Coordination and Hydrogen Bond Chemistry in Tungsten Oxide@Polyaniline Composite toward High-Capacity Aqueous Ammonium Storage.

Aqueous ammonium ion batteries (AAIBs) have garnered significant attention due to their unique energy storage mechanism. However, their progress is hindered by the relatively low capacities of NH4 + host materials. Herein, the study proposes an electrodeposited tungsten oxide@polyaniline (WOx@PANI) composite electrode as a NH4 + host, which achieves an ultrahigh capacity of 280.3 mAh g-1 at 1 A g-1, surpassing the vast majority of previously reported NH4 + host materials. The synergistic interaction of coordination chemistry and hydrogen bond chemistry between the WOx and PANI enhances the charge storage capacity. Experimental results indicate that the strong interfacial coordination bonding (N: →W6+) effectively modulates the chemical environment of W atoms, enhances the protonation level of PANI, and thus consequently the conductivity and stability of the composites. Spectroscopy analysis further reveals a unique NH4 +/H+ co-insertion mechanism, in which the interfacial hydrogen bond network (N-H···O) accelerates proton involvement in the energy storage process and activates the Grotthuss hopping conduction of H+ between the hydrated tungsten oxide layers. This work opens a new avenue to achieving high-capacity NH4 + storage through interfacial chemistry interactions, overcoming the capacity limitations of NH4 + host materials for aqueous energy storage.

Amine-aldehyde resin derived porous N-doped hollow carbon nanorods for high-energy capacitive energy storage.

Electrochemical double layer capacitors (EDLCs) are known for their high power density but hampered by low energy density. Herein, N-doped hollow carbon nanorods (NHCRs) have been constructed by a hard templating method using MnO2nanorods as the hard templates andm-phenylenediamine-formaldehyde resin as the carbon precursor. The NHCRs after activation (NHCRs-A) manifest abundant micropores/mesopores and an ultrahigh surface area (2166 m2g-1). When employed in ionic liquid (IL) electrolyte-based EDLCs, the NHCRs-A delivers a high specific capacitance (220 F g-1at 1 A g-1), an impressive energy density (110 Wh kg-1), and decent cyclability (97% retention over 15 000 cycles). The impressive energy density is derived from the abundant ion-available micropores, while the decent power density is originated from the hollow ion-diffusion channels as well as excellent wettability in ILs.In situinfrared spectroscopy together within situRaman unveil that both counter-ion adsorption and ion exchange are involved in the charge storage of NHCRs-A. This study provides insight into the construction of porous carbon materials for EDLCs.

Supramolecular Engineering of Cathode Materials for Aqueous Zinc-ion Energy Storage Devices: Novel Benzothiadiazole Functionalized Two-Dimensional Olefin-Linked COFs.

Two-dimensional covalent organic frameworks (COFs) have emerged as promising materials for energy storage applications exhibiting enhanced electrochemical performance. While most of the reported organic cathode materials for zinc-ion batteries use carbonyl groups as electrochemically-active sites, their high hydrophilicity in aqueous electrolytes represents a critical drawback. Herein, we report a novel and structurally robust olefin-linked COF-TMT-BT synthesized via the aldol condensation between 2,4,6-trimethyl-1,3,5-triazine (TMT) and 4,4'-(benzothiadiazole-4,7-diyl)dibenzaldehyde (BT), where benzothiadiazole units are explored as novel electrochemically-active groups. Our COF-TMT-BT exhibits an outstanding Zn2+ storage capability, delivering a state-of-the-art capacity of 283.5 mAh g-1 at 0.1 A g-1 . Computational and experimental analyses reveal that the charge-storage mechanism in COF-TMT-BT electrodes is based on the supramolecularly engineered and reversible Zn2+ coordination by the benzothiadiazole units.

Solid-Liquid Interfacial Coordination Chemistry Enables High-Capacity Ammonium Storage in Amorphous Manganese Phosphate.

Ammonium (NH4 + ) ion as charge carrier is attracting attention in aqueous batteries. Yet, most NH4 + host materials are still limited by the relatively low capacities. Here, we fabricated a manganese phosphate (MP-20) for NH4 + ion storage. MP-20 displays a high capacity of 299.6 mAh g-1 at 1 A g-1 in ammonium acetate (NH4 Ac) electrolyte, outperforming other reported NH4 + host materials. Spectroscopy studies suggest a new NH4 + /H+ co-insertion mechanism. We surprisingly discover that the NH4 Ac electrolyte plays an important role in improving the charge storage capability of the materials. Experimental and computational results indicate acetate ions can form coordination bonds with the Mn atoms, tailoring the electronic structure of the Mn atoms and the surrounding O atoms, and therefore facilitating the NH4 + storage process. Our findings provide a new NH4 + host material and propose the important role of the electrolyte-electrode coordination effect in aqueous ammonium batteries.

Understanding and Calibration of Charge Storage Mechanism in Cyclic Voltammetry Curves.

Noticeable pseudo-capacitance behavior out of charge storage mechanism (CSM) has attracted intensive studies because it can provide both high energy density and large output power. Although cyclic voltammetry is recognized as the feasible electrochemical technique to determine it quantitatively in the previous works, the results are inferior due to uncertainty in the definitions and application conditions. Herein, three successive treatments, including de-polarization, de-residual and de-background, as well as a non-linear fitting algorithm are employed for the first time to calibrate the different CSM contribution of three typical cathode materials, LiFePO4 , LiMn2 O4 and Na4 Fe3 (PO4 )2 P2 O7 , and achieve well-separated physical capacitance, pseudo-capacitance and diffusive contributions to the total capacity. This work can eliminate misunderstanding concepts and correct ambiguous results of the pseudo-capacitance contribution and recognize the essence of CSM in electrode materials.

Borocarbonitride-Based Emerging Materials for Supercapacitor Applications: Recent Advances, Challenges, and Future Perspectives.

Supercapacitors have emerged as a promising energy storage technology due to their high-power density, fast charging/discharging capabilities, and long cycle life. Moreover, innovative electrode materials are extensively explored to enhance the performance, mainly the energy density of supercapacitors. Among the two-dimensional (2D) supercapacitor electrodes, borocarbonitride (BCN) has sparked widespread curiosity owing to its exceptional tunable properties concerning the change in concentration of the constituent elements, along with an excellent alternative to graphene-based electrodes. BCN, an advanced nanomaterial, possesses excellent electrical conductivity, chemical stability, and a large specific surface area. These factors contribute to supercapacitors' overall performance and reliability, making them a viable option to address the energy crisis. This review provides a detailed survey of BCN, its structural, electronic, chemical, magnetic, and mechanical properties, advanced synthesis methods, factors affecting the charge storage mechanism, and recent advances in BCN-based supercapacitor electrodes. The review embarks on the scrupulous elaboration of ways to enhance the electrochemical properties of BCN through various innovative strategies followed by critical challenges and future perspectives. BCN, as an eminent electrode material, holds great potential to revolutionize the energy landscape and support the growing energy demands of the future.

One-Pot Facile Synthesis of a Cluster of ZnS Low-Dimensional Nanoparticles for High-Performance Supercapacitor Electrodes.

To maximize the use of ZnS low-dimensional nanoparticles as high-performance supercapacitor electrodes, this work describes a simple one-pot synthesis method for producing a cluster of these particles. The ZnS nanoparticles fabricated in this work exhibit a cluster with unique low-dimensional (0D, 1D, and 2D) characteristics. Structural, morphological, and electrochemical investigations are all part of the thorough characterization of the produced materials. An X-ray diffraction pattern of clustered ZnS nanoparticles reflects the phase formation with highly stable cubic blende sphalerite polymorph. The confirmation of nanoparticle cluster formation featuring multiple low-dimensional nanostructures was achieved through field emission scanning electron microscopy (FE-SEM), while the internal structure was assessed using transmission electron microscopy (TEM). Systematically assessing the ZnS nanoparticles' electrochemical performance reveals their prospective qualities as supercapacitor electrode materials. The electrode assembled with this material on Ni foam demonstrates elevated specific capacitance (areal capacitance) values, reaching 716.8 F.g⁻1 (2150.4 mF.cm-2) at a current density of 3 mA.cm⁻2. Moreover, it reflects 69.1% capacitance retention with a four times increase in current density, i.e., 495.5 F.g-1 (1486.56 mF.cm-2) capacitance was archived at 12 mA.cm-2 with 100% Coulombic efficiency. Furthermore, the electrode exhibits prolonged cycling capability with 77.7% capacitance retention, as evidenced by its charge-discharge measurements sustained over 15,000 cycles at a current density of 25 mA cm⁻2.

Gradient Pores Enhance Charge Storage Density of Carbonaceous Cathodes for Zn-Ion Capacitor.

Engineering carbonaceous cathode materials with adequately accessible active sites is crucial for unleashing their charge storage potential. Herein, activated meso-microporous shell carbon (MMSC-A) nanofibers are constructed to enhance the zinc ion storage density by forming a gradient-pore structure. A dominating pore size of 0.86 nm is tailored to cater for the solvated [Zn(H2O)6]2+. Moreover, these gradient porous nanofibers feature rapid ion/electron dual conduction pathways and offer abundant active surfaces with high affinity to electrolyte. When employed in Zn-ion capacitors (ZICs), the electrode delivers significantly enhanced capacity (257 mAh g-1), energy density (200 Wh kg-1 at 78 W kg-1), and cyclic stability (95% retention after 10 000 cycles) compared to nonactivated carbon nanofibers electrode. A series of in situ characterization techniques unveil that the improved Zn2+ storage capability stems from size compatibility between the pores and [Zn(H2O)6]2+, the co-adsorption of Zn2+, H+, and SO4 2-, as well as reversible surface chemical interaction. This work presents an effective method to engineering meso-microporous carbon materials toward high energy-density storage, and also offers insights into the Zn2+ storage mechanism in such gradient-pore structures.

The synergistic effect of NiCo2S4 and carbon nanosheets for supercapacitor: Enhanced adsorption/desorption of OH- on Ni and Co active sites.

To improve the low energy density, low conductivity, and poor cycling stability of NiCo2S4 in supercapacitors, a two-step hydrothermal method was used to prepare a composite material of NiCo2S4 and carbon nanosheets (NiCo2S4/CNs). The electrochemical tests revealed a high specific capacitance of 1576 F g-1 at 1 A/g for the composite, and the NiCo2S4/CNs//AC asymmetric supercapacitor showed a energy density of 49.7 Wh kg-1 at 818 W kg-1. This study confirmed the phase transformation of NiCo2S4 during charge/discharge in alkaline solution through ex-situ X-ray diffraction (ex-situ XRD) for the first time, and proposed a potential reaction pathway. Moreover, Density Functional Theory (DFT) confirmed that the NiCo2S4/CNs heterostructure enhances OH- adsorption/desorption on Ni and Co active sites and improves electronic conductivity. In conclusion, this study advances the application of transition metal sulfide in high-performance energy storage.

Averting H+-Mediated Charge Storage Chemistry Stabilizes the High Output Voltage of LiMn2O4-Based Aqueous Battery.

H+ co-intercalation chemistry of the cathode is perceived to have damaging consequences on the low-rate and long-term cycling of aqueous zinc batteries, which is a critical hindrance to their promise for stationary storage applications. Herein, the thermodynamically competitive H+ storage chemistry of an attractive high-voltage cathode LiMn2O4 is revealed by employing operando and ex-situ analytical techniques together with density functional theory-based calculations. The H+ electrochemistry leads to the previously unforeseen voltage decay with cycling, impacting the available energy density, particularly at lower currents. Based on an in-depth investigation of the effect of the Li+ to Zn2+ ratio in the electrolyte on the charge storage mechanism, a purely aqueous and low-salt concentration electrolyte with a tuned Li+/Zn2+ ratio is introduced to subdue the H+-mediated charge storage kinetically, resulting in a stable voltage output and improved cycling stability at both low and high cathode loadings. Synchrotron X-ray diffraction analysis reveals that repeated H+ intercalation triggers an irreversible phase transformation leading to voltage decay, which is averted by shutting down H+ storage. These findings unveiling the origin and impact of the deleterious H+-storage, coupled with the practical strategy for its inhibition, will inspire further work toward this under-explored realm of aqueous battery chemistry.

Tuning MXene Properties through Cu Intercalation: Coupled Guest/Host Redox and Pseudocapacitance.

MXenes are 2D transition metal carbides, nitrides, and/or carbonitrides that can be intercalated with cations through chemical or electrochemical pathways. While the insertion of alkali and alkaline earth cations into Ti3C2Tx MXenes is well studied, understanding of the intercalation of redox-active transition metal ions into MXenes and its impact on their electronic and electrochemical properties is lacking. In this work, we investigate the intercalation of Cu ions into Ti3C2Tx MXene and its effect on its electronic and electrochemical properties. Using X-ray absorption spectroscopy (XAS) and ab initio molecular dynamics (AIMD), we observe an unusual phenomenon whereby Cu2+ ions undergo partial reduction upon intercalation from the solution into the MXene. Furthermore, using in situ XAS, we reveal changes in the oxidation states of intercalated Cu ions and Ti atoms during charging. We show that the pseudocapacitive response of Cu-MXene originates from the redox of both the Cu intercalant and Ti3C2Tx host. Despite highly reducing potentials, Cu ions inside the MXene show an excellent stability against full reduction upon charging. Our findings demonstrate how electronic coupling between Cu ions and Ti3C2Tx modifies electrochemical and electronic properties of the latter, providing the framework for the rational design and utilization of transition metal intercalants for tuning the properties of MXenes for various electrochemical systems.

Amorphization-Driven Lithium Ion Storage Mechanism Change for Anomalous Capacity Enhancement.

Capacity fading as a function of lithiation/delithiation cycles is a major limitation of Li-ion batteries. Most Li storage materials are susceptible to this phenomenon due to the degradation of the crystal structure and particle integrity as a result of volume changes associated with lithiation/delithiation processes and/or irreversible redox reactions. However, some Li storage materials show an increase in capacity with an increase in cycles; this phenomenon has been termed "negative fading." Negative fading in Li host materials is usually associated with the additional charge storage at the particle/solid-electrolyte interface (SEI) layer, decomposition/formation of the SEI layer, or redox reactions of various Li species at the interface. In this work, we report the observation of negative fading in a newly discovered anode material, TiNbO4 (TNO), and reveal amorphization as a new mechanism for negative fading in Li host materials. This assertion was confirmed via a close relationship between changes in the crystal structure and the Li storage mechanism in TNO. Given that other titanium niobium oxide analogues (e.g., TiNb2O7) suffer from capacity loss due to amorphization, this unique electrochemical behavior of TNO may provide an interesting new direction to tune the titanium niobium oxides for high-performance, stable battery anodes.

Bimetallic Synergies Help the Application of Sodium Vanadyl Phosphate in Aqueous Sodium-Ion Batteries.

Aqueous sodium-ion batteries (ASIB) offer many potential applications in large-scale power grids since they are inexpensive, safe, and environmentally friendly. Sodium superionic conductors (NASICON), especially carbon-coated Na3 V2 (PO4 )3 (NVP), have attracted much attention due to the full use of their high ion migration speed. However, the poor cycle lifespan and capacity retention of NVP hinder its application in ASIB. Herein, a novel bimetal-doped Na3 V1.3 Fe0.5 W0.2 (PO4 )3 (NV1.3 Fe0.5 W0.2 P) cathode is designed and synthesized to achieve outstanding cycling stability (95 % of initial capacity at 50th cycle). The electrochemical behavior and charge storage mechanism of NV1.3 Fe0.5 W0.2 P are systematically investigated by various in situ and ex situ characterizations. The Fe and W codoping could stabilize the NASICON framework to suppress the proton attack on the Na site in the aqueous electrolyte, thus resulting in excellent cycling stability. DFT calculations show that bimetallic doping increases the structural stability of NVP. Moreover, an ASIB fabricated using a NV1.3 Fe0.5 W0.2 P cathode and a NaTi2 (PO4 )3 anode delivers 64 mAh g-1 at room temperature, 95 % capacity retention after 50 cycles (1 A g-1 ).

Amorphous Heterostructure Derived from Divalent Manganese Borate for Ultrastable and Ultrafast Aqueous Zinc Ion Storage.

Aqueous zinc-manganese (Zn-Mn) batteries have promising potential in large-scale energy storage applications since they are highly safe, environment-friendly, and low-cost. However, the practicality of Mn-based materials is plagued by their structural collapse and uncertain energy storage mechanism upon cycling. Herein, this work designs an amorphous manganese borate (a-MnBOx ) material via disordered coordination to alleviate the above issues and improve the electrochemical performance of Zn-Mn batteries. The unique physicochemical characteristic of a-MnBOx enables the inner a-MnBOx to serve as a robust framework in the initial energy storage process. Additionally, the amorphous manganese dioxide, amorphous Znx MnO(OH)2 , and Zn4 SO4 (OH)6 ·4H2 O active components form on the surface of a-MnBOx during the charge/discharge process. The detailed in situ/ex situ characterization demonstrates that the heterostructure of the inner a-MnBOx and surface multicomponent phases endows two energy storage modes (Zn2+ /H+ intercalation/deintercalation process and reversible conversion mechanism between the Znx MnO(OH)2 and Zn4 SO4 (OH)6 ·4H2 O) phases). Therefore, the obtained Zn//a-MnBOx battery exhibits a high specific capacity of 360.4 mAh g-1 , a high energy density of 484.2 Wh kg-1 , and impressive cycling stability (97.0% capacity retention after 10 000 cycles). This finding on a-MnBOx with a dual-energy storage mechanism provides new opportunities for developing high-performance aqueous Zn-Mn batteries.

Hierarchical spheroidal MOF-derived MnO@C as cathode components for high-performance aqueous zinc ion batteries.

Aqueous zinc-ion batteries (AZIBs) have shown great potential as energy storage devices owing to their high energy density, low cost, and low toxicity. Typically, high performance AZIBs incorporate manganese-based cathode materials. Despite their advantages, these cathodes are limited by significant capacity fading and poor rate performance due to the dissolution and disproportionation of manganese. Herein, hierarchical spheroidal MnO@C structures were synthesized from Mn-based metal-organic frameworks, which benefit from a protective carbon layer to prevent manganese dissolution. The spheroidal MnO@C structures were incorporated onto a heterogeneous interface to act as a cathode material for AZIBs, which exhibited excellent cycling stability (160 mAh g-1 after 1000 cycles at 3.0 A g-1), good rate capability (165.9 mAh g-1 at 3.0 A g-1), and appreciable specific capacity (412.4 mAh g-1 at 0.1 A g-1) for AZIBs. Moreover, the Zn2+ storage mechanism in MnO@C was comprehensively investigated using ex-situ XRD and XPS studies. These results demonstrate that hierarchical spheroidal MnO@C is a potential cathode material for high-performing AZIBs.

Dual-Ion Co-intercalation Mechanism on a Na2V6O16·3H2O Cathode with a Commercial-Level Mass Loading for Aqueous Zinc-Ion Batteries with High Areal Capacity.

A proton (H+) and zinc ion (Zn2+) co-insertion model is put forward in this study to elucidate the capacity origin of an aqueous zinc ion battery (ZIB) based on a heavily loaded (∼15 mg cm-2) cathode, which consists of Na2V6O16·3H2O (NVO) embedded particularly in the macropores of activated carbon cloth (ACC), coupled with a highly stable Zn/In anode. The confinement effect of these porous channels not only prevents the detachment of NVO from ACC but also well mitigates its volume change resulting from H+ and Zn2+ co-intercalation, which collectively render the stability of NVO/ACC markedly enhanced. Moreover, the bicontinuous structure of NVO/ACC, as a result of the self-interlacing of intrapore NVO, which is first engineered into the nanobelts, and their interlocking with the carbon fibers of ACC, simultaneously giving rise to a solid and a holey framework, is favorable to the electron and ion transport throughout the entire electrode. The synergistic effect of such facile charge transfer kinetics and the high packing density of NVO in the cathode endows ZIBs with not only a good rate performance but also an exceptional areal capacity amounting to 4.6 mAh cm-2, far surpassing those reported for additional vanadium-based counterparts reported in the literature.

Electrochemical Proton Storage: From Fundamental Understanding to Materials to Devices.

Simultaneously improving the energy density and power density of electrochemical energy storage systems is the ultimate goal of electrochemical energy storage technology. An effective strategy to achieve this goal is to take advantage of the high capacity and rapid kinetics of electrochemical proton storage to break through the power limit of batteries and the energy limit of capacitors. This article aims to review the research progress on the physicochemical properties, electrochemical performance, and reaction mechanisms of electrode materials for electrochemical proton storage. According to the different charge storage mechanisms, the surface redox, intercalation, and conversion materials are classified and introduced in detail, where the influence of crystal water and other nanostructures on the migration kinetics of protons is clarified. Several reported advanced full cell devices are summarized to promote the commercialization of electrochemical proton storage. Finally, this review provides a framework for research directions of charge storage mechanism, basic principles of material structure design, construction strategies of full cell device, and goals of practical application for electrochemical proton storage.

Charge-Discharge Mechanism of High-Entropy Co-Free Spinel Oxide Toward Li+ Storage Examined Using Operando Quick-Scanning X-Ray Absorption Spectroscopy.

Transition metal high-entropy oxides (HEOs) are an attractive class of anode materials for high-performance lithium-ion batteries (LIBs). However, owing to the multiple electroactive centers of HEOs, the Li+ storage mechanism is complex and debated in the literature. In this work, operando quick-scanning X-ray absorption spectroscopy (XAS) is used to study the lithiation/delithiation mechanism of the Cobalt-free spinel (CrMnFeNiCu)3 O4 HEO. A monochromator oscillation frequency of 2 Hz is used and 240 spectra are integrated to achieve a 2 min time resolution. High-photon-flux synchrotron radiation is employed to increase the XAS sensitivity. The results indicate that the Cu2+ and Ni2+ cations are reduced to their metallic states during lithiation but their oxidation reactions are less favorable compared to the other elements upon delithiation. The Mn2+/3+ and Fe2+/3+ cations undergo two-step conversion reactions to form metallic phases, with MnO and FeO as the intermediate species, respectively. During delithiation, the oxidation of Mn occurs prior to that of Fe. The Cr3+ cations are reduced to CrO and then Cr0 during lithiation. A relatively large overpotential is required to activate the Cr reoxidation reaction. The Cr3+ cations are found after delithiation. These results can guide the material design of HEOs for improving LIB performance.

Charge storage mechanism in vanadium telluride/carbon nanobelts as electroactive material in an aqueous asymmetric supercapacitor.

A novel one-step method for fabricating vanadium telluride nanobelt composites for high-performance supercapacitor applications is reported. The nanobelts are realized by direct tellurization of vanadium oxide in-situ formed via decomposition of ammonium metavanadate in argon atmosphere. Use of melamine as precursor helps in forming graphitic carbon layers during pyrolization on which the nanobelts are grafted. Morphological analysis suggests interconnected nanobelts of ∼23.0 nm width coming out of carbon structure. As pseudocapacitive electrode, vanadium telluride/carbon (C) composite exhibits interesting electrochemical performance within a potential window of 0-1.0 V in 1.0 M sodium sulfate electrolyte along with excellent capacitance retention during 5000 cycles. In-depth analysis suggests that the charge storage mechanism in the composite is governed by both diffusion-controlled and diffusion-independent processes with the former dominating at slower scan rates and later at faster scan rates. The asymmetric supercapacitor assembled using vanadium telluride/C and activated charcoal (AC) as respective positive and negative electrodes exhibited an energy/power combination of 19.3 Wh/kg and 1.8 kW/kg within a potential window of 0-1.8 V in aqueous electrolyte. This strategy to improve capacitance along with potential window in an aqueous electrolyte would facilitate development of high-performance energy storage devices with metal chalcogenides.

Electrochemical Activation of Oxygen Vacancy-Rich Nitrogen-Doped Manganese Carbonate Microspheres for High-Performance Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries (ZIBs) are considered as one of the ideal devices for large-scale energy storage because of their safety, low cost, and nontoxicity. Unfortunately, the choice of cathode materials for ZIBs is still limited. Herein, a novel oxygen vacancy-rich nitrogen-doped MnCO3 (MnCO3@N) microsphere is reported as a cathode material for rechargeable ZIBs, which displays a relatively high reversible capacity of 171.6 mAh g-1 at 100 mA g-1, outstanding rate performance, and long-term cyclic stability up to 1000 cycles at 1000 mA g-1. The better electrochemical performances of MnCO3@N should be attributed to the introduction of oxygen vacancies in the MnCO3 microcrystal by nitrogen doping, which not only improves the conductivity of MnCO3 microspheres but also creates more active sites for zinc-ion diffusion. In addition, the energy storage mechanism of the MnCO3@N microspheres is systematically investigated. During the initial charge process, the MnCO3@N microspheres are activated to form MnO@N due to the insertion of Zn2+, and partial MnO@N is further oxidized into layered-type MnO2@N, which becomes a part of the active material for subsequent energy storage. This work not only provides a new insight for the ZIB cathode but also deepens the understanding of the energy storage mechanism of carbonate materials.