High-performance Supercapacitors Research Articles

Copper Oxide Nanoparticles Anchored on Porous Carbon Nitride Nanosheets for Supercapacitor Applications

Electrochemical energy storage devices are vital for renewable energy integration and the deployment of electric vehicles. Ongoing research seeks to create new materials with innovative morphologies capable of delivering high specific capacitance for the next generation of customizable energy devices. Carbon nitride is an excellent candidate for electrochemical energy storage devices; however, it has limitations such as layer stacking, poor electric conductivity, a restricted number of electroactive sites, and static electrochemical reaction rates. This research objective is to make porous structures in carbon nitride nanosheets and integrate them with CuO particles to increase surface area and improve electrochemical performance. The use of thermal heating, acidic treatment, and hydrothermal processes accomplishes this. Along with X-ray diffraction peaks of the CuO phase, a prominent peak (002) at 27.67° indicates the presence of graphitic-structured carbon nitride. TEM images show that CuO particles are evenly attached to the surface of g-C3N4 nanosheets with lattice intervals of 0.336 and 0.232 nm, which are the (002) and (111) orientations of the g-C3N4 and CuO phases, respectively. Adding CuO nanoparticles to porous g-C3N4 nanosheets avoids layer stacking and provides micro- and mesopore channels, increasing the specific surface area (42.60 m2 g-1). The CuO@ porous g-C3N4 electrode delivered 817 F g-1 of specific capacitance at 1 A g-1 and admirable capacitance retention (92.3% after 6000 cycles) due to the synergistic impact of its unique composition and structural characteristics. Because of its outstanding electrochemical performance and fascinating discoveries, CuO@ porous g-C3N4 may be employed as a cathode material for high-performance supercapacitors.

Fabrication of NiCo2O4@NiCo2S4 Core@Shell nanostructured arrays decorated over the rGO sheets for High-Performance asymmetric supercapacitor

Reliable and cost-effective energy storage systems can only be designed using electrode materials that exhibit high energy densities and consistency. In this work, NiCo2S4@NiCo2O4 core@shell nanoneedle-like nanostructures (NCS@NCO/rGO) are synthesized over the rGO sheet using a new and easy hydrothermal approach. Electrolyte transport and sulfur incorporation during charge–discharge reactions are both made easier by the core@shell nanostructured arrays' large active surface area. The ternary electrodes made of NCS@NCO/rGO have a rich mesoporous framework, a large surface area of 156.5 m2g−1, and an ideal distribution of pore sizes centered at 8.1 nm. An impressive specific capacitance of 2011 Fg−1 at 10 mV s−1 demonstrates the exceptional performance of the NCS@NCO/rGO ternary electrode. The ternary electrodes made of NCS@NCO and rGO have been shown to have remarkable cyclic stability in reports, maintaining 91 % of their capacity after 10,000 cycles. With an impressive power density of 983 Wkg−1 and an outstanding cycling durability of 98.8 % retention of the original capacitance after 10,000 cycles, the manufactured NCS@NCO/rGO//AC ACS displays a noticeable energy density of 68.5 Whkg−1. The mesoporous structure is excellent for increasing the characteristics of supercapacitor electrodes, as these astounding results can attest.

Hydrochloric acid induced microstructural reconfiguration from bulk α-NiS microspheres to porous/hollow NiSx microspheres for high-performance hybrid supercapacitor

Nickel sulfide is well known as a promising energy storage/conversion material considering its high redox activity, high theoretical capacity, easy preparation, and rich phase structures. Unfortunately, nickel sulfide prepared by conventional methods usually exhibits a bulk structure, which significantly limited its charge storage. To overcome this obstacle, we developed a facile hydrochloric acid-induced structure reconstruction strategy to fabricate porous and hollow structured nickel sulfide via a one-step hydrothermal process. We found that nickel sulfide undergoes de-nickelization in the presence of 3 M hydrochloric acid, resulting in the transformation from bulk structure to porous/hollow structures, accompanied by a transition from nickel-rich phase (α-NiS) to nickel-deficient phase (Ni3S4 or NiS2). The electrochemical results demonstrated the obviously improved specific capacity of nickel sulfide after structure reconstruction, among which the porous NS-HCl-1 h (α-NiS/Ni3S4) microspheres delivers the highest specific capacity (204.4 mAh g-1 at 1 A g-1) and show a rate performance about 50.0% from 1 to 20 A g-1. The assembled NS-HCl-1 h//rGO supercapacitor delivers a maximum energy density of 47.1 Wh kg-1 at a power density of 803.6 W kg-1, and maintain a capacity retention rate about 88.6% after 10,000 cycles. This work provides a novel method and contributes new insight for the structural reconstruction of transition metal sulfides (TMSs).

Porous highly conductive PEDOT film for high-performance supercapacitors

Thick and highly conductive poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate films with ideal porous structure are fulfilling as electrodes for supercapacitors. However, the homogeneous micro-structure without the aid of templates or composite presents a significant obstacle, due to the intrinsic softness of the dominant PSS component. In this study, we have successfully developed a porous configuration by employing a solvothermal approach with ethylene glycol (EG) as the solvent. The synergistic action of elevated pressure and temperature was crucial in prompting EG to tailor the microstructure of the PEDOT:PSS films by removing non-conductive PSS chains and improving PEDOT crystallinity, and the formation of a porous network. The resulting porous PEDOT:PSS films exhibited a high conductivity of 1644 ​S ​cm−1 and achieved a volumetric capacitance record of 270 ​F ​cm−3, markedly exceeding previous records. The flexible all-solid-state supercapacitor assembled by the films had an outstanding volumetric capacitance of 97.8 ​F ​cm−3 and an energy density of 8.7 ​mWh cm−3, which is best one for pure PEDOT:PSS-based supercapacitors. Grazing-incidence wide-angle X-ray scattering, X-ray photo-electron spectroscopy, and other characterizations were carried out to characterize the structure evolution. This work offers an effective novel method for conducting polymer morphology control and promotes PEDOT:PSS applications in energy storage field.

Doping effect and oxygen vacancy engineering in nickel-manganese layered double hydroxides for high-performance supercapacitors

Design of electrode materials with high electrochemical capacitance and long lifetime remains a challenging issue for high-performance supercapacitors. Herein, we successfully synthesized a binder-free composite electrode comprising oxygen vacancy-abundant NiMnMg-layered double hydroxides grown on 3D graphene foam (Vo-NiMnMg-LDH@3DG) by Mg doping during hydrothermal process and subsequently Ar plasma etching. Thanks to the incorporation of electrochemically inert Mg element, the enhanced charge transfer capability, and enriched active sites that induced by plentiful oxygen vacancies, Vo-NiMnMg-LDH@3DG manifests a high specific capacity of 374.8 mAh g−1 at a current density of 1 A g−1 and satisfactory rate performance (74.26% at 20 A g−1). Furthermore, the asymmetric supercapacitor (ASC) assembled with Vo-NiMnMg-LDH@3DG cathode and activated carbon anode exhibits a specific capacitance up to 171 F g−1 at 1 A g−1, achieving a maximum energy density of 53.62 Wh kg−1 and the highest power density of 7500 W kg−1. This work not only provides innovative approaches for preparing oxygen vacancy-rich LDH materials, but also offers insights for the design and improvement of energy storage devices based on transition metal-based LDH.

Enzymatic synthesis of biocompatible polypyrrole with enhanced electrochemical properties for supercapacitors

This study focuses on the biocompatible and ecofriendly enzymatic synthesis of conductive polypyrrole (PPy) using mediators for supercapacitor electrode material. The work investigates the effects of various mediator systems on laccase-catalyzed oxidation of pyrrole and is confirmed through Fourier transform infrared spectroscopy (FTIR) and Ultraviolet (UV) visible spectroscopy. The x-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis has revealed that both mediators and laccase can produce crystalline and amorphous PPy with agglomeration of globular-shaped particles. The PPy-ABTS (2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonate) demonstrates higher decomposition temperatures, indicating superior thermal stability up to 400 °C. Electrochemical studies such as cyclic voltammetry (CV), galvanometric charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS) revealed that PPy-ABTS possesses good electrochemical properties. Compared to other laccase-mediated materials synthesized PPy in this study, PPy-ABTS exhibits higher specific capacitance values (242 F g−1 by CV at 10 mV s−1 and 153 F g−1 by GCD at 1 A g−1), with a capacitance retention of nearly 90 % after 10000 cycles. Cytotoxicity study shows that PPy-ABTS has an IC50 value of 528 μg ml−1 against human breast adenocarcinoma (MCF-7) cells, indicating its biocompatibility. Consequently, PPy-ABTS emerges as a promising electrode material for high-performance supercapacitors. Its unreported biocompatibility opens up possibilities for diverse biomedical applications.

Al-Ce co-doped BaTiO3 nanofibers as a high-performance bifunctional electrochemical supercapacitor and water-splitting electrocatalyst

Supercapacitors and water splitting cells have recently played a key role in offering green energy through converting renewable sources into electricity. Perovskite-type electrocatalysts such as BaTiO3, have been well-known for their ability to efficiently split water and serve as supercapacitors due to their high electrocatalytic activity. In this study, BaTiO3, Al-doped BaTiO3, Ce-doped BaTiO3, and Al-Ce co-doped BaTiO3 nanofibers were fabricated via a two-step hydrothermal method, which were then characterized and compared for their electrocatalytic performance. Based on the obtained results, Al-Ce co-doped BaTiO3 electrode exhibited a high capacitance of 224.18 Fg−1 at a scan rate of 10 mVs−1, high durability during over the 1000 CV cycles and 2000 charge–discharge cycles, proving effective energy storage properties. Additionally, the onset potentials for OER and HER processes were 11 and − 174 mV vs. RHE, respectively, demonstrating the high activity of the Al-Ce co-doped BaTiO3 electrode. Moreover, in overall water splitting, the amount of the overpotential was 0.820 mV at 10 mAcm−2, which confirmed the excellent efficiency of the electrode. Hence, the remarkable electrocatalytic performance of the Al-Ce co-doped BaTiO3 electrode make it a promising candidate for renewable energy technologies owing to its high conductivity and fast charge transfer.

Ultrasonic-Assisted Electrodeposition of Mn-Doped NiCo2O4 for Enhanced Photodegradation of Methyl Red, Hydrogen Production, and Supercapacitor Applications

This paper presents a novel ultrasonic-assisted electrodeposition process of Mn-doped NiCo2O4 onto a commercial nickel foam in a neutral electroplating bath (pH = 7.0) under an ultrasonic power of 1.2 V and 100 W. Different sample properties were studied based on their crystallinity through X-ray diffraction (XRD), morphology was studied through scanning electron microscopy (SEM), and photodegradation was studied through ultraviolet–visible (UV–Vis) spectrophotometry. Based on the XRD results, the dominant crystallite phase obtained was shown to be a pure single NiCo2O4 phase. The optical properties of the photocatalytic film showed a range of energy band gaps between 1.72 and 1.73 eV from the absorption spectrum. The surface hydroxyl groups on the catalytic surface of the Mn-doped NiCo2O4 thin films showed significant improvements in removing methyl red via photodegradation, achieving 88% degradation in 60 min, which was approximately 1.6 times higher than that of pure NiCo2O4 thin films. The maximum hydrogen rate of the composite films under 100 mW/cm2 illumination was 38 μmol/cm2 with a +3.5 V external potential. The electrochemical performance test also showed a high capacity retention rate (96% after 5000 charge–discharge cycles), high capacity (260 Fg−1), and low intrinsic resistance (0.8 Ω). This work concludes that the Mn-doped NiCo2O4 hybrid with oxygen-poor conditions (oxygen vacancies) is a promising composite electrode candidate for methyl red removal, hydrogen evolution, and high-performance hybrid supercapacitor applications.

Synthesis of Microscopic 3D Graphene for High-Performance Supercapacitors with Ultra-High Areal Capacitance.

Despite graphene being considered an ideal supercapacitor electrode material, its use in commercial devices is limited because few methods exist to produce high-quality graphene at a large scale and low cost. A simple method is reported to synthesize 3D graphene by graphenization of coal tar pitch with a K2CO3 catalyst. This produces 3D graphenes with high specific surface areas up to 2113 m2 g-1 and exceptional crystallinity (Raman ID/IG as low as ≈0.15). The material has an outstanding specific capacitance of 182.6 F g-1 at a current density of 1.0 A g-1. This occurs at a mass loading of 30mg cm-2 which is 3 times higher than commercial requirements, yielding an ultra-high areal capacitance of 5.48 F cm-2. The K2CO3 is recycled and reused over 10 cycles with material quality and electrocapacitive performance of 3D graphene retained and verified after each cycle. The synthesis method and resulting electrocapacitive performance properties create new opportunities for using 3D graphene more broadly in practical supercapacitor devices.

N, O-codoped porous carbon fiber cloth synthesized by molecular dispersed CaCl2·6H2O in situ activation for high performance supercapacitors

In this study, a nitrogen/oxygen co-doped carbon fiber cloth with a hierarchical porous structure was synthesized by one-step carbonization and in situ activation method and acted as binder-free electrode materials for supercapacitors. Cotton fiber cloth served as the carbon precursor, while molecular dispersed CaCl2·6H2O and urea functioned as activator and N dopant, respectively. The influence of molar concentration of CaCl2·6H2O and urea on the microstructure and capacitive performance of the resulting products were investigated. CaCl2·6H2O has an expansion effect on pores, resulting in reduction of micropores. Hence, the specific surface area of the resulting porous carbon increased first and then decreased with the increase of CaCl2·6H2O concentration. In addition, the erosion of NH3 and CO2 (produced by the decomposition of urea) at high temperature on the surface of the samples promoted the formation of porous structure. Urea plays the dual role of doping and activation agent. The morphology and structure analysis shown that the activated samples exhibited hierarchical pore structure, large specific surface area, and high heteroatom content. The optimal sample NAC-20 exhibited good capacitive performance, including high specific capacitance of 260.9 F g−1 at 0.1 A g−1 and good rate performance. Moreover, the symmetric supercapacitor exhibited a maximum energy density and power density of 16.2 Wh kg−1 and 19.0 kW kg−1, respectively, in 6 M KOH electrolyte. In this work, a green, low-cost molten salt activation method was proposed to synthesis biomass derived porous carbon materials for energy storage devices.

Lignosulfonate-Assisted Synthesis of Porous Carbon-Supported MnO2 Composites with Reinforced Interface Bonding for High-Performance Asymmetric Supercapacitors

Lignosulfonate-Assisted Synthesis of Porous Carbon-Supported MnO₂ Composites with Reinforced Interface Bonding for High-Performance Asymmetric Supercapacitors

Eco-friendly choline acetate/propionate ionic liquids as novel green electrolytes for high performance supercapacitors

Eco-friendly choline acetate/propionate ionic liquids as novel green electrolytes for high performance supercapacitors

Solution-processed Sb2O3: A promising electrode material for high-performance supercapacitors and electrocatalysts

Easy accessibility, wide range of redox states, affordable cost, and simple synthesis methods of metal oxides have gained a significant interest in the domains of electrochemical supercapacitors and electrocatalysts. The successive ionic layer adsorption and reaction (SILAR) chemical synthesis approach has been introduced to preparing nanocrystalline antimony oxide (Sb2O3) for both energy storage and water splitting applications. The Sb2O3 electrode demonstrates a remarkable specific capacitance of 3011 F/g at a current density of 2 A/g in a 1 M solution of potassium hydroxide (KOH). The current design of the Sb2O3//Bi2O3 (bismuth oxide) asymmetric electrochemical supercapacitor device has endowed a specific capacitance of 391 F/g, a maximum energy density of 78.2 Wh/Kg at a power density of 1000 W/Kg, and an outstanding capacitance retention of 77 % even after 5000 redox cycles. The Sb2O3 electrode demonstrates outstanding performance in the oxygen evolution process at a current density of 10 mA cm2, with an overpotential of 206 mV. The Sb2O3 as an electrocatalyst also exhibits exceptional results in the hydrogen evolution reaction with an overpotential of 124 mV/dec. Both of these electrochemical processes are distinguished by the evolution of oxygen which is capable of facilitating the process of water splitting to obtain clean energy for day by day growing population.

Nitrogen-doped porous carbon derived from cross-cutting bamboo for high-performance supercapacitors by one-pot ball milling method

In this work, Nitrogen-doped cross-cut KOH-activated porous carbon (NCKC) was obtained through a simple and effective fabrication process. Cross-cut bamboo, KOH, and urea are mixed through a one-pot ball milling strategy. The obtained sample (NCKC) has a high specific capacitance in the three-electrode test (367 F·g−1 at 0.2 A· g−1), and maintains a satisfactory specific capacitance of 183 F·g−1 at a high current of 50 A·g−1. Moreover, an aqueous supercapacitor based on NCKC with 1 M Na2SO4 as the electrolyte can provide an outstanding specific energy of 31.1 W h kg−1 with a specific power of 200 W·kg−1, without any noticeable reduction in capacity even after 40,000 cycles. This is attributed to the fact that NCKC has an abundant hierarchical pore structure. The cross-cutting process can shorten natural pores origin from bamboo native structures, and facilitate hydrophilicity in the resulting porous carbon. The results reveal that the synergistic effect of cross-cutting process, ball milling, and N-doping in carbon enhanced the electrochemical performance of carbon remarkably. The results show such one-pot ball milling method simplifies the preparation process and is of great interest for the innovation and application of high-performance electrode materials.

Novel sulfonated polyaniline/graphene oxide electrode with high cycling stability for all-solid-state flexible supercapacitors

Polyaniline (PANi) has high theoretical specific capacitance by storing energy through redox reactions and thus is widely used in supercapacitors. However, the skeleton of PANi expands and contracts during the process of ion inhalation and exfoliation, which leads to a decrease in electrochemical performance. To solve this problem, we graft the sulfonic acid group onto the PANi backbone via a borate ester bond, which serves as a proton reservoir to provide protons for PANi to undergo redox reactions and provide pseudocapacitance. SPANi is then polymerized in situ on graphene oxide (GO), and its comprehensive performance of the electrode is further enhanced by designing ordered structures and synergistic interactions. The SPANi5/GO5 composite that are created in-situ have a fantastic specific capacitance of 460.56 F g−1 at 1 A g−1 and maintained 85.19% of the primary capacitance after 10,000 cycles. The device is assembled with PAAM/H2SO4/GO as the gel electrolyte, which achieves a specific capacitance of 137.75 F g−1, and the capacitance is retains at 90.74% after 10,000 cycles. The supercapacitor exhibits a large energy density of 13.76 Wh kg−1 when the power density is 200.27 W kg−1. The present study presents a novel and efficient approach for the fabrication of high-performance supercapacitor electrodes.

Prussian blue analogue-based superstructure nanoarrays for sodium ion hybrid supercapacitors

Supercapacitors (SCs) have attracted significant attention due to their remarkable traits of high-power density and prolonged cyclability. Despite the extensive exploration of Prussian blue analogues (PBAs) with three-dimensional (3D) open frameworks as SC electrodes, their instability and low conductivity have impeded their advancement in practical SC applications. In this study, we present a straightforward immersion-based technique to produce a superstructure nanoarray of CoNiFe-based PBA (CoNiFePBA). The unique superstructure comprises ultrathin nanosheets assembled into a half-open hollow configuration, fostering abundant active surface sites, a stable framework, and efficient channels for ion/electron transfer, consequently enabling effective charge storage. Furthermore, the integration of ternary metals not only offers numerous redox reaction centers but also heightens synergistic effects, resulting in enhanced capacity and cycling stability. As a result, the CoNiFePBA electrode delivers outstanding specific capacity (96.85 mAh g−1 at 0.5 A g−1) and enduring cycling stability (92.25 % after 10,000 cycles). Notably, the hybrid SC built on the CoNiFePBA demonstrates an exceptionally broad voltage window (2.1 V) and a high energy density. This work underscores the immense potential of CoNiFePBA superstructure nanoarrays for driving high-performance SC technology forward.

Electrodeposited three-dimensional hierarchical architecture of MgO anchored with Ag nanoparticles for high-performance symmetric supercapacitors

A blossom-like, three-dimensional (3D) hierarchical architecture of MgO anchored with silver nanoparticles (Ag NPs) is developed using a simple galvanostatic electrodeposition method. This study shows how electrochemical performance is improved by the incorporation of Ag NPs within a 3D framework. The 3D blossom-like scaffold comprises thin 2D petals, whose porous lace-like patterns provide a large surface area and many channels for the rapid diffusion of electrolyte ions. The anchored Ag NPs increase the electrical conductivity of the MgO structure and enhance redox reactions. An optimum Ag loading of 10 vol% on MgO (MgO@Ag-10) affords a 100-fold enhancement in specific capacitance over that of MgO. This hybrid MgO@Ag-10 electrode on a stainless-steel substrate yields a specific capacitance of 388.6 F.g−1 (134.85 mF.cm−2) at a current density (CD) of 1 mA.cm−2, whereas pure MgO delivers only 3.72 F.g−1 (3.1 mF.cm−2) at the same CD in a three-electrode system. The MgO@Ag-10 electrode also exhibits 88.6 % capacitance retention over 5000 charge–discharge cycles. A symmetric supercapacitor device comprising two MgO@Ag-10 electrodes exhibits a specific capacitance of 42 F.g−1, an energy density of 23.33 Wh.kg−1, and a power density of 8000 W.kg−1 at 4 mA.cm−2 in aqueous KOH.

Carbamide-mediated facile sol-gel synthesis of porous flower-like ZnCo2O4 microspheres for high-performance asymmetric coin cell supercapacitors

The design and development of ultrahigh-performance nanomaterials possessing novel characteristics are needed to achieve reliable energy storage performance. To satisfy the needs, diverse electrode materials are explored. Even though carbon-based materials hold high surface area and conductivity, their specific capacitance value fails to deliver high-performance applications. Therefore, pseudocapacitive transition metal oxide is adopted to overcome these issues. Among all Zinc Cobaltite, a binary transition metal oxide is widely explored owing to its fascinating electrochemical properties. As most of the synthesis of these kinds of materials requires the hydro/solvothermal method, herein, we have proposed the concept of a facile sol-gel method to prepare this class of materials by using Carbamide as both structure director and fuel to achieve the porous flower-like Zinc Cobaltite. The prepared material delivers the notable gravimetric specific capacitance of 513.3 F g−1. Owing to its unique morphology and porous structure, ion channelization is feasible, which will enhance the electrochemical reaction. Constructed asymmetric coin cell supercapacitor showed an extraordinary specific capacitance of 106.5 F g−1 and energy density of 56.2 Wh kg−1, demonstrating an impressive ability to retain 89.6 % of its capacitance after 4000 cycles at a current density of 6 A g−1. Due to the remarkable electrochemical behavior, this work can act as a guiding tool for designing efficient and cost-effective energy storage devices that will hold prodigious potential in commercial energy storage applications.

Facile synthesis of cryogenically controlled cobalt-nickel-based Prussian blue analogues for high-performance symmetric supercapacitors

Cobalt hexacyanoferrate (CoHCF) with high energy density as a potentially useful electrode for energy storage systems still suffers from inferior rate capability and low cycling performance due to high-spin nitrogen-coordinated Co ions. While nickel hexacyanoferrate (NiHCF) with low energy density can exhibit great cycling stability due to the electrochemical inertness of Ni. Herein, we have developed a series of cobalt nickel hexacyanoferrate (CoNiHCF) via a facile cryogenically controlled co-precipitation method. We explored the Co/Ni molar ratio and synthesis temperature on the effects of the specific capacitance in detail. As supercapacitor cathode, the Co0.7Ni0.3HCF with the Co/Ni molar ratio of 0.7:0.3 synthesized at 0 °C can exhibit a high specific capacitance of 406 F g−1 at 1 A·g−1 with capacitance retention of 81.89 % after 5000 cycles. The exceptional electrochemical performance is ascribed to the upgraded conductivity resulting from the coexistence of bimetallic components, the low particle size caused by the moderate introduction of Ni, the low interstitial water content, and the synergistic effect between Co and Ni. Moreover, the symmetric supercapacitor (SSC) of Co0.7Ni0.3HCF//Co0.7Ni0.3HCF can provide a high energy density of 72.96 W h kg−1 and 40.96 W h kg−1 at specific powers of 2876 W kg−1 and 28,577 W kg−1, respectively with a capacitance retention of 74.83 % after 4000 cycles.

Cation-driven self-assembly of core–shell covalent organic frameworks@Ti3CN MXene nanospheres for high-performance aqueous zinc-ion hybrid supercapacitors

Rechargeable aqueous Zn-ion hybrid supercapacitors (ZISCs) with the superiorities of high theoretical capacity, low redox potential and aqueous electrolytes with superior ionic conductivity (∼1 S cm−1) are promising energy storage systems. However, a primary concern persists due to the absence of cathode materials with both high energy densities and satisfactory cycling stability for robust ZISCs. In this study, we design a spherical core–shell covalent organic frameworks@Ti3CN MXene (CM-P) cathode via a cation-driven electrostatic self-assembly strategy. The CM-P with the constructed heterostructures shows both well-organized pore channels and excellent intrinsic conductivity, facilitating fast accessibility to intrinsic redox-active sites (such as C = O and N), and promoting effective ion diffusion characterized by low energy barriers. Consequently, the CM-P cathodes demonstrate excellent electrochemical performance, featuring an ultrahigh specific capacity of 260 mAh/g at 0.1 A, a high-rate capability with 68 % retention at 1 A/g, and long-term cycling stability. First-principle calculations elucidate that the enhanced charge-storage mechanism relies on the heterostructures of CM-P, accelerating ion adsorption/diffusion and electron transfer. Furthermore, the assembled CM-P//Zn ZISCs devices show a high energy density of 217.1 Wh kg−1 along with power density of 22.3 kW kg−1. This work provides an innovative approach to design COFs-based heterostructures for advanced ZISCs.