Electrocatalysts For Rechargeable Zinc-air Batteries Research Articles

Graphene-supported Fe/Ni single atoms and FeNi alloy nanoparticles as bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries

The development of inexpensive and high-performance bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is of crucial significance for rechargeable metal-air batteries, but remains challenging. Herein, we report an ingenious bifunctional oxygen electrocatalyst integrating ZIF-derived carbon-anchored Fe/Ni single atoms, FeNi alloy nanoparticles, and graphene support (denoted as Fe/Ni-NC||FeNi@G). Synergizing highly active Fe single atoms for the ORR and highly efficient FeNi alloy nanoparticles for the OER, the as-constructed Fe/Ni-NC||FeNi@G catalyst exhibits outstanding bifunctionality; the potential gap between the OER potential at 10 mA cm–2 and the ORR half-wave potential is only 0.618 V, outperforming the benchmark Pt/C + Ir/C catalyst and most transition metal-based bifunctional catalysts reported in the literature. More importantly, the Fe/Ni-NC||FeNi@G-driven zinc-air battery (ZAB) delivers a maximum power density of ∼200 mW cm–2, a specific capacity of 876 mAh g–1, and excellent cycling stability with negligible voltage decay up to 500 hours (3000 cycles). This work provides an effective approach to designing highly efficient non-noble metal multifunctional catalysts for practical applications in rechargeable metal-air batteries.

1,2,4-triazole-assisted metal-organic framework-derived nitrogen-doped carbon nanotubes with encapsulated Co4N particles as bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries

The design of high-performance oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) dual-functional catalysts is not only important for the further applications of zinc-air batteries (ZABs) but also a major challenge in the field of energy conversion. The cheap 1,2,4-triazole (1,2,4-TZ) can be decomposed easily by heat, making it a high research value in carbon catalysts derived from metal-organic frameworks (MOFs). Here, Co4N particles encapsulated at the top of N-doped carbon nanotubes (Co4N@NCNTs) were conveniently prepared by 1,2,4-TZ-assisted pyrolysis of Co-MOF-74 for the first time. Owing to the excellent activity of Co4N particles and the highly graphitized N-doped carbon nanotubes (NCNTs), Co4N@NCNTs obtained at 900 °C (Co4N@NCNT-900) exhibited astonishing catalytic performance in both ORR and OER, and high reversible oxygen bifunctional activity (ΔE = 0.685 V). Moreover, Co4N@NCNT-900 displayed a larger discharge power density (122 mW cm−2), a better specific capacity (811.8 mAh g−1), and more excellent durability during the ZAB test, implying that Co4N@NCNT-900 can act as a bifunctional high active catalyst in ZABs.

N, S codoped carbon matrix-encapsulated CoFe/Co0.2Fe0.8S heterostructure as a highly efficient and durable bifunctional oxygen electrocatalyst for rechargeable zinc-air batteries

The realization of durable and efficient oxygen evolution reactions (OER) at large current densities and low overpotentials is of significant importance but remains a great challenge. In this study, a CoFe/Co0.2Fe0.8S@NS-CNTs/CC (CF/CFS@NS-CNTs/CC) heterogeneous structure was fabricated by isolating CoFe/Co0.2Fe0.8S (CF/CFS) particles locked in nitrogen/sulfur codoped carbon nanotubes (NS-CNTs). Appreciable oxygen evolution reaction activity and durability was achieved with an ultralow overpotential of 110 mV at 10 mA•cm−2. The operation was stable for 300 h at a current density of 500 mA•cm−2. The structure was then assembled into a zinc-air battery (ZAB), which delivered a high power density of 194 mW•cm−2, a specific capacity of 837.3 mAh•gZn-1, and stable operation for 788 h without obvious voltage attenuation and altered morphology. The electronic interactions were studied by X-ray photoelectron spectroscopy (XPS), which revealed that both the bimetal components and the synergistic effect at the interface stimulated the transfer of Co and Fe sites to higher chemical valence states. Theoretical calculations indicated that the synergistic effect of the bimetal components, build-in interfacial potential, and surface chemical reconstruction adjusted the Fermi level to optimize the thermodynamic formation of O* to OOH*, thus enhancing the intrinsic activity.

Experimental and theoretical insights into cobalt nanoparticles encapsulated in N- and S-codoped carbon as advanced bifunctional electrocatalyst for rechargeable zinc-air batteries

Experimental and theoretical insights into cobalt nanoparticles encapsulated in N- and S-codoped carbon as advanced bifunctional electrocatalyst for rechargeable zinc-air batteries

Simultaneously Engineering the Synergistic-Effects and Coordination-Environment of Dual-Single-Atomic Iron/Cobalt-sites as a Bifunctional Oxygen Electrocatalyst for Rechargeable Zinc-Air Batteries

Simultaneously Engineering the Synergistic-Effects and Coordination-Environment of Dual-Single-Atomic Iron/Cobalt-sites as a Bifunctional Oxygen Electrocatalyst for Rechargeable Zinc-Air Batteries

Tunable phosphorization degree of CoxPy@N,P-doped carbon as a highly-active bifunctional electrocatalyst for rechargeable zinc–air batteries

CoxPy@NPPC was developed by precise control the degree of phosphorylation in one-step carbonization of CoCo-PBA and MPSA. The prepared nanocatalyst can be used as a highly-active bifunctional electrocatalyst for rechargeable zinc–air batteries.

N,S co-doped porous carbon with Co9S8 prepared with a Co-FF-derived Co3O4 template: a bi-functional electrocatalyst for rechargeable zinc-air batteries.

To achieve broad commercialization of rechargeable metal-air batteries, the development of non-precious metal-based bi-functional oxygen electrocatalysts is critical. In this study, we prepared N,S co-doped porous carbon materials containing Co9S8 nanoparticles (Co9S8/NSC) through a one-step pyrolysis process. The process involved the pyrolysis of a polydopamine (PDA) coated Co-formic acid framework (Co-FF) derived Co3O4 and thiourea. The improved catalyst Co9S8/NSC-1 exhibited satisfactory long-term durability and superior oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity, the half-wave potential (E1/2) of the ORR reached 0.83 V, and the OER overpotential at 10 mA cm-2 (η10) was 300 mV. The zinc-air battery (ZAB) based on Co9S8/NSC-1 assembly had a maximum power density of 102.0 mW cm-2 and the cycle life reached 500 cycles. The material preparation method was simple, environmentally friendly and inexpensive, providing a feasible strategy for the development of non-precious metal-based electrocatalysts.

Iron phthalocyanine coupled with nickel-iron selenide layered hydroxide derivative as dual-functional oxygen electrocatalyst for rechargeable zinc-air batteries

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.

Hybrid Carbon Sphere Chain-MnO2 Nanorods as Bifunctional Oxygen Electrocatalysts for Rechargeable Zinc-Air Batteries.

It is now recognized that the development of self-supported and efficient bifunctional air cathodes via the direct growth of earth-abundant catalysts onto the surface of the conductive collector would be a cutting-edge strategy to reduce interfacial resistance, enhance the mechanical tenure, and reduce the final weight and cost of manufacturing of rechargeable Zn-air batteries (ZABs). This work reports an innovative self-supported precious metal-free electrode, comprising carbon sphere chains (CSCs) directly grown onto a carbon paper (CP) substrate, wherein the CSCs have a functionalized surface bearing carbon nanobud defects, oxygen functional groups, and high-density MnO2 hierarchical nanorods (NRs), uniformly coating the surface of CSCs. Not only is the metal-free functionalized CSC catalyst functional for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) but its combination with MnO2 NRs impressively enhances the ORR/OER activities. A homemade ZAB assembled with functionalized CSC/MnO2 air cathode can successfully power a timer for a period of 17 days with no voltage loss, whereas two series-connected ZABs can light up 39 red light-emitting diode (LED) bulbs. The self-supported and earth-abundant-based CSC/MnO2 materials open up an opportunity for lightweight and cost-effective ZABs and metal-air batteries in general.

Co-modified polyoxovanadoborates derived Co/BN-CNT/VN based bifunctional electrocatalysts for rechargeable zinc-air batteries

Rational design of high-performance bifunctional electrocatalysts to accelerate the sluggish oxygen reduction reactions (ORR) and oxygen evolution reactions (OER) in rechargeable Zn–air batteries remain an enduring challenge. The construction of multicomponent catalysts is a promising solution to achieve this goal. Herein, B and N co-doped interconnecting graphite carbon and carbon nanotube with the decoration of Co and vanadium nitride (VN) nanoparticles (Co/BN-CNT/VN) are synthesized using Co-modified polyoxovanadoborates as precursors. The optimized composite achieves superior bifunctional oxygen electrocatalytic activity and stability, which is comparable to noble metal catalysts and reported bifunctional electrocatalysts. Specifically, the half-potential of ORR reaches 0.85 V, and the overpotential of OER is low to 296 mV at a current density of 10 mA cm−2. Strikingly, zinc–air batteries assembled based on Co/BN-CNT/VN demonstrate a small charge–discharge voltage gap of 0.873 V, a remarkable peak-power density of 156.3 mW cm−2, and outstanding cycling durability (∼1000 cycles at 10 mA cm−2). This work affords a new alternative strategy to create cost-effective and high-potency bifunctional oxygen electrocatalysts for advanced air batteries.

Y and Fe co-doped LaNiO3 perovskite as a novel bifunctional electrocatalyst for rechargeable zinc-air batteries

Perovskite oxides are widely regarded as the promising air electrode catalytic materials for zinc-air batteries (ZABs). In the present work, A-site Y and B-site Fe co-doped La0.85Y0.15Ni0.7Fe0.3O3 perovskite catalyst was prepared by self-propagating high-temperature synthesis, and this material was evaluated as a bifunctional electrocatalyst for ZABs. The effect of co-doping on crystal structure and reaction activities, which can promote oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), was investigated. Results show that Y and Fe co-doping substantially improved the ORR and OER of LaNiO3. In comparison with LaNiO3, the ORR performance of La0.85Y0.15Ni0.7Fe0.3O3 exhibited a higher limiting current density (3.8 mA cm−2 at 0.4 V vs. RHE) and more positive onset potential (0.75 V vs. RHE) at 1600 rpm. It also had an excellent OER performance of 1.74 V vs. RHE at 10 mA cm−2. When La0.85Y0.15Ni0.7Fe0.3O3 was used as an air electrode catalyst for ZABs, it exhibited a high power density of 93.6 mW cm−2, which increased by 84.8% compared with that of LaNiO3. Moreover, the full cell with La0.85Y0.15Ni0.7Fe0.3O3 air electrode catalyst was operated for more than 80 h, maintaining good stability. Therefore, La0.85Y0.15Ni0.7Fe0.3O3 can be used as a promising bifunctional air electrode catalyst for ZABs. The characterization analysis reveals that A-site Y and B-site Fe co-doped catalyst transforms crystal structure from trigonal system to cubic system, retain the valence state of Ni3+ and increases the contents of O22−/O−, and these properties are more conducive for LaNiO3 catalysis.

Cuboid-like phosphorus-doped metal–organic framework-derived CoSe2 on carbon cloth as an advanced bifunctional oxygen electrocatalyst for rechargeable zinc-air batteries

Zinc-air batteries (ZABs) are regarded as attractive devices for electrochemical energy storage and conversion due to their outstanding electrochemical performance, low price, and high safety. However, it remains a challenge to design a stable and efficient bifunctional oxygen catalyst that can accelerate the reaction kinetics and improve the performance of ZABs. Herein, a phosphorus-doped transition metal selenide/carbon composite catalyst derived from metal-organic frameworks (P-CoSe2/C@CC) is constructed by a self-supporting carbon cloth structure through a simple solvothermal process with subsequent selenization and phosphatization. The P-CoSe2/C@CC exhibits a low overpotential of 303.1 mV at 10 mA cm−2 toward the oxygen evolution reaction and an obvious reduction peak for the oxygen reduction reaction. The abovementioned electrochemical performances for the P-CoSe2/C@CC are attributed to the specific architecture, the super-hydrophilic surface, and the P-doping effect. Remarkably, the homemade zinc-air battery based on our P-CoSe2/C@CC catalyst shows an expected peak power density of 124.4 mW cm−2 along with excellent cycling stability, confirming its great potential application in ZABs for advanced bifunctional electrocatalysis.

Nitrogen-doped carbon fibers loaded with Co/Co2Mn3O8 alloy nanoparticles as bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries

The lack of low-cost and high-activity bifunctional electrocatalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is an important factor restricting the massive application of rechargeable zinc-air batteries (ZABs). Herein, nitrogen-doped carbon fibers (NCFs) loaded with Co/Co2Mn3O8 alloy nanoparticles (Co/Co2Mn3O8@NCFs) were reported as a bifunctional oxygen electrocatalyst for rechargeable ZABs. The hierarchical porous structure of NCFs and strong synergetic coupling between Co/Co2Mn3O8 alloys and Co-Nx sites accelerated the kinetics of ORR reaction. The abundant lattice oxygen and N-doped sites promoted the efficient OER process. Benefiting from the above advantages, a rechargeable ZAB assembled with Co/Co2Mn3O8@NCFs delivered an excellent energy density of 968.10 Wh kg−1 (normalized to the mass of consumed zinc) and outstanding stable cyclability (steady cycle charge and discharge at 10 mA cm−2 for 120 h), surpassing state-of-the-art Pt/C catalyst (830.86 Wh kg−1/75 h). This study demonstrated the potential value of Co/Co2Mn3O8 alloys in energy conversion and storage.

N, S co-doped carbon with embedment of FeNi alloy as bifunctional oxygen electrocatalysts for rechargeable Zinc-air batteries

Zinc-air batteries (ZABs) have sparked great interest, but their wide-ranging applications are limited by sluggish cathode reactions (ORR and OER). In this work, a multifunctional 3D catalyst (FeNi alloy/porous carbon) was easily fabricated by introducing Fe3+ and Ni2+ to modulate in-situ vapor phase grown carbon nanotubes. The as-prepared catalyst FNSNC73-800 displays abundant mesoporous, massive structural defects, and multiple active sites, which greatly facilitate the transport of oxygen species and charge transfer during the reaction. Due to the excellent ORR and OER performance, FNSNC73-800 shows a narrow voltage gap (ΔE) of 0.76 V, which is superior to recent reports. Notably, the secondary zinc-air battery with this catalyst displays a high-peak power density (210 mW cm−2), while maintaining an ultra-low potential gap (0.74 V) after a long-term charge-discharge cycle of 200 h. This effort presents a facile strategy for designing economical and efficient 3D catalysts for zinc-air batteries and more energy devices.

Co/N nanoparticles supported on a C3N4/polydopamine framework as a bifunctional electrocatalyst for rechargeable zinc-air batteries

• An electrocatalyst with Co NPs on a graphitized N -doped carbon framework are prepared. • The synthetic strategy avoids the excessive growth and aggregation of metal nanoparticles. • The catalyst has an improved ORR and OER activity compared with Pt/C and Ir/C, respectively. • The synthetic catalyst-containing ZABs present an outstanding discharging performance. Metal N -doped carbons (M N C) and specifically cobalt-based N -doped carbons (Co N C) have attracted extensive attention as suitable multifunctional catalysts. Their high catalytic activity, originating from the strong coupling effect of Co with N, lead to the formation of active sites with suitable binding energies for promoting the discharging and charging reactions. Herein, we propose the synthesis of an efficient bifunctional electrocatalyst (ZIFCNDA) prepared by the introduction of Co ions during the polymerisation of dopamine, which lead to the direct doping of a carbon framework and the localized growth of Co-based MOFs polyhedrons, generating Co-based nanoparticles (Co NPs) upon pyrolysis. The C 3 N 4 -controlled polydopamine growth formed thin graphitized carbon nanosheets which can facilitate the transfer of electrons to the catalytically active sites. The ZIFCNDA catalyst was able to efficiently catalyse both the oxygen reduction (ORR) and oxygen evolution (OER) reactions). The ZAB containing the developed catalyst presented a stable discharge voltage of 1.1 V at a high current density of 10 mA cm −2 with higher stability and longer cycle life compared to their counterparts constructed using Pt/C and Ir/C in air–cathode. This study illustrates a platform to enhance the catalytic activity of the ORR and OER catalyst via promoting the formation of well distributed cobalt active sites, achieved due to the insertion of cobalt ions during the polymerization process of dopamine, instead of on a previously prepared framework and their application for rechargeable metal–air batteries.

In-situ construction of Ruddlesden-Popper/perovskite heterointerface induces efficient bifunctional oxygen electrocatalyst for rechargeable zinc-air batteries

• Hierarchical RP-PSNC/P-PNC nanofibers with core-shell structure are synthesized. • RP-PSNC/P-PNC displays efficient bifunctional catalytic activities. • The interfacial vacancies and hierarchical structure increase the catalytic activities. • RP-PSNC/P-PNC-based batteries exhibit excellent power density and durability. Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are the prerequisite reactions in rechargeable zinc-air batteries (ZABs), but their kinetics are usually slow. In order to develop energy-efficient ZABs, it is highly desirable to pursue bifunctional catalysts with the accelerated reaction kinetics and the reduced overpotentials. Transition metal oxides are expected as promising alternatives to replace noble metal-based catalysts, but their catalytic activities are still far from desirable. Herein, we propose a modified layer of Ruddlesden-Popper perovskite (Pr,Sr) 2 Ni 0.5 Co 0.5 O 4-δ (RP-PSNC) on the perovskite PrNi 0.5 Co 0.5 O 3-δ (P-PNC) nanofiber by a simple impregnation method, receiving a (Pr,Sr) 2 Ni 0.5 Co 0.5 O 4-δ / PrNi 0.5 Co 0.5 O 3-δ (RP-PSNC/P-PNC) heterostructured nanofibers. The RP-PSNC/P-PNC hybrid catalyst exhibits a small overpotential and an excellent stability due to the large number of vacancies in the two-phase interface. The RP-PSNC/P-PNC-based liquid rechargeable ZAB reaches a power density of 145 mW cm −2 , and 230 h of long-term cycle performance. When assembled into flexible ZABs, it can also reach a power density of 51 mW cm −2 and a stable open circuit voltage (∼1.35 V) for 44 h. These results indicate that the bifunctional electrocatalyst of heterostructured RP-PSNC/P-PNC provides a new path for the modification of perovskites through multi-phase catalysts system, and has great potential in rechargeable ZABs and other energy conversion devices.

Ball mill-assisted synthesis of NiFeCo-NC as bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are the core of clean energy technology. Oxygen electrocatalysts based on earth-abundant metals are of prime importance. Trimetallic catalysts have demonstrated reliable activities but their average performance, difficult synthesis techniques, and high synthesis costs limit their widespread use. Herein, the facile ball milling technique is introduced as an efficient and low-cost method for the synthesis of catalysts based on trimetallic NiFeCo nanometer-scale particles distributed over a CNT-graphene-like (NiFeCo-NC) structure. NiFeCo-NC is synthesized instantaneously from ball milling of melamine with industrial carbon nanotubes (CNTs) along with trimetallic particles. Results demonstrate that the NiFeCo-NC2 catalyst, synthesized from 2 g of melamine per 1 g of each metal salt, performed well in both ORR and OER. The potential difference between the half-wave reduction potential of the ORR (E1/2) and the oxidation potential at 10 mA cm−2 (E10) in OER reveals a better performance of the NiFeCo-NC2 as a bifunctional catalyst than other synthesized materials and reference catalysts. A zinc-air battery (ZAB) having the NiFeCo-NC2 catalyst performs better than the batteries using other catalysts. The NiFeCo-NC2 catalyst also exhibits excellent methanol tolerance, revealing its applicability for direct methanol fuel cell (DMFC) applications. Ball milling offers a simple, effective, versatile, and cost-effective mechano-chemical procedure for the concomitant one-pot mixing-synthesis of materials.

FeS2/CoS2 nanoparticles supported on N, S co-doped carbon nanotubes as advanced bifunctional electrocatalysts for rechargeable zinc-air batteries

Designing a highly active and durable bifunctional catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is of crucial importance to the commercial development of zinc-air batteries (ZABs). Herein, a facile strategy is employed to synthesize FeS2/CoS2 nanoparticles anchored on N, S co-doped carbon nanotubes (NSCNTs). The obtained FeS2/CoS2/NSCNTs displays superior bifunctional electrocatalytic activities for both ORR and OER in an alkaline electrolyte, with a relative low potential difference value of only 0.66 V. Importantly, FeS2/CoS2/NSCNTs based solid-state ZAB endows a high specific capacity of 786.9 mAh g−1 at the current density of 10 mA cm−2, outstanding long-term charge-discharge stability over 70 h, as well as excellent flexibility. This research provides a new pathway for the construction of robust and low-cost bifunctional catalysts for ZABs.

Iron-nickel alloy nanoparticles encapsulated in nitrogen-doped carbon nanotubes as efficient bifunctional electrocatalyst for rechargeable zinc-air batteries

In this work, we present an efficient bifunctional electrocatalyst comprising iron-nickel (FeNi) alloy nanoparticles confined in nitrogen-doped carbon nanotubes (denoted FeNi-NCNT) for zinc-air batteries. The FeNi-NCNT electrocatalyst is fabricated by anion-exchange of nickel(II) ion/zinc(II) ion-2,4,6-tris-(di(pyridin-2-yl)amino)-1,3,5-triazine complex with ferricyanide anion followed by mixing with melamine and then carbonization. The resultant FeNi-NCNT electrocatalyst displays excellent bifunctional activity with a low reversible oxygen electrode index of 0.725 V. The rechargeable aqueous zinc-air battery fabricated with FeNi-NCNT air cathode manifests both high specific capacity (819 mAh g−1Zn at 5.0 mA cm−2) and long cycle life (1500 cycles/1000 h at 10 mA cm−2, 600 cycles/400 h at 25 mA cm−2, and 165 cycles/110 h at 50 mA cm−2). Moreover, flexible solid-state zinc-air battery assembled with FeNi-NCNT air cathode can deliver a specific capacity of 765 mAh g−1Zn at 5.0 mA cm−2, a power density of 84.8 mW cm−2, and a cycle life of 110 h (330 cycles) at 2.0 mA cm−2.

Interface Engineering of CoO/N-Doped Carbon Nanomaterials as a Bifunctional Electrocatalyst for Rechargeable Zinc-Air Batteries

Robust bifunctional and highly efficient electrocatalysts for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) exhibits great prospect in a zinc-air battery (ZAB). Here, we demonstrated a facile route to synthesize a bifunctional electrocatalyst with CoO nanoparticles embedded in N-doped carbon by interface engineering. The precursor which consists of ball-milled polyaniline (BM-PANI), carbon nanotubes (CNTs) and cobalt acetate tetrahydrate (Co(Ac)2·4H2O) was obtained via homogeneous mixture in the presence of ethanol, and thus, satisfactory interface was formed. After calcination, the synthesized CoO/N-doped carbon composite material presents a half-wave potential of 0.818 V for ORR and an overpotential of 0.417 V at 10 mA cm−2 for OER, which endows it a power density of 92.04 mW cm−2 in a homemade rechargeable ZAB and a high stability outperforming commercial Pt/C. This work highlights the mixture of precursors by interface engineering, thus improving the synergistic effect between metal oxide and carbon and elevating the electrocatalytic activity.