Rechargeable Metal-air Batteries Research Articles

Transition Metal-Based Polyoxometalates for Oxygen Electrode Bifunctional Electrocatalysis

Polyoxometalates (POMs) with transition metals (Co, Cu, Fe, Mn, Ni) of Keggin structure and lamellar-stacked multi-layer morphology were synthesized. They were subsequently explored as bifunctional electrocatalysts for oxygen electrodes, i.e., oxygen reduction (ORR) and evolution (OER) reaction, for aqueous rechargeable metal-air batteries in alkaline media. The lowest Tafel slope (85 mV dec−1) value and the highest OER current density of 93.8 mA cm−2 were obtained for the Fe-POM electrocatalyst. Similar OER electrochemical catalytic activity was noticed for the Co-POM electrocatalyst. This behavior was confirmed by electrochemical impedance spectroscopy, where Fe-POM gave the lowest charge transfer resistance of 3.35 Ω, followed by Co-POM with Rct of 15.04 Ω, during the OER. Additionally, Tafel slope values of 85 and 109 mV dec−1 were calculated for Fe-POM and Co-POM, respectively, during the ORR. The ORR at Fe-POM proceeded by mixed two- and four-electron pathways, while ORR at Co-POM proceeded exclusively by the four-electron pathway. Finally, capacitance studies were conducted on the synthesized POMs.

Cobalt@Ruthenium Core@Shell nanoparticles embedded within nitrogen-doped carbon nanosheets as reversible oxygen electrocatalysts

Rational design and engineering of cost-effective, high-performance reversible oxygen electrocatalysts for both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is imperative in advancing the progress of rechargeable metal-air batteries (r-MABs). Herein, nanocomposites based on Co@Ru core@shell nanoparticles embedded within N-doped carbon nanosheets (Co@Ru/CS) are prepared via facile galvanic exchange reactions of RuCl3 with Co/NC and used as an effective oxygen electrocatalyst for rechargeable zinc-air battery (r-ZAB). Electrochemical studies demonstrate a remarkable bifunctional catalytic performance of Co@Ru/CS towards both ORR and OER, featuring a low potential gap (ΔE) of only 0.69 V between the OER potential (E10,OER) at 10 mA cm−2 and half-wave potential (E1/2,ORR) of ORR, which is much lower than that of commercial Pt/C + RuO2 catalysts (0.76 V). Combined studies of experimental characterizations and density functional theory calculations show that the ORR activity arises primarily from the N-doped carbon and CoNx moieties in the composites, whereas RuO2/CoOOH produced at high electrode potentials is responsible for the OER activity. Co@Ru/CS based r-ZAB exhibits an open circuit voltage of 1.447 V, specific capacity of 781 mAh gZn−1, and maximum power density of 115 mW cm−2 at 0.83 V, a performance better than that with commercial Pt/C + RuO2 (1.412 V, 760.56 mAh gZn−1, and 91 mW cm−2). Results from this research underline the substantial impact of structural engineering on optimizing the electrocatalytic activity of nanocomposites for r-MABs.

Intercalated and Surface-Adsorbed Phosphate Anions in NiFe Layered Double-Hydroxide Catalysts Synergistically Enhancing Oxygen Evolution Reaction Activity.

The oxygen evolution reaction (OER), a crucial semireaction in water electrolysis and rechargeable metal-air batteries, is vital for carbon neutrality. Hindered by a slow proton-coupled electron transfer, an efficient catalyst activating the formation of an O-H bond is essential. Here, we proposed a straightforward one-step hydrothermal procedure for fabricating PO43--modified NiFe layered double-hydroxide (NiFe LDH) catalysts and investigated the role of PO43- anions in enhancing OER. Phosphate amounts can efficiently regulate LDH morphology, crystallinity, composition, and electronic configuration. The optimized sample showed a low overpotential of 267 mV at 10 mA cm-2. Density functional theory calculations revealed that intercalated and surface-adsorbed PO43- anions in NiFe LDH reduced the Gibbs free energy in the rate-determining step of *OOH formation, balancing oxygen-containing intermediate adsorption/dissociation and promoting the OER. Intercalated phosphate ions accelerated precatalyst dehydrogenation kinetics, leading to a rapid reconstruction into active NiFe oxyhydroxide species. Surface-adsorbed PO43- interacted favorably with adsorbed *OOH on the active Ni sites, stabilizing *OOH. Overall, the synergistic effects of intercalated and surface-adsorbed PO43- anions significantly contributed to enhanced OER activity. Achieving optimal catalytic activity requires a delicate equilibrium between thermodynamic and kinetic factors by meticulously regulating the quantity of introduced PO43- ions. This endeavor will facilitate a deeper comprehension of the influence of anions in electrocatalysis for OER.

Theoretical regulating the M-site composition of Janus MXenes enables the tailoring design for highly active bifunctional ORR/OER catalysts

Rechargeable metal-air batteries generally require efficient, durable, and safe bifunctional electrocatalysts to simultaneously support oxygen reduction/evolution reactions (ORR/OER). Herein, we employed first-principles calculations to explore the structure-activity relationship between the composition control of metal atoms and the catalytic activity of Pt-doped Ti2–xMnxCO2 single-atom catalysts (SACs). The research found a clear linear relationship between the proportion of Mn and bifunctional performance, which can effectively modulate catalytic activity. Additionally, it shows excellent bifunctional catalytic activity at medium concentrations, among which the catalyst of Pt-VO-Ti0.89Mn1.11CO2 displays the lowest overpotential (ηORR/OER = 0.26/0.28 V). Attributed to the modulation of the average magnetism of Mn and the d-band center of Pt by different components, the bonding strength of the active center of Pt to adsorption intermediates is changed, resulting in the enhancement of the catalyst activity. Crucially, the molecular orbital-level bonding between the active site Pt and the adsorbed intermediate OH is clarified, shedding light on the involvement of the partially occupied antibonding state of Pt's d orbital in the activation process. The research extensively explores the control of catalyst activity through composition, offering strong support for designing and optimizing highly active Janus MXene-supported SACs.

Earthworm-Inspired Co/Co3O4/CoF2@NSC Nanofibrous Electrocatalyst with Confined Channels for Enhanced ORR/OER Performance.

The rational construction of highly active and durable oxygen-reactive electrocatalysts for oxygen reduction/evolution reaction (ORR/OER) plays a critical role in rechargeable metal-air batteries. It is pivotal to achieve optimal utilization of electrocatalytically active sites and valid control of the high specific internal surface area. Inspiration for designing electrocatalysts can come from nature, as it is full of precisely manipulated and highly efficient structures. Herein, inspired by earthworms fertilizing soil, a 3D carbon nanofibrous electrocatalyst with multiple interconnected nanoconfined channels, cobalt-based heterojunction active particles and enriched N, S heteroatoms (Co/Co3O4/CoF2@NSC with confined channels) is rationally designed, showing superior bifunctional electrocatalytic activity in alkaline electrolyte, even outperforming that of benchmark Pt/C-RuO2 catalyst. This work demonstrates a new method for porous structural regulation, in which the internal confined channels within the nanofibers are controllably formed by the spontaneous migration of cobalt-based nanoparticles under a CO2 atmosphere. Theoretical analysis reveals that constructing Co/Co3O4/CoF2@NSC electrocatalyst with confined channels can greatly adjust the electron distribution, effectively lower the reaction barrier of inter-mediate and reduce the OER/ORR overpotential. This work introduces a novel and nature-inspired strategy for designing efficient bifunctional electrocatalysts with well-designed architectures.

Optimizing Oxygen Electrode Bifunctionality with Platinum and Nickel Nanoparticle-Decorated Nitrogen-Doped Binary Metal Oxides

Developing bifunctional oxygen electrode materials with superior activity for oxygen reduction (ORR) and oxygen evolution (OER) reactions is essential for advancing regenerative fuel cell and rechargeable metal–air battery technologies. This present work deals with the synthesis and characterization of electrocatalysts containing Pt and Ni nanoparticles supported on nitrogen-doped mixed metal oxides (Mn2O3-NiO) and the systematic evaluation of their bifunctional ORR/OER performance in an alkaline medium. These electrocatalysts have been successfully synthesized by a simple and fast microwave method. PtNi/Mn2O3-NiO-N with a binary metal oxide-to-N ratio of 1:2 demonstrated the best performance among the studied materials regarding bifunctional electrocatalytic activity (∆E = 0.96 V) and robust stability.

Highly Porous Metal-Organic Framework Entrapped by Cobalt Telluride-Manganese Telluride as an Efficient Bifunctional Electrocatalyst.

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.

Single Transition-Metal Atom Anchored on a Rhenium Disulfide Monolayer: An Efficient Bifunctional Electrocatalyst for the Oxygen Evolution and Oxygen Reduction Reactions.

Developing efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) bifunctional electrocatalysts is attractive for rechargeable metal-air batteries. Meanwhile, single metal atoms embedded in 2D layered transition metal chalcogenides (TMDs) have become a very promising catalyst. Recently, many attentions have been paid to the 2D ReS2 electrocatalyst due to its unique distorted octahedral 1T' crystal structure and thickness-independent electronic properties. Here, the catalytic activity of different transition metal (TM) atoms embedded in ReS2 using the density functional theory is investigated. The results indicate that TM@ReS2 exhibits outstanding thermal stability, good electrical conductivity, and electron transfer for electrochemical reactions. And the Ir@ReS2 and Pd@ReS2 can be used as OER/ORR bifunctional electrocatalysts with a lower overpotential for OER (ηOER ) of 0.44 V and overpotentials for ORR (ηORR ) of 0.26 V and 0.27 V, respectively. The excellent catalytic activity is attributed to the optimal adsorption strength for oxygen intermediates coming from the effective modulation of the electronic structure of ReS2 after Ir/Pd doping. The results can help to deeply understand the catalytic activity of TM@ReS2 and develop novel and highly efficient OER/ORR electrocatalysts.

Excellent Bifunctional Oxygen Evolution and Reduction Electrocatalysts (5A1/5)Co2O4 and Their Tunability.

Hastening the progress of rechargeable metal-air batteries and hydrogen fuel cells necessitates the advancement of economically feasible, earth-abundant, inexpensive, and efficient electrocatalysts facilitating both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Herein, a recently reported family of nano (5A1/5)Co2O4 (A = combinations of transition metals, Mg, Mn, Fe, Ni, Cu, and Zn) compositionally complex oxides (CCOs) [Wang et al., Chemistry of Materials, 2023,35 (17), 7283-7291.] are studied as bifunctional OER and ORR electrocatalysts. Among the different low-temperature soft-templating samples, those subjected to 600 °C postannealing heat treatment exhibit superior performance in alkaline media. One specific composition (Mn0.2Fe0.2Ni0.2Cu0.2Zn0.2)Co2O4 exhibited an exceptional overpotential (260 mV at 10 mA cm-2) for the OER, a favorable Tafel slope of 68 mV dec-1, excellent onset potential (0.9 V) for the ORR, and lower than 6% H2O2 yields over a potential range of 0.2 to 0.8 V vs the reversible hydrogen electrode. Furthermore, this catalyst displayed stability over a 22 h chronoamperometry measurement, as confirmed by X-ray photoelectron spectroscopy analysis. Considering the outstanding performance, the low cost and scalability of the synthesis method, and the demonstrated tunability through chemical substitutions and processing variables, CCO ACo2O4 spinel oxides are highly promising candidates for future sustainable electrocatalytic applications.

Surface Tailoring-Modulated Bifunctional Oxygen Electrocatalysis with CoP for Rechargeable Zn-Air Battery and Water Splitting.

The transition metal phosphide (TMP)-based functional electrocatalysts are very promising for the development of electrochemical energy conversion and storage devices including rechargeable metal-air batteries and water electrolyzer. Tuning the electrocatalytic activity of TMPs is one of the vital steps to achieve the desired performance of these energy devices. Herein, we demonstrate the modulation of the bifunctional oxygen electrocatalytic activity of nitrogen-doped carbon-encapsulated CoP (CoP@NC) nanostructures by surface tailoring with ultralow amount (0.56 atomic %) of Ru nanoparticles (2.5 nm). The CoP at the core and the Ru nanoparticles on the shell have a facile charge transfer interaction with the encapsulating NC. The strong coupling of Ru with CoP@NC boosts the electrocatalytic performance toward oxygen reduction (ORR), oxygen evolution (OER), and hydrogen evolution (HER) reactions. The surface-tailored catalyst requires only 35 mV to deliver the benchmark current density of 10 mA·cm-2 for HER. A small potential gap of 620 mV between ORR and OER is achieved, making the catalyst highly suitable for the development of rechargeable zinc-air batteries (ZABs). The homemade ZAB delivers a specific capacity of 780 mA·hgZn-1 and peak power density of 175 mW·cm-2 with a very small voltaic efficiency loss (1.1%) after 300 cycles. The two-electrode water splitting cell (CoP@NC-Ru||CoP@NC-Ru) delivers remarkably low cell voltage of 1.47 V at the benchmark current density. Stable current density of 25 mA·cm-2 for 25 h without any significant change is achieved. Theoretical studies support the charge transfer interaction-induced enhanced electrocatalytic activity of the surface-tailored nanostructure.

Bifunctional 2D structured catalysts for air electrodes in rechargeable metal-air batteries

The inherent technical challenges of metal-air batteries (MABs), arising from the sluggish redox electrochemical reactions on the air electrode, significantly affect their efficiency and life cycle. Two-dimensional (2D) nanomaterials with near-atomic thickness have potential as bifunctional catalysts in MABs because of their distinct structures, exceptional physical properties, and tunable surface chemistries. In this study, the chemistry of representative 2D materials was elucidated, and the comprehensive analysis of the primary modification techniques, including geometric structure manipulation, defect engineering, crystal facet selection, heteroatom doping, single-atom catalyst construction, and composite material synthesis, was conducted. The correlation between material structure and activity is illustrated by examples, with the aim of leading the development of advanced catalysts in MABs. We also focus on the future of MABs from the perspective of bifunctional catalysts, definite mechanisms, and standard measurement. We expect this work to serve as a guide for the design of air electrode materials that can be used in MABs.

Mechanistic study of Eu single atoms occupying four vacancy centers as potential electrocatalysts for the oxygen reduction reaction.

The oxygen reduction reaction (ORR) on the oxygen electrode plays a critical role in rechargeable metal-air batteries, and the development of electrochemical energy storage and conversion technologies for the ORR is of great significance. In this study, the catalytic performance of rare earth-doped graphene (EuNxC6-x-Gra) as an electrocatalyst for the ORR was investigated. The results showed that a majority of the catalysts exhibited good ORR catalytic activity under acidic conditions, with some approaching or even surpassing commercial Pt-based catalysts (ηORR = 0.45 V). Particularly, EuN2C4-2-Gra demonstrated an ηORR of 0.38 V. It has been observed that the f-band center of Eu atoms increases with an increasing number of N atoms, and the charge distribution exhibits a "U" shape. There is a decreasing trend from N0 to N3 and an increasing trend from N4 to N6. By incorporating the proportional relationship of the adsorption free energies of reaction intermediates (ΔG*ads), a volcano diagram was constructed to rapidly assess catalytic activity. Finally, an intrinsic characteristic descriptor φ was formulated to quantitatively describe the relationship between φ and ηORR, providing a new tool for predicting and designing catalysts. This will provide guidance for the development and design of high-performance rare earth single atom catalysts.

Built-in electric field and extra electric filed in oxygen evolution reaction

Developing new green energy storage and conversion technologies is an important approach to solving energy problems. In this regard, both water splitting and rechargeable metal-air batteries have certain research value....

Non-Ir based catalysts for the electrocatalytic oxygen evolution reaction: progress and challenges

Oxygen evolution reaction (OER) electrocatalysis is the key to solve the problem of hydrogen production by hydrolyzing water and secondary metal–air batteries.

Rechargeable Zinc–Air versus Lithium–Air Battery: from Fundamental Promises Toward Technological Potentials

AbstractAs battery technologies that can potentially increase the energy density and expand application scenarios of the lithium‐ion batteries, rechargeable metal‒air batteries have attracted extensive research interests. Among a variety types of metal anodes investigated, zinc (Zn)‒air and lithium (Li)‒air batteries hold best prospects for real‐world applications and attract the most scientific community interests. It has been more than 10 years since Cho et al. first compared Li–air and Zn–air batteries, during which great progress has been made. In this review, these two representative metal‒air battery technologies are compared in view of the most recent progresses and improvements in the last decade, especially efforts that push these technologies toward real world applications. It starts with the fundamentals of Zn–air and Li–air batteries, and discusses the progress made in electrolyte design, anode protection, and cathode catalysts development. It ends with an evaluation of the current research state along with an overall future perspective. Such a comprehensive comparison of typical non‐aqueous and aqueous battery systems with a focus on practical application criteria would be a timely review of metal‒air battery development in the last decade, which shed light for fundamental and applied research, eventually leading to real‐world application.

Evaluating the Oxygen Electrode Reactions of La Single-Atom Catalysts with the N/C Coordination Effect.

There is a growing demand for bifunctional electrocatalysts for oxygen electrodes in rechargeable metal-air batteries. This article investigates the bifunctional activity of La single-atom catalysts with N/C coordination (LaNxC6-x@Gra) using density functional theory (DFT). The augmentation of N coordination will result in enhanced synthetic stability. The coordination between nitrogen and carbon (N/C) has a significant influence on the working stability of the system under consideration. In the context of active atoms, the coordination between nitrogen and carbon (N/C coordination) has a significant impact on the electronic structure. This, in turn, influences the adsorption performance and catalytic activity of the catalysts. In the case of stable coordination environments, a correlation exists between the f-orbital center (εf) and the overpotential (η) via the adsorption free energy of intermediates (ΔG*ads). This correlation serves as a useful tool for predicting catalytic performance. The LaNxC6-x@Gra exhibits remarkable bifunctional activity due to its complementary performance, with an overpotential for the oxygen reduction reaction (ηORR) of 0.66 V and an overpotential for the oxygen evolution reaction (ηOER) of 0.43 V. This makes it a promising candidate for use as a bifunctional electrocatalyst in oxygen electrodes.

NiFe Nanoparticle Nest Supported on Graphene as Electrocatalyst for Highly Efficient Oxygen Evolution Reaction.

Designing cost-efffective electrocatalysts for the oxygen evolution reaction (OER) holds significant importance in the progression of clean energy generation and efficient energy storage technologies, such as water splitting and rechargeable metal-air batteries. In this work, an OER electrocatalyst is developed using Ni and Fe precursors in combination with different proportions of graphene oxide. The catalyst synthesis involved a rapid reduction process, facilitated by adding sodium borohydride, which successfully formed NiFe nanoparticle nests on graphene support (NiFe NNG). The incorporation of graphene support enhances the catalytic activity, electron transferability, and electrical conductivity of the NiFe-based catalyst. The NiFe NNG catalyst exhibits outstanding performance, characterized by a low overpotential of 292.3mV and a Tafel slope of 48mVdec-1, achieved at a current density of 10mAcm- 2. Moreover, the catalyst exhibits remarkable stability over extended durations. The OER performance of NiFe NNG is on par withthat of commercial IrO2 in alkaline media. Such superb OER catalytic performance can be attributed to the synergistic effect between the NiFe nanoparticle nests and graphene, which arises from their large surface area and outstanding intrinsic catalytic activity. The excellent electrochemical properties of NiFe NNG hold great promise for further applications in energy storage and conversion devices.

Engineering of heterointerface of ultrathin carbon nanosheet-supported CoN/MnO enhances oxygen electrocatalysis for rechargeable Zn–air batteries

Designing bifunctional electrocatalysts with outstanding reactivity and durability towards the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) has remained a long-term aim for metal-air batteries. Achieving the high level of fusion between two distinct metal components to form bifunctional catalysts with optimized heterointerfaces and well-defined morphology holds noteworthy implications in the enhancement of electrocatalytic activity yet challenging. Herein, the fabrication of numerous heterointerfaces of CoN/MnO is successfully realized within ultrathin carbon nanosheets via a feasible self-templating synthesis strategy. Experimental results and theoretic calculations verify that the interfacial electron transfer from CoN to MnO at the heterointerface engenders an ameliorated charge transfer velocity, finely tuned energy barriers concerning reaction intermediates and ultimately accelerated reaction kinetics. The as-prepared CoN/MnO@NC demonstrates exceptional bifunctional catalytic performance, excelling in both OER and ORR showcasing a low reversible overpotential of 0.69 V. Furthermore, rechargeable liquid and quasi-solid-state flexible Zn-air batteries employing CoN/MnO@NC as the air-cathode deliver remarkable endurance and elevated power density, registering values of 153 and 116 mW cm−2 respectively and exceeding Pt/C + RuO2 counterparts and those reported in literature. Deeply exploring the effect of electron-accumulated heterointerfaces on catalytic activity would contribute wisdom to the development of bifunctional electrocatalysts for rechargeable metal-air batteries.

A facile and green strategy for mass production of dispersive FeCo-rich phosphides@N,P-doped carbon electrocatalysts toward efficient and stable rechargeable Zn-air battery and water splitting

One key step for advancing the widespread practical application of rechargeable metal-air batteries and water electrolysis fundamentally relies on the development of cost-effective multifunctional electrocatalysts toward oxygen and hydrogen-involving reactions. The present work initiates a tofu-derived one-pot strategy for green, facile, and mass production of highly active and stable catalyst toward oxygen reduction/evolution and hydrogen evolution reactions, through the preparation of Fe/Co cross-linked tofu gel and the subsequent pyrolysis. Despite the free use of additional N/P precursors or pore-forming agents, the as-prepared materials comprise highly dispersive FeCo-rich phosphides nanoparticles and porous N,P co-doped carbon network inherited from the tofu skeleton. The resultant catalysts exhibit remarkably enhanced trifunctional activities as compared to the Fe2P and Co2P counterparts, along with better long-term stabilities than the benchmark RuO2 and Pt/C catalysts. Accordingly, the as-assembled Zn-air battery delivers a large power density (174 mW cm−2) with excellent cycle stability (the gap of charge/discharge voltage@10 mA cm−2 increases by 0.01 V after 720 h of operation, vs. 0.16 V of Pt/C-RuO2 based battery after 378 h). Furthermore, the as-constructed alkaline electrolyzer just requires a small voltage of 1.55 V@10 mA cm−2, which outperforms nearly all of those of biomass-derived electrocatalysts ever reported, and that of noble metal catalysts-based electrolyzers (1.72 V@10 mA cm−2 for Pt/C-RuO2), underscoring their bright future toward commercial applications in green energy conversion devices.

3D coordination polymer derived CoNi@GO as a highly efficient OER/ORR bifunctional catalyst for Zn-air rechargeable batteries

Developing highly active and durable non-noble metal based bifunctional electrocatalysts is still a key step for rechargeable metal-air batteries. In the current work, a new three-dimensional cyanide-bridged CoNi complex {{[Ni(pn)2]3[Co(CN)6]2}·3H2O}n (pn = 1, 3-diaminopropane) was synthesized and characterized. And a bifunctional electrocatalyst CoNi@GO for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) was prepared by pyrolyzing process with graphene oxide (GO) as template and CoNi complex as precursor. Density functional theory calculations revealed that the nanostructured CoNi alloy embedded in the lamellar porous GO and there was strong synergistic coupling between the carbon based material and CoNi alloy. The as-obtained catalyst showed the outstanding electrocatalytic activity and the excellent potential difference between ORR and OER is 0.697 V versus Pt/C+RuO2 (0.708 V). The Zinc-air battery prepared with CoNi@GO as an air electrode has a small charge-discharge voltage gap of 0.91 V, a high energy efficiency of 59.5%, and could be cycled stably for more than 240 h at 10 mA cm−2. This work confirmed the feasibility of developing coordination polymer (CP) based non-noble metal bi-functional electrocatalysts for energy storage and conversion, and provided a valuable strategy for the rational design of new non-noble metal electrocatalysts in future.