Great Cycling Performance Research Articles

Tuning the morphology of argan shells-based activated carbon towards applications as an anode for lithium-ion battery

The application of carbonaceous materials other than graphite as an anode for lithium-ion batteries can generate significant advantages, mainly in terms of cost and sustainability while achieving high specific capacities. In this work, we successfully managed to tune the morphology of activated carbon prepared from argan shells to be used as an electrode material for lithium-ion batteries. Both Nanosphere-AC and Honeycomb-AC are obtained from the same precursor. The AC samples were comprehensively characterized using sorption isotherms, scanning electron microscopy, X-ray diffraction and Fourier-transforming infrared spectroscopy. Both materials were tested as anodes for lithium-ion batteries. It was found that Nanosphere-AC permitted great specific capacity (700 mAh.g−1at 50 mAh.g−1) and long-term cycling, showing no apparent capacity fade even after 200 cycles, offering promising application potential. Whereas Honeycomb-AC only achieved 220 mAh.g−1 at 50 mAh.g−1, but still exhibited great long-term cycling performance after 200 cycles and rate capability properties.

A Stable Matrix Assisting Highly Compatible and Maintainable Lithium-Garnet Interface for Solid-State Batteries.

Solid-state Li metal batteries (SSLMBs) are attractive due to their capability to simultaneously offer high energy density and high-level safety when combining Li metal anodes, solid-state electrolytes (SSEs), and high-voltage cathodes together. However, SSLMBs may well incur short circuits caused by Li dendrites penetrations, which mainly originate from the instability and poor contact between Li metal and SSEs. Herein, by taking full advantage of the reaction products of Li and Li1.3Al0.3Ti1.7(PO4)3 (LATP), a lithium-LATP composite anode (Li-LATP) is obtained, in which a stable matrix is formed to enhance the contact between Li and the garnet-type SSEs, alleviating the volume change and preserving an intact interface during the charge/discharge process. Consequently, the Li-LATP/garnet/Li-LATP symmetric cell displays a fairly low interfacial resistance of 6Ωcm2 and stable cycling performance for over 2500h with a low overpotential. Furthermore, the LiCoO2/garnet/Li-LATP full cell also shows a high discharge capacity of 159mAhg-1 and great cycling performance.

TiB4 and SrB8 monolayers: high capacity and zero strain-like anode materials for Li/Na/K/Ca ion batteries.

Storage capacity, average open circuit voltage (OCV), diffusion barrier, lattice parameter changes, etc. are key indicators of whether a material would be suitable for use as a Li-ion or non-Li-ion battery (LIB or NLIB) anode. The rapid development of 2D materials over the past few decades has opened up new possibilities for these metrics. Using first-principles calculations, we prove that two 2D materials, TiB4 and SrB8, show excellent performance in terms of the above metrics when used as anodes for LIBs or NLIBs. As detailed, TiB4 has an Li\Na\K\Ca storage capacity of 588 mA h g-1, 588 mA h g-1, 588 mA h g-1, and 1176 mA h g-1, respectively, and SrB8 has an Li\Na\K\Ca storage capacity of 308 mA h g-1, 308 mA h g-1, 462 mA h g-1, and 616 mA h g-1, respectively, and they show good electrical conductivity whether existing Li, Na, K or Ca is adsorbed or not. The diffusion barriers on both surfaces are low, indicating good rate performance. The average OCV is also very low. In particular, the lattice parameters of the two materials change very little during the embedding of Li\Na\K\Ca. For Ti9B36 the corresponding values are about 0.37% (Li), 0.33% (Na), 0.64% (K) and 0.03% (Ca), and for Sr8B64 the corresponding values are about 0.70% (Li), 0.16% (Na), 0.13% (K) and 0.004% (Ca), which imply zero strain-like character and great cycling performance. All the above results show that TiB4 and SrB8 monolayers are very promising Li\Na\K\Ca ion battery anodes.

Stainless steel corrugated web girders for composite road bridges: Optimization and parametric studies

To achieve sustainability in bridge design, it is critical to ensure both economic viability and low environmental impact. While stainless steel has great mechanical properties and life cycle performance, the material is expensive, which has limited its use in bridges. This research aims at exploring the benefits of using stainless steel corrugated web girders as an alternative to carbon steel flat web girders in composite road bridges. This concept is expected to lower the investment cost, which enables a broader utilization of the good properties offered by stainless steel. A genetic algorithm optimization routine has been developed to produce bridge designs with minimum weight, investment cost, life cycle cost (LCC), or life cycle impact. Multiple parametric studies are conducted using a simply supported reference bridge. The optimal design solutions are compared for two main design alternatives: conventional S355 flat web girders and duplex (EN 1.4162) corrugated web girders. The parametric studies consider the effects of different design parameters, including the span length, available girder depth, average daily traffic (ADT) with the corresponding indicated number of heavy vehicles in the slow lane (Nobs), and the paint maintenance schedule, on the optimal solutions. Furthermore, a sensitivity analysis is carried out to analyse the impact of inflation and discount rates on the obtained results. The results show that the concept of stainless steel corrugated web girders offers significant potential LCC and environmental impact saving for the examined span lengths, particularly in the case of deeper girders, high ADTs, and more intensive maintenance activities. Also, despite the influence of inflation and discount rates on LCC results, the studied concept consistently demonstrated favorable results.

Chemical Prelithiation/Presodiation Strategies Toward Controllable and Scalable Synthesis of Microsized Nanoporous Tin at Room Temperature for High‐Energy Sodium‐Ion Batteries

AbstractPorous Sn (PSn) has aroused extensive attention as an advanced anode for sodium‐ion batteries due to its high theoretical capacity and small volume expansion. However, as a low‐melt metal, the preparation of PSn at room temperature is a difficult problem. Herein, universal chemical prelithiation/presodiation strategies are reported to rapidly synthesize PSn from commercial Sn powders at ambient temperature. The recyclable pre‐metallation solvents are selected by redox potential analysis to react with Sn to form alloy precursors in a short time. Benefiting from the application of delithiation/desodiation agents with suitable proton concentrations, PSn perfectly inherits the Sn skeleton from precursors. With this method, porous Al, Pb, Bi, and Sb are successfully produced. Finally, the half‐cell with PSn anode prepared by presodiation strategy achieves a great rate property (663 mAh g−1 at 10 A g−1) and prominent cycling performance with 71% capacity retention after 7500 cycles (502 mAh g−1) at 5 A g−1. This work may contribute to the controllable synthesis of other porous metals at room temperature.

Modulating the surfaces functional groups and defects in carbon via salt template method for high-performance capacitor deionization

Conventional carbon-based materials have been widely applied for capacitive deionization (CDI) because of their excellent electrical conductivity and specific surface area. The surface functional group and defect of carbon materials have a critical impact on CDI performance. Hence, a hierarchical mesoporous/macropores carbon (MPC) with abundant quinone functional groups (C = O) and defects were synthesized by a salt template method. The introduction of C = O functional groups and defects not only effectively shortens the ions transport path, but also enhances the pseudocapacitive behavior of carbon materials. As a result, the MPC represents a fantastic desalting capacity of 31.3 mg g−1 for sodium salt (500 mg L–1 NaCl) at an applied voltage of 1.2 V. Meanwhile, the MPC also shows superior salt adsorption rate and great cycling performance. In addition, the desalination mechanism was analyzed in detail by systematic ex-situ measurements. Here, this work presents a novel perspective for designing high-performance carbon-based CDI electrode materials.

N, S, O Self-Doped Carbon Derived from Grapefruit Peel for High-Performance Supercapacitors.

The development of high-capacity carbon for supercapacitors is highly desirable but challenging. In this work, we design a N, S, O self-doped carbon electrode (NSOC-800) with high capacitance and good stability via the carbonization of grapefruit peel via a one-step KOH activation method without extra dopants. The existence of heteroatoms enables the NSOC-800 to have a high specific capacitance of 280 F/g and a great cycling performance, with 90.1% capacitance retention after 5000 cycles. Moreover, the symmetric supercapacitor with NSOC-800 electrodes delivers a maximum energy density of 5 Wh/kg with a power density of 473 W/kg. Such a promising method to achieve carbon materials with self-doping heteroatwoms is of great significance for developing highly efficient electrodes for energy storage devices.

Highly Conductive Iodine and Fluorine Dual-Doped Argyrodite Solid Electrolyte for Lithium Metal Batteries

Sulfide-type argyrodite solid electrolytes (SEs) with halide doping have attracted serious interest. Although other halides such as Cl and Br have been found to enhance Li-ion transport in argyrodites, the direct synthesis of efficiently conductive Li6PS5I without postprocessing has rarely been investigated. In this work, we report the one-step synthesis of highly conductive Li6PS5I with an impressive ionic conductivity of 2.5 × 10–4 S cm–1 at room temperature through a solvent-based method. Moreover, by introducing F– to partially replace I–, hybrid-doped argyrodites Li6PS5FxI1–x (x = 0.25, 0.5, 0.75) have been synthesized. Li6PS5F0.25I0.75 achieves the highest conductivity of 3.5 × 10–4 S cm–1 due to the energetic preference for anion-disordering among F–/I– and S2–, which facilitate faster Li transport as supported by density functional theory (DFT) calculations. With higher F content in argyrodites, Li6PS5F0.75I0.25 displays the best electrochemical stability toward Li metal, as evidenced by long-term stable cycling in Li symmetric cells up to 1100 h. Solid-state Li metal batteries with an active cathode of Li4Ti5O12 (LTO) display an initial specific capacity of 140 mAh g–1 and remain at 105 mAh g–1 after 200 cycles, suggesting great battery cycling performance. This research has developed new compositions in the argyrodite SE family which could lead to advancements in the development of solid-state Li metal batteries.

High-Performance Aqueous Zinc-Ion Battery Based on Laser-Induced Graphene

Zn-ion batteries (ZIBs) have a broad application prospect because of their advantages of high power, large capacity, and high energy density. However, the development of high-capacity, long-lifespan ZIBs is challenging because of the faster dendrite growth and the occurrence of the hydrogen evolution reaction. Laser-induced graphene (LIG) is a material with many defects and heteroatoms. Because of these characteristics, it plays an important role in improving nucleation. A simple and effective method for preparing LIG was proposed in this paper, and the LIG was covered on the surface of Zn foil to form a composite structure. This structure substantially reduces the nucleation overpotential of Zn and slows down the dendrite growth of Zn by improving the nucleation behavior of Zn2+. Simultaneously, the three-dimensional porous structure increases the specific surface area of the electrode, so the battery has a larger specific capacity. Compared with the bare Zn electrode, the composite electrode possesses lower overpotential and longer cycle life. In addition, the full battery using activated carbon as the active material exhibits great rate and cycle performance. This facile and scalable approach may solve the problem of Zn dendrite growth, which is crucial for the large-scale application of ZIBs.

VN quantum dots anchored N-doped carbon nanosheets as bifunctional interlayer for high-performance lithium-metal and lithium-sulfur batteries

Lithium dendrite growth and shuttling of lithium polysulfides (LiPSs) seriously hinder the industrialization of lithium-sulfur (Li-S) batteries. Herein, elaborately designed VN quantum dots anchored N-doped carbon nanosheets (VN@NC) is employed as a bifunctional separator. The strong absorption and catalytic conversion of polar VN quantum dots effectively suppress the shuttling effect of LiPSs, confirmed by experimental and theoretical calculations studies; moreover, lithiophilic VN@NC acts as Li-ion redistributor to regulate and redistribute the interfacial ionic flux, thus effectively inhibit the uncontrollable growth of Li dendrites. As a result, the Li-S cell with VN@NC interlayer delivers ultralong cycle life (0.036 % per cycle at 2C over 1000 cycles) and high-rate capability (752 mAh/g at 4C). Even with sulfur loading (5.4 mg cm−2) and lean electrolyte/sulfur (E/S) usage (4.6 μL mg−1), the pouch cell can deliver an initial areal capacity of 5.16 mAh cm−2 and still retain 4.02 mAh cm−2 at 0.1C over 50 cycles. The VN@NC-based Li-Li symmetric cells demonstrate great cycling and rate performance in protecting the Li anode. This work offers a bi-functionally integrated interlayer strategy to simultaneously suppress the shuttling of LiPSs and dendrite growth of Li anode for high-performance Li-S and Li-metal batteries.

Preparation of high performance porous carbon by microwave synergistic nitrogen/phosphorus doping for efficient removal of Cu2+ via capacitive deionization

Sargassum biochar has potential advantages as an electrode material due to its natural microscopic pore channels. However, conventional pyrolysis method is prone to thermal damage to the biochar, and incapable to form a complete pore structure resulting in poor biochar electrode performance. In this study, a strategy of microwave pyrolysis coupled with KOH activation was used to prepare nitrogen/phosphorus double-doped graded porous biochar (STC) using ammonium dihydrogen phosphate as dopant. The carbon material STC-1.24-800 prepared by the optimal parameters had a high specific surface area (SSA) of 1367.6 m2 g −1 and a total pore volume of 1.499 cm3 g−1. The precise inside-out heating characteristics of microwave facilitated the generation of suitable meso-micropore distribution ratios in carbon, and the graded porous structure provided abundant active sites for charge accumulation and ion diffusion. The doped nitrogen/phosphorus atoms responding to the microwave field, generated spin to promote microwave absorption, introducing surface structural defects to produce electron density differences. The change in the nature of the electron donor and its electron density enhanced the electrical conductivity and chemical stability of STC. Nitrogen/phosphorus polar surface functional groups improved hydrophilicity and wettability. STC-1.24-800 had a higher specific capacitance of 531 F g−1 and exhibits great cycle performance in capacitive deionization (CDI) applications (1.0 V, 50 mg L−1 Cu2+) as well as adsorption performance (56.16 mg g −1). The present work can provide a novel feasible idea for preparing diatomically doped graded porous biochar for CDI electrode application by microwave irradiation.

Reduced graphene oxide bubbles boosting 3D hierarchically porous carbon confined transition metal chalcogenides for high-performance Na/K-ion capacitors

Confining active nanoparticles in hierarchically porous carbon to construct intercalation and conversion coupling mechanisms is one promising way to achieve high-performance energy storage electrodes. However, this carbon with fragile mesoporous walls always suffer from fragmentation during the ion intercalation/deintercalation process, which would lead to the blocking of the whole electron transport network and the detachment of active particles, resulting in the capacity attenuation. Herein, reduced graphene oxide (rGO) bubbles are successfully introduced into N-doped hierarchically porous carbon (rGO-NPC) confined conversion-type nanoparticles to enhance their electrochemical performance. The rGO bubbles not only can afford an uninterrupted electron transport network, accelerating the reaction kinetics of active nanoparticles, and thus improving the capacity, but also can buffer the volume change of porous carbon, maintaining the integrity of electrode materials, and thereby, enhancing the cycling performance. With FeS2 as an example, when employed in Na/K-ion capacitors (SICs/KICs), the FeS2@rGO-NPC electrode can reach a high maximum energy/power density (110 Wh kg−1/20935 W kg−1 for SICs and 134 Wh kg−1/17973 W kg−1 for KICs) with a great cycling performance (82%/91% of capacitance retentions at 2 A g−1 after 10000/15000 cycles for SICs/KICs). This work indicates a promising way for designing porous carbon-based anodes with high-performance for alkali metal ions storage.

Insights into the regulation of energy storage behaviors of antimonene in aqueous electrolytes

Advanced secondary energy storage technologies and key components are crucial to the efficient use of energy resources. Layered antimonene can facilitate ions transport and intercalation. However, the electrochemical mechanism of antimonene is very much a gray area. Herein, we show that the electrolyte ions can make appreciable differences in the energy storage behavior of antimonene. Accordingly, a high value of 599 F g−1 can be obtained by scanning antimonene electrode in 1 M H2SO4 at a rate of 5 mV s−1, which is more than twice the capacitance of those KOH, LiOH and LiCl based electrolyte systems. Systematic investigation including kinetics simulation and extrapolation of surface charge suggests a mixture of surface-controlled and battery-like Faradaic responses of antimonene in acid electrolyte. Electrochemical quartz crystal microbalance (EQCM) combined with first-principles calculation further reveals that hydrated H+ is expected to access the “inner” surface sites of antimonene and thus insert or intercalate into the antimonene nanosheets. Notably, an asymmetric supercapacitor composed of antimonene positrode and carbon nanotube negatrode exhibits a wide operating voltage of 1.8 V, a relatively high energy density of 46 Wh Kg−1 at a power density of 450 W Kg−1 and great cycling performance (capacitance retention of up to 112.7% after 5000 cycles, 1.5 A g−1). The paper offers fundamental insights into the influence of electrolyte ions on the electrochemical behavior of 2D Xenes and pushes back the frontiers of designing energy storage systems.

Constructing Highly Conductive and Thermomechanical Stable Quasi‐Solid Electrolytes by Self‐Polymerization of Liquid Electrolytes within Porous Polyimide Nanofiber Films

AbstractSolid electrolytes are being considered as an effective solution to replace liquid ones for building safer batteries, but they suffer either low ionic conductivity or large contact ohmic impedance. Here, a highly conductive and thermomechanically stable quasi‐solid electrolytes (QSE) by self‐polymerization of a commercially available liquid electrolytes (1,3‐dioxolane (DOL), 1,2‐dimethoxyethane (DME), lithium trifluoromethane sulfonimide (LiTFSI) and LiPF6) at room temperature in a porous polyimide nanofiber film are reported. LiPF6 initiates the ring‐opening reaction of DOL and LiTFSI promotes the self‐polymerization to form poly‐DOL (PDOL), while the plasticizer of DME solidifies the PDOL. On the other hand, polyimide has a great affinity with PDOL that facilitates to form stable QSE network. As a result, the QSE film shows a high room‐temperature ionic conductivity of 2.9 × 10−3 S cm−1, a high mechanical strength of 31 MPa, and high heat resistance to 160 °C. The LiFePO4||QSE||Li batteries with a high cathode loading of ≈18.7 mg cm−2 show great cycling performance and stable electrode/electrolyte interfaces at a high current rate of 0.5 C with a capacity retention of 91.8% over 200 cycles at room temperature.

Synthesis of Needle-like Nanostructure Composite Electrode of Co3O4/rGO/NF for High-Performance Symmetric Supercapacitor

In this work, a hierarchical electrode structure of cobaltosic oxide (Co3O4) growing on a reduced graphene oxide (rGO)-covered nickel foam (NF) substrate (named Co3O4/rGO/NF) is fabricated by a facile hydrothermal and subsequent annealing process. Thousands of nanoneedle units uniformly arranged on the surface of the rGO sheet stimulate the evident increase in the specific surface area and thus produce more active sites. Because of the special hierarchical structure, the Co3O4/rGO/NF electrode shows a high specific capacitance of 1400 F g−1 at 1 A g−1 and retains 58% capacitance even when the current density increases to 30 A g−1. In addition, a symmetric supercapacitor based on the Co3O4/rGO/NF electrode is assembled, exhibiting high specific capacitance of 311 F g−1 at 1 A g−1, as well as remarkable power density and energy density (40.67 Wh kg−1 at 12 kW kg−1). The device also demonstrates a great cycling performance after 10,000 cycles under the current density of 10 A g−1, acquiring 89.69% capacitance retention of the initial state. The accessible synthetic method and superior electrochemical performance of the Co3O4/rGO/NF composite electrode implicate its extensive application prospects in terms of new energy storage.

Highly Dispersive Co@N‐C Catalyst as Freestanding Bifunctional Cathode for Flexible and Rechargeable Zinc–air Batteries

The design of efficient cathode with great cycle performance, high flexibility, and low cost is essential for the commercialization of zinc–air battery (ZAB). Herein, we report the exploration of freestanding bifunctional cathode with rationally designed structures, namely, tiny Co nanoparticles embedded in N‐doped carbon nanofiber aerogels, which have desired features including uniform Co dispersity, balanced distribution of N‐C species, hierarchically porous structure with increased fraction of meso‐ to micropores, and moderate amounts of defects. Accordingly, the as‐fabricated cathodes exhibit positive half‐wave potential of 0.82 V for oxygen reduction and small overpotential of 350 mV at 10 mA cm−2 for oxygen evolution, respectively, which deliver smaller reversible oxygen electrode index (0.76 V) than the commercial Pt/C+RuO2 (0.80 V) and most Co‐based electrocatalysts ever reported. Impressively, the as‐constructed liquid rechargeable ZAB behaves high peak power density (160 mW cm−2), large specific capacity (759.7 mAh g−1 at 10 mA cm−2, tested after 120 h of OCV tests), and robust stability over 277 h. Moreover, the as‐assembled quasi‐solid‐state ZAB using such freestanding cathode represents excellent mechanical flexibility and outstanding cycle performance, regardless of being serviced under extremely bending conditions from 0° to 180°, underscoring their promising applications as durable bifunctional cathode for portable metal–air batteries.

Superior Rate Mesoporous Carbon Sphere Array Composite via Intercalation and Conversion Coupling Mechanisms for Potassium‐Ion Capacitors

AbstractCarbonaceous materials have been usually adopted as the anode for high energy density potassium‐ion hybrid capacitors (KICs) owing to their low voltage plateau, high conductivity, and excellent electrochemical compatibility. The improvements of their specific capacity and sluggish intercalation mechanism are still challenges to further boost the energy density of KICs while maintaining high power density and long cycle life. Herein, a N‐doped mesoporous carbon sphere array composite is developed by a dual‐templates method. The N‐doped carbon sphere array with interpenetrated macro‐ and meso‐pores facilitates the fast electron transport and rapid K+ diffusion. The uniformly introduced Co3O4 nanoparticles (NPs) confined in the array enable a kinetically boosted conversion reaction for excess and fast K+ storage. The partially oxidized Co NPs can efficiently enhance the conductivity of the entire composite. By introducing this optimized conversion capacity from encapsulated Co3O4 NPs, the composite with intercalation and conversion coupling mechanisms displays superior capacity and cycle life. The assembled KICs exhibit high energy/power densities (148 Wh kg−1/124 W kg−1) and great cycling performance (94% after 5000 cycles, 0.5 A g−1). This promising strategy demonstrates an example for carbonaceous composite anode with synergistic K+ storage hybrid mechanism toward high performance KICs.

Hydrangea-like NiMoO4-Ag/rGO as Battery-type electrode for hybrid supercapacitors with superior stability

It is a great challenge to design electrode materials with good stability and high specific capacitance for supercapacitors. Herein, a three-dimensional (3D) hydrangea-like NiMoO4 micro-architecture with Ag nanoparticles anchored on the surface has been designed by adding EDTA-2Na, which was assembled with reduced graphene oxide (rGO) and named as NiMoO4-Ag/rGO composite. Benefiting from the synergetic contributions of structural and componential properties, NiMoO4-Ag/rGO composite exhibits a high specific capacitance of 566.4 C g−1 at 1 A g−1, and great cycling performance with 90.5% capacitance retention after 1000 cycles at 10 A g−1. The NiMoO4-Ag/rGO electrode shows an enhanced cycling stability due to the two-dimensional towards two-dimensional (2D-2D) interface coupling between rGO and NiMoO4 nanosheets, and the stable 3D hydrangea-like micro-architecture. Moreover, NiMoO4-Ag/rGO with 5–15 nm pore structure and enhanced conductivity exhibits improved charge transfer and ions diffusion. Besides, NiMoO4-Ag/rGO//AC capacitor displays an outstanding energy density of 40.98 Wh kg−1 at 800 kW kg−1, and an excellent cycling performance with 73.3% capacitance retention at 10 A g−1 after 8000 cycles. The synthesis of NiMoO4-Ag/rGO composite can provide an effective strategy to solve the poor electrochemical stability and slow electron/ion transfer of NiMoO4 material as supercapacitors electrode.

GaP-TiO₂-C Nanocomposite as High-Performance Sodium-Ion Batteries Anode.

GaP-TiO₂-C composites with three different C concentrations are synthesized via a high-energy mechanical milling. The analysis of the structural characteristics of GaP-TiO₂-C using X-ray diffraction and high-resolution transmission electron microscopy reveals that the nanosized GaP and TiO₂ crystallites are uniformly distributed in the amorphous C matrix. The GaP-TiO₂-C(20%) composite exhibits a high Na storage capacity of 266 mAh g-1 at the current density of 0.1 A g-1 after 100 cycles, and the remarkable rate capability of 224 mAh g-1 even at the higher current density of 10 A g-1. In addition, the GaP-TiO₂-C(20%) composite presents great cycling performance and the capacity of 213 mAh g-1 at the current density of 0.5 A g-1 after 300 cycles. The outstanding cycling performance and rate capability of GaP-TiO₂-C(20%) anode can be attributed to the favorable morphology of GaP-TiO₂-C composite that accommodates large volume changes during cycling.

Hollow Co3O4-x nanoparticles decorated N-doped porous carbon prepared by one-step pyrolysis as an efficient ORR electrocatalyst for rechargeable Zn-air batteries

Composites of cobalt oxides and nitrogen-doped porous carbon, as electrocatalysts for oxygen reduction reaction (ORR), offer considerable potential in new-style energy conversion and storage devices. Herein, a straightforward method for production of N-doped porous carbon (Co3O4-‍x@N–C) decorated by hollow Co3O4-x nanoparticles with oxygen vacancies has been studied by one-step pyrolysis of Co-doped quinone-amine polymer in gas mixture of NH3 and Ar. The nanosized CoO/Co3O4 heterostructure can boost the electron transport, while the hollow structure can ensure the structural and chemical stability of the catalyst, and the oxygen vacancy can change the surface electron structure and lower the activation energy barrier for oxygen reduction. Consequently, the as-prepared catalyst Co3O4-x@N–C exhibits excellent ORR catalytic performance (E1/2 = 0.845 V vs. RHE), exceeding that of Pt/C and most recently reported ORR catalysts. The Zn-air batteries assembled with Co3O4-x@N–C present a high open circuit potential (1.524 V), a large peak power density (105.2 mW cm−‍2) and great discharge-charge cycling performance, superior to the Zn-air batteries assembled with Pt/C. The excellent electrocatalytic performances of Co3O4-x@N–C make it an ideal alternative for precious metal catalyst (Pt/C) in rechargeable Zn-air batteries.