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1.
Rechargeable flexible solid Zn‐air battery, with a high theoretical energy density of 1086 Wh kg?1, is among the most attractive energy technologies for future flexible and wearable electronics; nevertheless, the practical application is greatly hindered by the sluggish oxygen reduction reaction/oxygen evolution reaction (ORR/OER) kinetics on the air electrode. Precious metal‐free functionalized carbon materials are widely demonstrated as the most promising candidates, while it still lacks effective synthetic methodology to controllably synthesize carbocatalysts with targeted active sites. This work demonstrates the direct utilization of the intrinsic structural defects in nanocarbon to generate atomically dispersed Co–Nx–C active sites via defect engineering. As‐fabricated Co/N/O tri‐doped graphene catalysts with highly active sites and hierarchical porous scaffolds exhibit superior ORR/OER bifunctional activities and impressive applications in rechargeable Zn‐air batteries. Specifically, when integrated into a rechargeable and flexible solid Zn‐air battery, a high open‐circuit voltage of 1.44 V, a stable discharge voltage of 1.19 V, and a high energy efficiency of 63% at 1.0 mA cm?2 are achieved even under bending. The defect engineering strategy provides a new concept and effective methodology for the full utilization of nanocarbon materials with various structural features and further development of advanced energy materials.  相似文献   

2.
Metal–organic frameworks (MOFs) and MOF‐derived materials have recently attracted considerable interest as alternatives to noble‐metal electrocatalysts. Herein, the rational design and synthesis of a new class of Co@N‐C materials (C‐MOF‐C2‐T) from a pair of enantiotopic chiral 3D MOFs by pyrolysis at temperature T is reported. The newly developed C‐MOF‐C2‐900 with a unique 3D hierarchical rodlike structure, consisting of homogeneously distributed cobalt nanoparticles encapsulated by partially graphitized N‐doped carbon rings along the rod length, exhibits higher electrocatalytic activities for oxygen reduction and oxygen evolution reactions (ORR and OER) than that of commercial Pt/C and RuO2, respectively. Primary Zn–air batteries based on C‐MOF‐900 for the oxygen reduction reaction (ORR) operated at a discharge potential of 1.30 V with a specific capacity of 741 mA h gZn–1 under 10 mA cm–2. Rechargeable Zn–air batteries based on C‐MOF‐C2‐900 as an ORR and OER bifunctional catalyst exhibit initial charge and discharge potentials at 1.81 and 1.28 V (2 mA cm–2), along with an excellent cycling stability with no increase in polarization even after 120 h – outperform their counterparts based on noble‐metal‐based air electrodes. The resultant rechargeable Zn–air batteries are used to efficiently power electrochemical water‐splitting systems, demonstrating promising potential as integrated green energy systems for practical applications.  相似文献   

3.
Synergistic improvements in the electrical conductivity and catalytic activity for the oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) are of paramount importance for rechargeable metal–air batteries. In this study, one‐nanometer‐scale ultrathin cobalt oxide (CoOx) layers are fabricated on a conducting substrate (i.e., a metallic Co/N‐doped graphene substrate) to achieve superior bifunctional activity in both the ORR and OER and ultrahigh output power for flexible Zn–air batteries. Specifically, at the atomic scale, the ultrathin CoOx layers effectively accelerate electron conduction and provide abundant active sites. X‐ray absorption spectroscopy reveals that the metallic Co/N‐doped graphene substrate contributes to electron transfer toward the ultrathin CoOx layer, which is beneficial for the electrocatalytic process. The as‐obtained electrocatalyst exhibits ultrahigh electrochemical activity with a positive half‐wave potential of 0.896 V for ORR and a low overpotential of 370 mV at 10 mA cm?2 for OER. The flexible Zn–air battery built with this catalyst exhibits an ultrahigh specific power of 300 W gcat ?1, which is essential for portable devices. This work provides a new design pathway for electrocatalysts for high‐performance rechargeable metal–air battery systems.  相似文献   

4.
Proper design and simple preparation of nonnoble bifunctional electrocatalysts with high cost performance and strong durability for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is highly demanded but still full of enormous challenges. In this work, a spontaneous gas‐foaming strategy is presented to synthesize cobalt nanoparticles confined in 3D nitrogen‐doped porous carbon foams (CoNCF) by simply carbonizing the mixture of citric acid, NH4Cl, and Co(NO3)2·6H2O. Thanks to its particular 3D porous foam architecture, ultrahigh specific surface area (1641 m2 g?1), and homogeneous distribution of active sites (C–N, Co–Nx, and Co–O moieties), the optimized CoNCF‐1000‐80 (carbonized at 1000 °C, containing 80 mg Co(NO3)2·6H2O in precursors) catalyst exhibits a remarkable bifunctional activity and long‐term durability toward both ORR and OER. Its bifunctional activity parameter (ΔE) is as low as 0.84 V, which is much smaller than that of noble metal catalyst and comparable to state‐of‐the‐art bifunctional catalysts. When worked as an air electrode catalyst in rechargeable Zn–air batteries, a high energy density (797 Wh kg?1), a low charge/discharge voltage gap (0.75 V), and a long‐term cycle stability (over 166 h) are achieved at 10 mA cm?2.  相似文献   

5.
An efficient and low‐cost electrocatalyst for reversible oxygen electrocatalysis is crucial for improving the performance of rechargeable metal?air batteries. Herein, a novel oxygen vacancy–rich 2D porous In‐doped CoO/CoP heterostructure (In‐CoO/CoP FNS) is designed and developed by a facile free radicals–induced strategy as an effective bifunctional electrocatalyst for rechargeable Zn–air batteries. The electron spin resonance and X‐ray absorption near edge spectroscopy provide clear evidence that abundant oxygen vacancies are formed in the interface of In‐CoO/CoP FNS. Owing to abundant oxygen vacancies, porous heterostructure, and multiple components, In‐CoO/CoP FNS exhibits excellent oxygen reduction reaction activity with a positive half‐wave potential of 0.81 V and superior oxygen evolution reaction activity with a low overpotential of 365 mV at 10 mA cm?2. Moreover, a home‐made Zn–air battery with In‐CoO/CoP FNS as an air cathode delivers a large power density of 139.4 mW cm?2, a high energy density of 938 Wh kgZn?1, and can be steadily cycled over 130 h at 10 mA cm?2, demonstrating great application potential in rechargeable metal–air batteries.  相似文献   

6.
Rational design and synthesis of highly active and robust bifunctional non‐noble electrocatalysts for both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are urgently required for efficient rechargeable metal–air batteries. Herein, abundant MnO/Co heterointerfaces are engineered in porous graphitic carbon (MnO/Co/PGC) polyhedrons via a facile hydrothermal‐calcination route with a bimetal–organic framework as the precursor. The in situ generated Co nanocrystals not only create well‐defined heterointerfaces with high conductivity to overcome the poor OER activity but also promote the formation of robust graphitic carbon. Owing to the desired composition and formation of the heterostructures, the resulting MnO/Co/PGC exhibits superior activity and stability toward both OER and ORR, which makes it an efficient air cathode for the rechargeable Zn–air battery. Importantly, the homemade Zn–air battery is able to deliver excellent performance including a peak power density of 172 mW cm?2 and a specific capacity of 872 mAh g?1, as well as excellent cycling stability (350 cycles), outperforming commercial mixed Pt/C||RuO2 catalysts. This work highlights the synergy from heterointerfaces in oxygen electrocatalysis, thus providing a promising approach for advanced metal–air cathode materials.  相似文献   

7.
Developing non‐precious‐metal bifunctional oxygen reduction and evolution reaction (ORR/OER) catalysts is a major task for promoting the reaction efficiency of Zn–air batteries. Co‐based catalysts have been regarded as promising ORR and OER catalysts owing to the multivalence characteristic of cobalt element. Herein, the synthesis of Co nanoislands rooted on Co–N–C nanosheets supported by carbon felts (Co/Co–N–C) is reported. Co nanosheets rooted on the carbon felt derived from electrodeposition are applied as the self‐template and cobalt source. The synergistic effect of metal Co islands with OER activity and Co–N–C nanosheets with superior ORR performance leads to good bifuctional catalytic performances. Wavelet transform extended X‐ray absorption fine spectroscopy and X‐ray photoelectron spectroscopy certify the formation of Co (mainly Co0) and the Co–N–C (mainly Co2+ and Co3+) structure. As the air‐cathode, the assembled aqueous Zn–air battery exhibits a small charge–discharge voltage gap (0.82 V@10 mA cm?2) and high power density of 132 mW cm?2, outperforming the commercial Pt/C catalyst. Additionally, the cable flexible rechargeable Zn–air battery exhibits excellent bendable and durability. Density functional theory calculation is combined with operando X‐ray absorption spectroscopy to further elucidate the active sites of oxygen reactions at the Co/Co–N–C cathode in Zn–air battery.  相似文献   

8.
Searching for highly efficient bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) using nonnoble metal‐based catalysts is essential for the development of many energy conversion systems, including rechargeable fuel cells and metal–air batteries. Here, Co9–xFexS8/Co,Fe‐N‐C hybrids wrapped by reduced graphene oxide (rGO) (abbreviated as S‐Co9–xFexS8@rGO) are synthesized through a semivulcanization and calcination method using graphene oxide (GO) wrapped bimetallic zeolite imidazolate framework (ZIF) Co,Fe‐ZIF (CoFe‐ZIF@GO) as precursors. Benefiting from the synergistic effect of OER active CoFeS and ORR active Co,Fe‐N‐C in a single component, as well as high dispersity and enhanced conductivity derived from rGO coating and Fe‐doping, the obtained S‐Co9–xFexS8@rGO‐10 catalyst shows an ultrasmall overpotential of ≈0.29 V at 10 mA cm?2 in OER and a half‐wave potential of 0.84 V in ORR, combining a superior oxygen electrode activity of ≈0.68 V in 0.1 m KOH.  相似文献   

9.
Highly active and durable air cathodes to catalyze both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are urgently required for rechargeable metal–air batteries. In this work, an efficient bifunctional oxygen catalyst comprising hollow Co3O4 nanospheres embedded in nitrogen‐doped carbon nanowall arrays on flexible carbon cloth (NC‐Co3O4/CC) is reported. The hierarchical structure is facilely derived from a metal–organic framework precursor. A carbon onion coating constrains the Kirkendall effect to promote the conversion of the Co nanoparticles into irregular hollow oxide nanospheres with a fine scale nanograin structure, which enables promising catalytic properties toward both OER and ORR. The integrated NC‐Co3O4/CC can be used as an additive‐free air cathode for flexible all‐solid‐state zinc–air batteries, which present high open circuit potential (1.44 V), high capacity (387.2 mAh g?1, based on the total mass of Zn and catalysts), excellent cycling stability and mechanical flexibility, significantly outperforming Pt‐ and Ir‐based zinc–air batteries.  相似文献   

10.
Iron–nitrogen–carbon materials (Fe–N–C) are known for their excellent oxygen reduction reaction (ORR) performance. Unfortunately, they generally show a laggard oxygen evolution reaction (OER) activity, which results in a lethargic charging performance in rechargeable Zn–air batteries. Here porous S‐doped Fe–N–C nanosheets are innovatively synthesized utilizing a scalable FeCl3‐encapsulated‐porphyra precursor pyrolysis strategy. The obtained electrocatalyst exhibits ultrahigh ORR activity (E1/2 = 0.84 V vs reversible hydrogen electrode) and impressive OER performance (Ej = 10 = 1.64 V). The potential gap (ΔE = Ej = 10 ? E1/2) is 0.80 V, outperforming that of most highly active bifunctional electrocatalysts reported to date. Furthermore, the key role of S involved in the atomically dispersed Fe–Nx species on the enhanced ORR and OER activities is expounded for the first time by ultrasound‐assisted extraction of the exclusive S source (taurine) from porphyra. Moreover, the assembled rechargeable Zn–air battery comprising this bifunctional electrocatalyst exhibits higher power density (225.1 mW cm?2) and lower charging–discharging overpotential (1.00 V, 100 mA cm?2 compared to Pt/C + RuO2 catalyst). The design strategy can expand the utilization of earth‐abundant biomaterial‐derived catalysts, and the mechanism investigations of S doping on the structure–activity relationship can inspire the progress of other functional electrocatalysts.  相似文献   

11.
Obtaining bifunctional electrocatalysts with high activity for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is a main hurdle in the application of rechargeable metal‐air batteries. Earth‐abundant 3d transition metal‐based catalysts have been developed for the OER and ORR; however, most of these are based on oxides, whose insulating nature strongly restricts their catalytic performance. This study describes a metallic Ni‐Fe nitride/nitrogen‐doped graphene hybrid in which 2D Ni‐Fe nitride nanoplates are strongly coupled with the graphene support. Electronic structure of the Ni‐Fe nitride is changed by hybridizing with the nitrogen‐doped graphene. The unique heterostructure of this hybrid catalyst results in very high OER activity with the lowest onset overpotential (150 mV) reported, and good ORR activity comparable to that for commercial Pt/C. The high activity and durability of this bifunctional catalyst are also confirmed in rechargeable zinc‐air batteries that are stable for 180 cycles with an overall overpotential of only 0.77 V at 10 mA?2.  相似文献   

12.
Freestanding bifunctional electrodes with outstanding oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) properties are of great significance for zinc–air batteries, attributed to the avoided use of organic binder and strong adhesion with substrates. Herein, a strategy is developed to fabricate freestanding bifunctional electrodes from the predeposited nickel nanoparticles (Ni‐NCNT) on carbon fiber paper. The steric effect of monodispersed SiO2 nanospheres limits the configuration of carbon atoms forming 3D interconnected nanotubes with uniformly distributed NiN2 active sites. The bifunctional electrodes (Ni‐NCNT) demonstrate ideal ORR and OER properties. The zinc–air batteries assembled with Ni‐NCNT directly exhibit extremely outstanding long term stability (2250 cycles with 10 mA cm?2 charge/discharge current density) along with high power density of 120 mV cm?2 and specific capacity of 834.1 mA h g?1. This work provides a new view to optimize the distribution of active sites and the electrode structure.  相似文献   

13.
High‐performance bifunctional oxygen electrocatalysis constitutes the key technique for the widespread application of clean and sustainable energy through electrochemical devices such as rechargeable Zn–air batteries. Single‐atom electrocatalysts with maximum atom efficiency are highly considered as an alternative of the present noble‐metal‐based electrocatalysts. However, the fabrication of transition metal single‐atoms is very challenging, requiring extensive attempts of precursors with novel design principles. Herein, an all‐covalently constructed cobalt‐coordinated framework porphyrin with graphene hybridization is innovatively designed and prepared as the pyrolysis precursor to fabricate single‐atom Co–Nx–C electrocatalysts. Excellent electrochemical performances are realized for both bifunctional oxygen electrocatalysis and rechargeable Zn–air batteries with regard to reduced overpotentials, improved kinetics, and prolonged cycling stability comparable with noble‐metal‐based electrocatalysts. Design principles from multiple scales are proposed and rationalized with detailed mechanism investigation. This work not only provides a novel precursor for the fabrication of high‐performance single‐atom electrocatalysts, but also inspires further attempts to develop advanced materials and emerging applications.  相似文献   

14.
The development of rechargeable metal–air batteries and water electrolyzers are highly constrained by electrocatalysts for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). However, the construction of efficient trifunctional electrocatalysts for ORR/OER/HER are highly desirable yet challenging. Herein, hollow carbon nanotubes integrated single cobalt atoms with Co9S8 nanoparticles (CoSA + Co9S8/HCNT) are fabricated by a straightforward in situ self‐sacrificing strategy. The structure of the CoSA + Co9S8/HCNT are verified by X‐ray absorption spectroscopy and aberration‐corrected scanning transmission electron microscopy. Theoretical calculations and experimental results embrace the synergistic effects between Co9S8 nanoparticles and single cobalt atoms through optimizing the electronic configuration of the CoN4 active sites to lower the reaction barrier and facilitating the ORR, OER, and HER simultaneously. Consequently, rechargeable liquid and all‐solid‐state flexible Zn–air batteries based on CoSA + Co9S8/HCNT exhibit remarkable stability and excellent power density of 177.33 and 51.85 mW cm?2, respectively, better than Pt/C + RuO2 counterparts. Moreover, the as‐fabricated Zn–air batteries can drive an overall water splitting device assembled with CoSA + Co9S8/HCNT and achieve a current density of 10 mA cm?2 at a low voltage of 1.59 V, also superior to Pt/C + RuO2. Therefore, this work presents a promising approach to an efficient trifunctional electrocatalyst toward practical applications.  相似文献   

15.
Designing rational nanostructures of metal–organic frameworks based carbon materials to promote the bifunctional catalytic activity of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is highly desired but still remains a great challenge. Herein, an in situ growth method to achieve 1D structure‐controllable zeolitic imidazolate frameworks (ZIFs)/polyacrylonitrile (PAN) core/shell fiber (PAN@ZIFs) is developed. Subsequent pyrolysis of this precursor can obtain a heteroatom‐doped carbon nanofiber network as an efficient bifunctional oxygen electrocatalyst. The electrocatalytic performance of derived carbon nanofiber is dominated by the structures of PAN@ZIFs fiber, which is facilely regulated by efficiently controlling the nucleation and growth process of ZIFs on the surface of polymer fiber as well as optimizing the components of ZIFs. Benefiting from the core–shell structures with appropriate dopants and porosity, as‐prepared catalysts show brilliant bifunctional ORR/OER catalytic activity and durability. Finally, the rechargeable Zn‐air battery assembled from the optimized catalyst (CNF@Zn/CoNC) displays a peak power density of 140.1 mW cm?2, energy density of 878.9 Wh kgZn?1, and excellent cyclic stability over 150 h, giving a promising performance in realistic application.  相似文献   

16.
The development of highly active and stable oxygen evolution reaction (OER) electrocatalysts is crucial for improving the efficiency of water splitting and metal–air battery devices. Herein, an efficient strategy is demonstrated for making the oxygen vacancies dominated cobalt–nickel sulfide interface porous nanowires (NiS2/CoS2–O NWs) for boosting OER catalysis through in situ electrochemical reaction of NiS2/CoS2 interface NWs. Because of the abundant oxygen vacancies and interface porous nanowires structure, they can catalyze the OER efficiently with a low overpotential of 235 mV at j = 10 mA cm?2 and remarkable long‐term stability in 1.0 m KOH. The home‐made rechargeable portable Zn–air batteries by using NiS2/CoS2–O NWs as the air–cathode display a very high open‐circuit voltage of 1.49 V, which can maintain for more than 30 h. Most importantly, a highly efficient self‐driven water splitting device is designed with NiS2/CoS2–O NWs as both anode and cathode, powered by two‐series‐connected NiS2/CoS2–O NWs‐based portable Zn–air batteries. The present work opens a new way for designing oxygen vacancies dominated interface nanowires as highly efficient multifunctional electrocatalysts for electrochemical reactions and renewable energy devices.  相似文献   

17.
Mechanically stable and foldable air cathodes with exceptional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities are key components of wearable metal–air batteries. Herein, a directional freeze-casting and annealing approach is reported for the construction of a 3D honeycomb nanostructured, N,P-doped carbon aerogel incorporating in situ grown FeP/Fe2O3 nanoparticles as the cathode in a flexible Zn–air battery (ZAB). The aqueous rechargeable Zn–air batteries assembled with this carbon aerogel exhibit a remarkable specific capacity of 648 mAh g−1 at a current density of 20 mA cm−2 with a good long-term durability, outperforming those assembled with commercial Pt/C+RuO2 catalyst. Furthermore, such a foldable carbon aerogel with directional channels can serve as a freestanding air cathode for flexible solid-state Zn–air batteries without the use of carbon paper/cloth and additives, giving a specific capacity of 676 mAh g−1 and an energy density of 517 Wh kg−1 at 5 mA cm−2 together with good cycling stability. This work offers a new strategy to design and synthesize highly effective bifunctional air cathodes to be applied in electrochemical energy devices.  相似文献   

18.
Herein, an approach is reported for fabrication of Co‐Nx‐embedded 1D porous carbon nanofibers (CNFs) with graphitic carbon‐encased Co nanoparticles originated from metal–organic frameworks (MOFs), which is further explored as a bifunctional electrocatalyst for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Electrochemical results reveal that the electrocatalyst prepared by pyrolysis at 1000 °C (CoNC‐CNF‐1000) exhibits excellent catalytic activity toward ORR that favors the four‐electron ORR process and outstanding long‐term stability with 86% current retention after 40 000 s. Meanwhile, it also shows superior electrocatalytic activity toward OER, reaching a lower potential of 1.68 V at 10 mA cm?2 and a potential gap of 0.88 V between the OER potential (at 10 mA cm?2) and the ORR half‐wave potential. The ORR and OER performance of CoNC‐CNF‐1000 have outperformed commercial Pt/C and most nonprecious‐metal catalysts reported to date. The remarkable ORR and OER catalytic performance can be mainly attributable to the unique 1D structure, such as higher graphitization degree beneficial for electronic mobility, hierarchical porosity facilitating the mass transport, and highly dispersed CoNxC active sites functionalized carbon framework. This strategy will shed light on the development of other MOF‐based carbon nanofibers for energy storage and electrochemical devices.  相似文献   

19.
A critical bottleneck limiting the performance of rechargeable zinc–air batteries lies in the inefficient bifunctional electrocatalysts for the oxygen reduction and evolution reactions at the air electrodes. Hybridizing transition‐metal oxides with functional graphene materials has shown great advantages due to their catalytic synergism. However, both the mediocre catalytic activity of metal oxides and the restricted 2D mass/charge transfer of graphene render these hybrid catalysts inefficient. Here, an effective strategy combining anion substitution, defect engineering, and the dopant effect to address the above two critical issues is shown. This strategy is demonstrated on a hybrid catalyst consisting of sulfur‐deficient cobalt oxysulfide single crystals and nitrogen‐doped graphene nanomeshes (CoO0.87S0.13/GN). The defect chemistries of both oxygen‐vacancy‐rich, nonstoichiometric 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 to and much better stability than the best‐known benchmark noble‐metal catalysts. In application to quasi‐solid‐state zinc–air batteries, CoO0.87S0.13/GN as a freestanding catalyst assembly benefits from both structural integrity and enhanced charge transfer to achieve efficient and very stable cycling operation over 300 cycles with a low discharge–charge voltage gap of 0.77 V at 20 mA cm?2 under ambient conditions.  相似文献   

20.
Electrocatalysts for oxygen‐reduction and oxygen‐evolution reactions (ORR and OER) are crucial for metal–air batteries, where more costly Pt‐ and Ir/Ru‐based materials are the benchmark catalysts for ORR and OER, respectively. Herein, for the first time Ni is combined with MnO species, and a 3D porous graphene aerogel‐supported Ni/MnO (Ni–MnO/rGO aerogel) bifunctional catalyst is prepared via a facile and scalable hydrogel route. The synthetic strategy depends on the formation of a graphene oxide (GO) crosslinked poly(vinyl alcohol) hydrogel that allows for the efficient capture of highly active Ni/MnO particles after pyrolysis. Remarkably, the resulting Ni–MnO/rGO aerogels exhibit superior bifunctional catalytic performance for both ORR and OER in an alkaline electrolyte, which can compete with the previously reported bifunctional electrocatalysts. The MnO mainly contributes to the high activity for the ORR, while metallic Ni is responsible for the excellent OER activity. Moreover, such bifunctional catalyst can endow the homemade Zn–air battery with better power density, specific capacity, and cycling stability than mixed Pt/C + RuO2 catalysts, demonstrating its potential feasibility in practical application of rechargeable metal–air batteries.  相似文献   

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