Assembled Zn-air Battery Research Articles

Electro-functionalized 2D nitrogen-carbon nanosheets decorated with symbiotic cobalt single-atoms/clusters

Two-dimensional (2D) materials loaded with single atoms and clusters are being set at the forefront of catalysis due to their distinctive geometric and electronic features. However, the usually-complicated synthesis procedures impede in-depth clarification of their catalytic mechanisms. To this end, herein we developed an efficient one-step dimension-reduction carbonization strategy, with which we successfully architected a highly-efficient catalyst for oxygen reduction reaction (ORR), featured with symbiotic cobalt single atoms and clusters decorated in two-dimensional (2D) ultra-thin (3.5 nm thickness) nitrogen-carbon nanosheets. The synergistic effects of the two components afford excellent oxygen reduction activity in alkaline media (E1/2=0.823 V vs. RHE) and thereof a high power density (146.61 mW cm−2) in an assembled Zn-air battery. As revealed by theoretical calculations, the cobalt clusters can regulate electrons surrounding those individual atoms and affect the adsorption of intermediate species. As a consequence, the derived active sites of single cobalt atoms lead to a significant improvement of the ORR performance. Thus, our work may fuel interests to delicate architecture of single atoms and clusters coexisting 2D support toward optimal electrocatalytic performance.

Size tuning of vanadium nitride particles from atomic to micron level as efficient catalysts for zinc-air battery

Transition metal nitrides present superior electrocatalytic activities on the air electrode for fuel cells or metal-air batteries. Despite that, the weak intrinsic activity and ease of aggregation have hampered their catalytic kinetic properties and practical application. Herein, vanadium nitride (VN) particles of different sizes, micron to molecular level, have been fabricated using a facile, in-situ urea-nitridation method, and embedded in an N-doped graphitic carbon aerogel electrocatalyst (VN@CA), the doped material serving as an oxidation catalyst. Having a balance of atomic-level dispersed VN clusters and a high active site density, the obtained VN@CA catalytic material exhibits enhanced catalytic efficiency for the oxygen reduction reaction (ORR), the values of onset and half-wave voltages were measured to be 0.97 V and 0.90 V, respectively, compared to Pt/C (which had voltages of 0.95 V and 0.87 V). Furthermore, the assembled Zn-air battery using VN@CA as catalyst exhibits a high-power density of 176 mW cm−2, a substantial specific discharge capacity of 851 mAh gZn−1 at 20 mA cm−2, a narrow gap between charging and discharging voltages (0.73 V at 50 mA cm−2), and an excellent charge-discharge cycling stability, exceeding 270 cycles with a 66 % round-trip efficiency. This work confirms that the particle size and the density both are responsible for the enhanced electrochemical activity.

Cu-based active sites supported on nitrogen-rich polymer derived porous carbon fibers as an oxygen reduction electrocatalyst for zinc-air batteries

The rational design of electrocatalysts with highly exposed active sites and maximized active sites utilization is challenging and urgent problem. Herein, a facile strategy is employed to fabricate Cu-based active sites anchored in nitrogen doped porous carbon nanofiber as an effective and enduring oxygen reduction reaction (ORR) electrocatalyst, which is achieved by the coordination-pyrolysis way of the pre-designed covalent organic polymer (COP) precursors with unique molecular structure. Meanwhile, COP-derived N-doped carbon nanofiber could provide porous structure and facilitate the rapid mass/electron transport, which can insure the strong fastness and high reaction activity of Cu-based active sites. The as-obtained catalyst (Cu0·4/NPC) displays excellent activity (E1/2 = 0.845 V) and stability for ORR performance. Remarkably, the Cu0·4/NPC as cathode catalyst assembled Zn-air battery achieves the peak power density of 142 mA cm−2 and a large specific capacity of 829 mA h g−1 at large current. Additionally, the Cu0·4/NPC catalyst assembled in the solid Zn-air battery achieves the peak power density of 157 mA cm−2. This work offers great opportunity to design advanced ORR catalysts with high density and maximum utilization of active sites.

Multifunctional carbon armor: Synchronously improving oxygen reaction kinetics, mass transfer dynamics, and robustness of transition metal alloy based hybrid catalyst

Construction of robust protective cover on delicate active sites is a frequently-used scheme to enhance the durability of air-cathode catalyst working in harsh environment, thus the lifespan of rechargeable Zinc-air batteries (ZABs). Paradoxically, this would degrade the activity due to the constricted accessibility of active sites to reactants. Herein, carbon nanotubes with abundant mesoporous defects and Fe-N4 species were elaborately designed to be multifunctional protective armor to encapsulate Ni3Fe nano-alloys (Ni3Fe@CNTs/Fe-N4) for bifunctional oxygen electrocatalyst. In/ex-situ spectroscopy analysis and theoretical calculations reveal that the constructed mesoporous carbon defects effectively facilitate the multiphase mass transfer and the oxygen evolution reaction kinetics via strong electrons coupling with packaged Ni3Fe nano-alloys. Meanwhile, the synchronously introduced Fe-N4 moieties could serve as oxygen reduction active sites. Thus, the obtained Ni3Fe@CNTs/Fe-N4 hybrid electrocatalyst simultaneously exhibits remarkable bifunctional catalytic activity (E1/2=0.86/Ej=10=1.59 V vs RHE) and durability over 450 h in the chronoamperometric test at 1.59 V, endowing the assembled Zn-air batteries (ZABs) with a high power density (150 mW cm−2) and lifespan (307 h), much better than that employing benchmark Pt/C+RuO2 mixed catalyst. This work demonstrates an innovative design route for the multifunctional armor to concurrently enhance the durability, activity and robustness of air-cathode-catalyst for ZABs.

Atomically dispersed Fe-N-C catalyst with densely exposed Fe-N4 active sites for enhanced oxygen reduction reaction

Atomically dispersed Fe-N-C catalysts are a promising alternative to platinum group metal (PGM) catalysts for oxygen reduction reaction (ORR). However, attaining efficient ORR activity and superior stability in Fe-N-C catalysts is still crucial yet challenging. Herein, we report a rational SiO2-mediated two-step pyrolysis strategy for stabilizing densely exposed Fe-N4 active sites on hierarchically porous carbon (HP-Fe-N-C/2). Benefiting from the high density of accessible Fe-N4 sites and the high graphitization degree of carbon support, the obtained HP-Fe-N-C/2 catalyst demonstrates outstanding activity and stability for ORR in both alkaline and acidic media. When used as the cathode catalyst, the assembled Zn-air battery shows a high peak power density of 217 mW cm−2 and ultra-long cycling stability for 1342 h without noticeable degradation. As a PGM-free cathode in proton exchange membrane fuel cells, it delivers a maximum output power density of 0.66 W cm−2.

Fe3 C/Fe Decorated N-doped Carbon Derived from Tetrabutylammonium tetrachloroferrate Complex as Bifunctional Electrocatalysts for ORR, OER and Zn-Air Batteries in Alkaline Medium.

The emergence of non-precious metal-based robust and economic bifunctional oxygen electrocatalysts for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is crucial for the rational design of commercial rechargeable Zn-air batteries (RZAB) with safe energy conversion and storage systems. Herein, a facile strategy to fabricate a cost-efficient, bifunctional oxygen electrocatalyst Fe3 C/Fe decorated N doped carbon (FeC-700, the catalyst prepared at carbinization temperature of 700 °C) with a unique structure has been developed by carbonization of a single source precursor, tetrabutylammonium tetrachloroferrate(III) complex. The ORR and OER activity revealed excellent performance (ΔE=0.77 V) of the FeC-700 electrocatalyst, comparable to commercial Pt/C and RuO2, respectively. The designed temperature-tuneable structure provided sufficiently accessible active sites for the continuous passage of electrons by shortening the mass transfer pathway, leading to extremely durable electrocatalysts with high ECSA and amazing charge transfer performance. Remarkably, the assembled Zn-air batteries with the FeC-700 catalyst as the bifunctional air electrode delivers gratifying charging-discharging ability with an impressive power density of 134 mW cm-2 with a long lifespan, demonstrating prodigious possibilities for practical application.

Salt Effect Engineering Single Fe-N2P2-Cl Sites on Interlinked Porous Carbon Nanosheets for Superior Oxygen Reduction Reaction and Zn-Air Batteries.

Developing efficient metal-nitrogen-carbon (M-N-C) single-atom catalysts for oxygen reduction reaction (ORR) is significant for the widespread implementation of Zn-air batteries, while the synergic design of the matrix microstructure and coordination environment of metal centers remains challenges. Herein, a novel salt effect-induced strategy is proposed to engineer N and P coordinated atomically dispersed Fe atoms with extra-axial Cl on interlinked porous carbon nanosheets, achieving a superior single-atom Fe catalyst (denoted as Fe-NP-Cl-C) for ORR and Zn-air batteries. The hierarchical porous nanosheet architecture can provide rapid mass/electron transfer channels and facilitate the exposure of active sites. Experiments and density functional theory (DFT) calculations reveal the distinctive Fe-N2P2-Cl active sites afford significantly reduced energy barriers and promoted reaction kinetics for ORR. Consequently, the Fe-NP-Cl-C catalyst exhibits distinguished ORR performance with a half-wave potential (E1/2) of 0.92V and excellent stability. Remarkably, the assembled Zn-air battery based on Fe-NP-Cl-C delivers an extremely high peak power density of 260mWcm-2 and a large specific capacity of 812mAhg-1, outperforming the commercial Pt/C and most reported congeneric catalysts. This study offers a new perspective on structural optimization and coordination engineering of single-atom catalysts for efficient oxygen electrocatalysis and energy conversion devices.

Constructing delocalized electronic structures to motivate the oxygen reduction activity of zinc selenide for high-performance zinc-air battery

Rechargeable zinc-air battery (ZAB) typically necessitates highly efficient, durable, and cost-effective electrocatalysts to accelerate oxygen reduction reaction (ORR). Zinc selenide (ZnSe) has been demonstrated as a superior energy storage material due to its unique electronic structure for various energy-related applications but is still rarely developed in electrocatalysis field. Herein, the efficient interfacial engineering is reported to motivate and sufficiently boost the ORR performances of ZnSe to an unprecedented level. Density functional theory (DFT) calculations demonstrate that the introduction of robust Se-C interactions and N species regulation could efficiently modulate the local electronic structure of ZnSe and improve the interaction with oxygen-containing intermediate, thus producing lower reaction energy barrier of O2 → OOH* conversion. The optimized ZnSe@PNC catalyst manifests remarkable ORR activity with a half-wave potential of 0.905 VRHE in alkaline. Furthermore, the assembled Zn-air batteries with ZnSe@PNC cathodes show large peak power density (126 mW cm−2), high specific capacity (818 mAh/g) and long cycling life (200 h). This work provides more possibilities for the electrocatalytic applications of nonprecious metal selenide electrocatalyst for future energy storage.

Ice-templating co-assembly of dual-MOF superstructures derived 2D carbon nanobelts as efficient electrocatalysts

Here, we propose a novel synthetic strategy to fabricate a two-dimensional (2D) N-doped carbon nanobelt with high electrocatalytic activity using a dual-MOF superstructure precursor. The self-assembly mechanism induced by Van der Waals forces ensures the successful formation of a 2D ZIF-8/ZIF-67 dual-MOF superstructure through a straightforward ice-templating co-assembly method. Additionally, N-doped carbon derived from ZIF-8 can capture cobalt species from the adjacent ZIF-67 during the pyrolysis process, resulting in the coexistence of atomically dispersed Co single atoms and nanoparticles within the carbon nanobelt, effectively enhancing the intrinsic activity for the electrocatalytic oxygen reduction reaction (ORR). Furthermore, the interconnected hierarchically porous carbon nanocubes in the kinetic-favorable 2D carbon nanobelt superstructure can maximize the exposure of accessible active sites, overcome macroscopic mass transfer limitations, and accelerate the reaction kinetics. Hence, the as-prepared carbon nanobelt exhibits outstanding alkaline ORR catalytic activity with a half-wave potential of 0.888 V versus RHE, and the assembled Zn–air batteries display a prominent peak power density of 179 mW cm−1. The present work highlights the simplicity and versatility of the ice-templating assisted co-assembly strategy in preparing efficient 2D carbon-based superstructure electrocatalysts.

Confinement pyrolysis of FeCo dual-single atoms electrocatalyst for significantly boosting oxygen reduction reaction and rechargeable Zn-air battery

To address the energy crisis, it is critical to pursuit economic, high-energy density and stable electrocatalysts for oxygen reduction reaction (ORR). Herein, N,P-codoped hollow mesoporous carbon spheres supported FeCo dual-single atoms (FeCo-N,P-HCS) are synthesized via one-step confinement pyrolysis of the mixed metal salts, hollow mesoporous carbon spheres and dicyandiamide. Impressively, the gained FeCo-N,P-HCS exhibited a positive onset potential (Eonset = 1.01 V) and half wave potential (E1/2 = 0.85 V) in a 0.1 M KOH electrolyte, revealing the superior ORR characteristics. Later on, the FeCo-N,P-HCS assembled Zn-air battery displayed an open circuit voltage of 1.491 V, a high power density of 140 mW cm−2 and great cyclic stability over the Pt/C + RuO2 based counterpart. This research affords some constructive insights for searching high-efficiency catalyst in relevant energy storage and conversion fields.

Rational design of a CoFe-prussian blue analogue-derived three-dimensional ternary nanocatalyst with efficient ORR/OER catalytic performance for Zn-air batteries

To effectively alleviate the aggregation of catalytic active sites, the rational design and simple preparation of a nanocatalyst with an ideal configuration plays a decisive role. Herein, a CoFe-prussian blue analogue (PBA) decorated with composite carbon/nitrogen sources (C/Ns) is prepared as the precursor to synthesize a three-dimensional (3D) ternary nanocomposite by a two-step calcination method. In this 3D nanocomposite, the 0D CoFe alloy nanoparticles derived from the PBA are mostly embedded in 1D N-doped carbon nanotubes (NCNTs) and partially loaded on 2D N-doped carbon nanosheets. Accordingly, the aggregation of alloy nanoparticles is greatly alleviated while a 3D nanostructure with large specific surface area, porosity, good electron transport properties and exposed active sites can be formed. The alloy nanoparticles are excellent electrocatalysts for oxygen reduction/oxygen evolution reactions, while also facilitating the formation of conductive NCNTs. Density Functional Theory calculations confirm the synergy between the Fe, N doped carbon and (110) crystal plane of the CoFe alloy that accounts for the electrocatalytic activity. The assembled Zn-air batteries show an open circuit voltage of 1.510 V, power density of 196.1 mW cm−2 and an operational durability of 300 h. Moreover, the assembled all-solid-state batteries display the potential for practical applications. This work demonstrates that the configuration of the electrocatalyst can significantly affect its catalytic performance.

Tuning the Bonding Behavior of d‐p Orbitals to Enhance Oxygen Reduction through Push–Pull Electronic Effects

AbstractThe regulation of electronic structure is intricately linked to the intrinsic activity of oxygen reduction. Herein, a strategy for electronic structure modulation induced by bimetallic push–pull electronic effects in dual‐atom catalysts (Fe,Ni/N‐C@NG) is developed. Experiments and theoretical analysis reveal that Fe sites exhibit favorable bonding behaviors (Fe–O: dxz‐p, dyz‐p, and dz2‐p) and spin configurations, which can enable rapid desorption of *OH and thus enhance the intrinsic activity of oxygen reduction. In situ monitoring techniques and Gibbs free energy diagram further demonstrate that the adjacent Ni could serve as second active center to participate in oxygen reduction. The Fe,Ni/N‐C@NG exhibits enhanced oxygen reduction reaction activity and excellent stability. Meanwhile, the assembled Zn–air battery maintains stability for over 300 h with a small voltage gap. This study provides multiple insights into the orbital scale laws of oxygen reduction.

Formulating N-Doped Carbon Hollow Nanospheres with Highly Accessible Through-Pores to Isolate Fe Single-Atoms for Efficient Oxygen Reduction.

It is challenging yet promising to design highly accessible N-doped carbon skeletons to fully expose the active sites inside single-atom catalysts. Herein, mesoporous N-doped carbon hollow spheres with regulatable through-pore size can be formulated by a simple sequential synthesis procedure, in which the condensed SiO2 is acted as removable dual-templates to produce both hollow interiors and through-pores, meanwhile, the co-condensed polydopamine shell is served as N-doped carbon precursor. After that, Fe─N─C hollow spheres (HSs) with highly accessible active sites can be obtained after rationally implanting Fe single-atoms. Microstructural analysis and X-ray absorption fine structure analysis reveal that high-density Fe─N4 active sites together with tiny Fe clusters are uniformly distributed on the mesoporous carbon skeleton with abundant through-pores. Benefitted from the highly accessible Fe─N4 active sites arising from the unique through-pore architecture, the Fe─N─C HSs demonstrate excellent oxygen reduction reaction (ORR) performance in alkaline media with a half-wave potential up to 0.90V versus RHE and remarkable stability, both exceeding the commercial Pt/C. When employing Fe─N─C HSs as the air-cathode catalysts, the assembled Zn-air batteries deliver a high peak power density of 204mWcm-2 and stable discharging voltage plateau over 140h.

Hierarchical wood cells impose well-textured carbon nanotubes with cobalt single atoms: Bioinspired construction and application in zinc–air battery

The construction of oxygen reduction reaction (ORR) electrocatalysts with well-textured structure and desirable activity remains great challenge for the complicated procedures and poor interface. Herein, inspired by sea anemones, the highly ordered Co–based carbon nanotubes electrocatalysts were elaborately assembled on wood fibers via stoichiometry. The porous cell-wall and abundant oxygen groups in lignocellulosic scaffold impose such preferable structure, in which the Co–based carbon nanotubes with Co single atoms and Co nanoparticles were tuned to possess higher catalytic activity and capture more oxygen species. As expected, the as-prepared electrocatalyst displays outstanding ORR performance with a half-wave potential of 0.9 V. The assembled Zn–air battery using this cathode catalyst shows a high-power density of 196 mW cm−2, superior to the commercial Pt/C catalysts. This work could inspire developing other biomimetic architectures for high-performance energy storage and conversion systems.

Coexisting Fe single atoms and nanoparticles on hierarchically porous carbon for high-efficiency oxygen reduction reaction and Zn-air batteries

Fe single-atom catalysts still suffer from unsatisfactory intrinsic activity and durability for oxygen reduction reaction (ORR). Herein, the coexisting Fe single atoms and nanoparticles on hierarchically porous carbon (denoted as Fe-FeN-C) are prepared via a Zn5(OH)6(CO3)2-assisted pyrolysis strategy. Theoretical calculation reveals that the Fe nanoparticles can optimize the electronic structures and d-band center of Fe active center, hence reducing the reaction energy barrier for enhancing intrinsic activity. The Zn5(OH)6(CO3)2 self-sacrificial template not only can promote the formation of Fe single atoms, but also contributes to the construction of microporous/mesoporous/macroporous structures. Therefore, the obtained Fe-FeN-C exhibits impressive ORR activity with a half-wave potential of 0.921 V, which far exceeds Pt/C. With Fe-FeN-C as the cathode catalyst, the assembled Zn-air batteries delivered a maximum power density of 206 mW cm−2 and a long-cycle life over 400 h.

Space‐Confined Growth of Co9S8 Nanoparticles in Covalent Organic Framework‐Derived Porous Carbon for Efficient Bifunctional Oxygen Electrocatalysis

AbstractFine regulation of the physicochemical structure of carbon‐based electrocatalysts to optimize the adsorption energies of oxygen intermediates is critically important to enhance the reaction kinetics of the oxygen evolution/reduction reaction (OER/ORR) but remains a huge challenge. Herein, nano‐space confined growth of Co9S8 nanoparticles (NPs) in porous carbon is realized through an in situ confined growth strategy by using thiol‐chains functionalized COF (COF‐S‐SH) as a confined template. COF‐S‐SH is used as binding sites to immobilize Co ions to improve the interaction between metal nanoparticles (NPs) and carbon skeletons, and simultaneously serves as a confined void to avoid the aggregation metal NPs. Impressively, as an efficient bifunctional catalyst, the resulting Co9S8/COF‐S800 shows significantly enhanced oxygen electrocatalysis with a small OER‐ORR voltage gap of 0.76 V, vastly superior to that of pristine COF‐S800. Furthermore, the assembled Zn–air battery with Co9S8/COF‐S800 catalyst displays a high peak power density of 181.5 mW cm−2 and great durability over 60 h charge–discharge cycles.

Salt-templated synthesis of carbon nanosheets decorated with high valence tungsten doped Co2P nanoparticles for efficient Zn-air battery

An ORR/OER bifunctional electrocatalyst, porous nitrogen-doped carbon nanosheet decorated with high valence tungsten doped Co2P nanoparticles, has been developed for efficient Zn-air battery through salt template in this work. This catalyst exhibits high ORR (half-wave potential of 0.861 V) and OER activities (overpotential of 310 mV). The results of density functional theory calculation verify that the introduction of high valence tungsten dopants is advantageous to regulate the electronic structure of Co2P, thereby has effectively optimized the adsorption energy of intermediate species for ORR/OER and density of states. Meanwhile, the energy barrier of the rate-determining step is greatly lowered. Assembled Zn-air battery (ZAB) exhibits a promising open-circuit voltage of 1.50 V, good power density (224.4 mW cm−2), excellent specific capacity (881 mAh g−1), and durability (130 h). This work elucidated that creating high-performance transition-metal based electrocatalysts for rechargeable Zn-air batteries would be feasible using 5d high valence metal ion doping.

Facet Engineering and Pore Design Boost Dynamic Fe Exchange in Oxygen Evolution Catalysis to Break the Activity-Stability Trade-Off.

The oxygen evolution reaction (OER) plays a vital role in renewable energy technologies, including in fuel cells, metal-air batteries, and water splitting; however, the currently available catalysts still suffer from unsatisfactory performance due to the sluggish OER kinetics. Herein, we developed a new catalyst with high efficiency in which the dynamic exchange mechanism of active Fe sites in the OER was regulated by crystal plane engineering and pore structure design. High-density nanoholes were created on cobalt hydroxide as the catalyst host, and then Fe species were filled inside the nanoholes. During the OER, the dynamic Fe was selectively and strongly adsorbed by the (101̅0) sites on the nanohole walls rather than the (0001) basal plane, and at the same time the space-confining effect of the nanohole slowed down the Fe diffusion from catalyst to electrolyte. As a result, a local high-flux Fe dynamic equilibrium inside the nanoholes for OER was achieved, as demonstrated by the Fe57 isotope labeled mass spectrometry, thereby delivering a high OER activity. The catalyst showed a remarkably low overpotential of 228 mV at a current density of 10 mA cm-2, which is among the best cobalt-based catalysts reported so far. This special protection strategy for Fe also greatly improved the catalytic stability, reducing the Fe leaching amount by 2 orders of magnitude compared with the pure Fe hydroxide catalyst and thus delivering a long-term stability of 130 h. An assembled Zn-air battery was stably cycled for 170 h with a low discharge/charge voltage difference of 0.72 V.

Covalent organic framework-derived fluorine, nitrogen dual-doped carbon as metal-free bifunctional oxygen electrocatalysts

The construction of heteroatom-doped metal-free carbon catalysts with bifunctional catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is highly desired for Zn-air batteries, but remains a great challenge owing to the sluggish kinetics of OER and ORR. Herein, a self-sacrificing template engineering strategy was employed to fabricate fluorine (F), nitrogen (N) co-doped porous carbon (F-NPC) catalyst by direct pyrolysis of F, N containing covalent organic framework (F-COF). The predesigned F and N elements were integrated into the skeletons of COF precursor, thus achieving uniformly distributed heteroatom active sites. The introduction of F is beneficial for the formation of edge-defects, contributing to the enhancement of the electrocatalytic activity. Attributing to the porous feature, abundant defect sites induced by F doping, as well as the strong synergistic effect between N and F atoms to afford a high intrinsic catalytic activity, the resulting F-NPC catalyst exhibits excellent bifunctional catalytic activities for both ORR and OER in alkaline mediums. Furthermore, the assembled Zn-air battery with F-NPC catalyst shows a high peak power density of 206.3 mW cm−2 and great stability, surpassing the commercial Pt/C + RuO2 catalysts.

Achieving in-system modification of Zn anode on stainless steel mesh for seawater-based energy storage with advanced dendrite-free self-regulation mechanism

In this work, Zn anode with a high compatibility to seawater system is fabricated on stainless steel mesh using an ultra-simple in-system synthesis technique. Physical characterizations reveal that the film electrode is composed by cross-linked Zn nanoflakes structure with outstanding adhesion and mechanical deformation tolerance. Being adopted as seawater-compatible anode, the as-synthesized Zn electrode exhibits a high reversible capacity of 30 mAh cm−2 with obvious advantages such as outstanding rate capability, strong tolerance to real-time varied current, low capacity decay, and good long-term cycling stability. The assembled Zn-air battery performs a maximum energy density of 285 Wh m−2 and successfully lights up various electronic devices. Furthermore, the self-regulation working mechanism and the growth kinetic of Zn electrode are further investigated using in-situ optical microscopy observations and in-situ electrochemical impedance spectroscopy (EIS) techniques. This work demonstrates a promising feasibility for fabricating highly reversible and low-cost Zn electrode in seawater system aiming to large-scale energy storage.