with lowest reversible oxygen electrode index â¼0.65 V, outperforms the highly active bifunctional and commercial (Pt/C and RuO2) catalysts. Density functional theory and experimental results reveal that the favorable electronic structure and atomic coordination of holey C-N skeleton enable the reversible oxygen reactions. The resulting Zn-air batteries with liquid electrolytes and the solid-state batteries with S-C2NA air cathodes exhibit superb energy densities (958 and 862 Wh kg-1), low charge-discharge polarizations, excellent reversibility, and ultralong cycling lives (750 and 460 h) than the commercial Pt/C+RuO2 catalysts, respectively. Notably, Li-O2 batteries with S-C2NA demonstrated an outstanding specific capacity of â¼648.7 mA h g-1 and reversible charge-discharge potentials over 200 cycles, illustrating great potential for commercial next-generation rechargeable power sources of flexible electronics.
RESUMEN
Rational design of optimal bifunctional oxygen electrocatalyst with low cost and high activity is greatly desired for realization of rechargeable Zn-air batteries. Herein, we fabricate mesoporous thin-walled CuCo2O4@C with abundant nitrogen-doped nanotubes via coaxial electrospinning technique. Benefiting from high catalytic activity of ultrasmall CuCo2O4 particles, double active specific surface area of mesoporous nanotubes, and strong coupling with N-doped carbon matrix, the obtained CuCo2O4@C exhibits outstanding oxygen electrocatalytic activity and stability, in terms of a positive onset potential (0.951 V) for oxygen reduction reaction (ORR) and a low overpotential (327 mV at 10 mA cm-2) for oxygen evolution reaction (OER). Significantly, when used as cathode catalyst for Zn-air batteries, CuCo2O4@C also displays a low charge-discharge voltage gap (0.79 V at 10 mA cm-2) and a long cycling life (up to 160 cycles for 80 h). With desirable architecture and excellent electrocatalytic properties, the CuCo2O4@C is considered a promising electrocatalyst for Zn-air batteries.
RESUMEN
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 (â¼0.80 V at 25 mA cm-2), superior reversibility, and stability exceeding prolonged charge-discharge cycles have been attained in rechargeable Zn-air batteries with a three-electrode system. The origin of the electrocatalytic activity of P,S-CNS was elucidated by density functional theory analysis for both oxygen reactions. This work stimulates an innovative prospect for the enrichment of rechargeable Zn-air battery viable for commercial applications such as armamentaria, smart electronics, and electric vehicles.