Metal organic frame work inserted NiCo 2 O 4 for asymmetric supercapacitor applications

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Malarkodi, J. C. Kannan This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8780253/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Porous metal-organic frameworks, or MOFs, hold great promise as elements for a wide range of functional materials with the potential to store and convert electrochemical energy with exceptional performance. For use in high-performance supercapacitors, this article introduces bimetallic oxide (NiCo 2 O 4 -MOF) electrode materials made from metal-organic frameworks (MOFs). The optimal Ni-MOF@NiCo 2 O 4 (NCO@MOF) electrode achieves a maximum specific capacity of 560 Fg − 1 at 1 Ag − 1 and an outstanding rate capability of 87% after 5000 cycles, significantly exceeding that of its separate components. The constructed asymmetric device (ASC) utilising NiCo2O4-MOF as the positive electrode and activated carbon as the negative electrode demonstrated an exceptional energy density of 30.6 Wh kg − 1 at a power density of 480 W kg − 1 , with 84% capacitance retention after 10,000 cycles. This paper presents a novel method for the synthesis and fabrication of metal oxides originating from MOFs, recognised for their elevated porosity, advantageous for electrochemical energy storage applications. Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Introduction In the last ten years, there has been rapid progress in next-generation flexible electronics, including wearable and portable appliances, rollable monitors, and electronic skins. In order to meet the increasing needs, it is crucial to develop new energy storage systems that are sustainable, efficient, and very flexible [ 1 – 9 ]. The various advantages of hybrid supercapacitors (HSCs)—including extended cycle life, lower maintenance expenses, enhanced safety, quick charge/discharge capabilities, elevated energy and power densities, and swift charge/discharge—have recently garnered significant interest as a potential alternative or complement to lithium-ion batteries[ 10 – 12 ]. The energy and power sources of HSC devices comprise a battery-type Faradaic cathode featuring transition metal oxides, hydroxides, sulphides, and phosphides, alongside an electrochemical double layer capacitance (EDLC)-type anode constructed from carbonaceous materials. The type of battery cathode significantly influences the overall performance of HSC devices. As a result, the primary objective of the current investigation into HSC devices is to identify novel battery-type materials that exhibit exceptional electrochemical properties. A new class of porous crystalline materials called metal-organic frameworks (MOFs) has recently attracted a lot of attention because of its many different topologies, configurable functions, and widespread porosity [ 13 , 14 ]. Metal-organic frameworks (MOFs) have recently attracted significant attention as a novel category of porous crystalline materials, owing to their extensive porosity, adjustable functionalities, and diverse range of topologies [ 15 ]. Multiple research teams have demonstrated that MOFs can serve as adaptable sacrificial templates for the synthesis of diverse forms of porous carbon, metal oxides, metal hydroxides, or composite materials comprising these components. Unfortunately, the process that involves heating the material to a high temperature is not only energy-intensive but also somewhat complicated. Additionally, the precursor MOFs' delicate porous interior structures are generally degraded to some extent, which limits how well they can be used for energy storage. A lot of people have been interested in using MOFs as supercapacitor electrode materials recently. Because of its excellent stability in alkaline electrolytes and relatively high specific capacity, a layered structure of nickel-based MOF has been widely chosen and used as electrode materials for supercapacitors among various metal-organic frameworks [ 16 ]. Using a solvothermal approach, Wei and colleagues successfully synthesized a two-dimensional (2D) layered Ni-MOF structure. This structure showed a rate capability of 60% and a specific capacity of 109.6 mA h/g [ 17 ]. The production of multi-nanosheet Ni-MOF microspheres was described in detail by Pei et al. utilizing a similar solvothermal method. According to the research, the specific capacity and rate capability of Ni-MOF were significantly enhanced when partially substituted with Co 2+ or Zn 2+ ions [ 18 ]. In a recent study, Pang's group detailed how bulk Ni-MOF can be ultrasonically treated into thin nanosheets, creating an accordion-like superstructure. This structure has impressive cycling stability, maintaining 96.5% of its initial capacity over 5000 cycles, and a specific capacity of 123.5 mA h/g [ 19 ]. Several electroactive materials with improved conductivity have been employed due to the fact that pure MOFs typically have a low electrical conductivity, which restricts their use in electrochemical applications. Graphene and carbon nanotubes are examples of carbonaceous compounds; polyaniline and polypyrrole are examples of conductive polymers. To improve the electrochemical characteristics of MOF-based composite materials, these components are being added. A recent demonstration by Lai and colleagues demonstrated the use of an in situ self-transformation technique to incorporate metal oxides into the MOF system. The outcome of this method was an increased rate capability and a specific capacity that was three times higher for the MOF−MnOx composite [ 20 ]. The direct use of MOFs as electrode materials still presents difficulties, despite considerable advancements in this field. Since these MOFs have a strong propensity to aggregate when mixed with water, they are often manufactured in powder form [ 21 ]. In addition, the electrode's electrochemical performance will be negatively affected because of the conductive additives and polymer binders that must be included during electrode preparation. These additives reduce the electrode's flexibility, decrease the effective surface area, and prevent the efficient penetration of electrolyte ions within the electrode. We propose a simple two-step solution-based process for fabricating hierarchical NiCo 2 O 4 @Ni-MOF hybrid arrays, which are advanced electrodes for HSC devices, taking into account the previously mentioned factors. Few articles have addressed the production of well-aligned MOF arrays on conductive three-dimensional (3D) matrices and their direct application in electrochemical energy storage, as far as we are aware [ 22 ]. This research details the methods used to methodically construct arrays of Ni-MOFs on NiCo 2 O 4 nanorodss by precisely controlling the MOF formation reaction. Anchored firmly on NiCo 2 O 4 are the Ni-MOF nanorodss, which include linked layers with a high surface area and abundant porosity. Not only does this arrangement improve the electrochemical characteristics in a synergistic way, but it also allows for more favorable kinetics of ion diffusion and electron transport inside the hybrid electrode. The optimized NiCo 2 O 4 @Ni-MOF hybrid electrode can reach a rate capability of 89% at a current density ten times higher and an impressive specific capacity of 506 Fg − 1 at 1 Ag − 1 . A flexible and durable solid-state HSC device is constructed using activated carbon (AC) as the anode and NiCo 2 O 4 @Ni-MOF as the cathode. The adaptive NiCo 2 O 4 @Ni-MOF//AC HSC device has a peak energy density of 30.6 W h/kg at a power density of 498 W/kg, indicating exceptional mechanical stability. The exceptional cycling stability—approximately 82% retention after 10,000 cycles—positions MOF-based hybrid arrays as a viable option for high-performance battery-type electrodes in HSC devices. Experimental Section Synthesis of NiCo 2 O 4 nanoparticles through hydrothermal method. The analytical grade chemicals were sourced from Aladin and utilised precisely as specified. In the standard procedure for synthesising NiCo 2 O 4 nanorods arrays, a mixture was prepared by combining 0.1 mmol of Ni(NO 3 ) 2 ·6H 2 O, 0.15 mmol of Co(NO 3)2 ·6H 2 O, and 0.10 mmol of CO(NH 2 ) 2 with 50 mL of deionised (DI) water, followed by stirring. Subsequently, the mixture was moved to a stainless steel autoclave lined with Teflon. A temperature of 140°C was maintained for 6 hours in the sealed autoclave. After cooling down to room temperature, the sample was washed with water and ethanol to remove the unwanted impurities. After washing the sample was dried at oven at 100˚C and sintered at 350 ˚C for 3h. A simple solvothermal method was used to create the hierarchical NiCo 2 O 4 @Ni-MOF hybrid arrays by growing Ni-MOF nanosheets on NiCo 2 O 4 nanorodss. The standard procedure involved dissolving 0.1mmol of Ni(NO 3 ) 2 ·6H 2 O and 0.05 mmol p-benzenedicarboxylic acid (PTA) in 20 mL of N,N-dimethylformamide (DMF) in separate solutions. Carefully, the nickel nitrate solution was added to the PTA solution dropwise at a controlled rate of 0.3 mL/min while stirring continuously, and the 0.12 g NiCo 2 O 4 was added to the mixed solution were then kept in the reaction autoclave, which was kept at 120°C for the duration of the reaction. After cooling down the sample was washed with ethanol and DMF rinses, the samples were dried for an entire night at 80°C. NiCo 2 O 4 @Ni-MOF hybrid arrays are then created and utilized for additional analysis. The prepared samples were named as NCO (NiCo 2 O 4 ) and NCO@MOF (NiCo 2 O 4 @Ni-MOF). Materials Characterization. X-ray diffraction (XRD, Bruker) was used to characterize the structure of the as-prepared samples. Field emission scanning electron microscopy (Zeiss Ultra 55) were used to acquire the microstructure and detailed morphology, respectively. The chemical compositions were examined with the help of a X-ray photoelectron spectroscope (XPS, MKLAB). Fabrication of Solid-State HSCs. Full-cell devices, designated as NCO@MOF//AC, were constructed utilising the optimised NCO@MOF for the cathode and AC for the anode, with cellulose paper serving as the separator. To prepare the gel electrolyte, combine the appropriate quantities of polyvinyl alcohol (PVA) and potassium hydroxide (KOH) in deionised water, stirring continuously while heating to 90°C until the mixture becomes clear. In addition, for the anode's construction, N-methyl-2-pyrrolidinone was mixed with 80% activated carbon, 10% polyvinylidene fluoride, and 10% acetylene black. The carbon fabric was evenly coated with the resulting slurry, and then it was vacuum-dried at 80°C for 12 hours. A two-electrode system was used to assess the electrochemical performance of the constructed HSC device, which was then sealed with PET films to avoid electrolyte leakage. Results and Discussion In Fig. 1 we can see the simplified version of the synthesis procedure for NCO@MOF core/shell hybrid arrays provided by this research. A post-annealing procedure successfully establishes a framework for the subsequent development of MOF shells from self-supported NCO nanorods arrays, which are initially produced via the hydrothermal reaction of Ni2 + and Co2 + ions with the hydrolysis product of urea. After that, NCO nanorodss are methodically coated with interconnected Ni-MOF nanosheets using a simple solvothermal technique. The intended NCO@MOF hybrid is eventually formed as a result of this method. With a NCO core and a Ni-MOF shell, these unique three-dimensional hierarchical nanostructures are expected to provide favorable kinetics for quick electron transport and ion diffusion. Furthermore, it is anticipated that the components will show notable synergistic effects, leading to significantly enhanced electrochemical characteristics. First, scanning electron microscopy (SEM) is used to analyze the surface morphologies of the NCO arrays synthesized and the NCO@MOF arrays. The nearly uniformly manufactured pure NCO composite has an average diameter of 18–20 nm, as shown in Figs. 2 a and 2 b. Figure 2 c, d shows a hybrid electrode that has been hydrothermally modified to cover the NCO structure with multiple layers of Ni-MOF nanosheets. The ability to regulate the ratios and hence the creation of Ni-MOF shells is crucial. This is because the Ni-MOF shells thicken with increasing ratio, leading to a marked increase in mass loading. At the same time, the interstitial space among the NCO nanorodss is substantially occupied by the Ni-MOF shells. Figure 2 (e-g) shows the elemental mapping of NCO@MOF samples which cleary shows that pure phase of sample was achieved with no impurities [ 23 ]. As shown in Figs. 4 , XPS characterization is used to investigate the surface states and chemical composition of the samples. Comparison of the standard survey spectra of pure NCO and NCO@MOF composite arrays synthesized by hydrothermal method is shown in Fig. 4 a. Figure 4 b shows the Ni 2p core-level spectra that were fitted with a Gaussian distribution. According to NiCo 2 O 4 , Ni 2+ is responsible for the peaks at 854 and 871 eV, while Ni3 + is responsible for the peaks at 855 and 873 eV, with their respective satellite peaks at 861 and 879 eV. In the Co 2p spectrum (Fig. 4 c), a single shifted satellite and two distinct spin-orbit doublets were observed. Co 3+ is indicated by the initial doublet at 778 eV in Co 2p 3/2 and 793 eV in Co 2p 1/2 , whereas Co 2+ is indicated by the subsequent doublet at 779 eV in Co 2p 3/2 and 796.7 eV in Co 2p 1/2 . Three distinct peaks at 529 to 532 eV are observed in the O 1s spectrum of NiCo 2 O 4 , as shown in Fig. 4 d. These peaks correspond to oxygen at defect sites, surface-adsorbed H 2 O, and lattice oxygen, respectively the other hand, the large O 1s peaks located at 531 and 532 eV, respectively, in NCO@MOF are thought to be O − C = O links in Ni-MOF and metal−oxygen bonds in Ni-MOF. Further evidence that the Ni-MOF shell completely covers NiCo 2 O 4 is the fact that the hybrid arrays of NCO@MOF do not show the lattice oxygen peak (529 eV) from NCO [ 26 – 28 ]. Figure 5 shows the surface area analysis and pore size distribution of NCO and NCO@MOF samples respectively. Compare of NCO (Fig. 5 a), the NCO@MOF (Fig. 5 b) delivers higher surface area of about 228 m 2 g − 1 with pore diameter of 2–4 nm. This clearly shows that NCO@MOF sample possess the larger surface area with mesopores nature which greatly enhances the electrochemical performance of NCO@MOF sample during cycling. Initially, electrochemical assessments were performed using a three-electrode setup with a 2 M KOH electrolyte to showcase the enhanced electrochemical characteristics of the NCO and NCO-MOF hybrid electrodes for supercapacitor applications. In Fig. 6 , we can see that the NCO-MOF hybrid electrode has the best electrochemical performance when compared to the NCO. This is based on a comparison of the CV and GCD curves, as well as the rate capabilities of the two electrodes. An appropriate reaction time for deposition of Ni-MOF shells on NiCo 2 O 4 arrays is required, as an excess of Ni-MOF shells may compromise electrochemical characteristics by preventing electrolyte ions from entering the underlying materials. Additionally, each CV curve displays a pair of redox peaks linked to the Faradaic redox reaction of transition-metal ions with the electrolyte, confirming their battery-type distinguishing characteristics. The hybrid electrode made of Ni-MOF shows a significantly larger CV enclosed area and peak current density when compared to pure NCO. Based on these findings, it can be concluded that the hybrid arrays' Ni-MOF nanosheets offer much more capacity compared to pure materials, even if the mass loading is almost the same. This discovery underscores the unique synergistic interaction between the core and shell nanostructures [29]. The CV curves were shown in Fig. 6 (a, b) Figure 6 c illustrates the logarithmic connection between peak current and scan rates of NCO@MOF derived from CV analysis at various scan rates. Diffusion-controlled battery behavior is demonstrated by the NCO@MOF hybrid electrode, as indicated by the calculated b values for the cathodic and anodic reaction processes of 0.55 and 0.65, respectively. The GCD curves for NCO and NCO@MOF at various current densities are displayed in Fig. 6 d, e. Additionally, as shown in Fig. 6 f,g this outstanding value is among the highest that have been recorded for NCO@MOF -based electrodes thus far. Compared to the pristine NCO, which exhibits a rate capability of 78.5%, the optimized NCO@MOF electrode exhibits a notable improvement in rate capability, reaching 87%. The Nyquist plots depicting the electrochemical impedance spectroscopy (EIS) spectra for the three electrodes are presented in Fig. 6 h. In the high-frequency regions, these plots will exhibit a semicircle that indicates the charge-transfer resistance (Rct) at the electrode/electrolyte interface. Conversely, in the low-frequency regions, a sloped straight line will represent the Warburg impedance (Zw) within the electrode [ 30 ]. The equivalent series resistance (Rs) will be indicated by the intercept with the real axis. According to the figures, NCO@MOF, the Rs is slightly lower at 0.38 Ω compared to pure Ni-MOF's 0.38 Ω, and the Rct is much lower at 4.0 Ω compared to Ni-MOF's 7.8 Ω. The ion diffusion dynamics of NCO are also comparable. Therefore, the enhanced electrochemical performance of the NCO@MOF hybrid electrode may be well explained by the combined benefits of fast electron conduction and ionic diffusion kinetics [ 31 ]. We have developed all-solid-state HSC devices to evaluate their practicality, leveraging the exceptional electrochemical properties of the NCO@MOF hybrid arrays. The solid-state HSC device incorporates activated carbon for the anode and utilises optimised NCO@MOF for the cathode.The electrolyte is PVA/KOH gel, as shown in Fig. 7 a. According to Fig. 7 , which shows the individual cyclic voltammetry curves of the two electrodes in a separate three-electrode setup, the HSC device appears to be capable of producing a consistent working voltage of 1.2 V. The device's CV curves, acquired at scan speeds ranging from 5 to 50 mV/s, are shown in Fig. 7 b. Both the EDLC and battery types of electrodes have an impact on the total capacity, as shown by the similarly distorted rectangular shape of the CV curves. To estimate the device's specific capacity values, Fig. 8c shows the discharge curves of the HSC device across a range of current densities from 1 to 10 Ag − 1 . The HSC apparatus demonstrates a notable specific capacity of 180 Ag − 1 at 1 Ag − 1 , resulting in a retention rate of 85% (Fig. 7 d, e). This decline may be attributed to restricted ion mobility within the gel electrolyte, especially at higher current densities [ 32 ]. At a current density of 1 Ag − 1 shows the HSC device's effectiveness in sustained cycling. It is remarkable that, even after 10,000 cycles, nearly all of the initial capacity can be maintained. This further proves the device's remarkable long-term cycling stability. Similar to other solid-state full-cell devices that use the improved NiCo 2 O 4 @Ni-MOF, we have observed an improvement in capacity during the device's cycling process. We studied the morphological change of the NiCo 2 O 4 @Ni-MOF hybrid electrode after cycling using various techniques. The calculated specific capacitance of solid state device was shown in Figure d Although the Ni-MOF shell's morphology has changed, showing many pores probably caused by the repeated intercalation and deintercalation of electrolyte ions, the hierarchical structure of the integrated electrode stays intact after 10 000 cycles, as shown in Fig. 7 e [ 33 ]. Energy density and power density serve as critical metrics for evaluating the performance of energy storage devices in real-world applications. Figure 7 f illustrates the Ragone plots of our NCO@MOF//AC hybrid supercapacitor device [ 34 – 40 ], in conjunction with other previously reported MOF-based hybrid supercapacitor devices for comparative evaluation. The multifunctional solid-state NCO@MOF//AC HSC device achieves a remarkable energy density of 30.6 W h/kg at 498 W/kg, while maintaining 12.6 W h/kg with a power density of 3846 W/kg. The energy density achieved by our flexible solid-state HSC device is equivalent to, or may exceed, that of other previously documented MOF-based HSC devices in an aqueous electrolyte. This further highlights the significant potential of MOF-based hybrid arrays as advanced battery-type electrodes for flexible energy storage solutions. Conclusions In conclusion, we have developed a two-step synthetic approach to facilitate the controlled assembly of hierarchical NiCo 2 O 4 @Ni-MOF hybrid arrays directly on carbon cloth, which function as advanced electrodes for flexible all-solid-state HSC devices. The integration of NiCo 2 O 4 and Ni-MOF in a unique 3D hierarchical structure offers significant benefits, enabling the optimised NiCo 2 O 4 @Ni-MOF hybrid electrode to attain an extraordinarily high specific capacity and impressive rate capability. The HSC device, incorporating the optimised NiCo 2 O 4 @Ni-MOF and AC, exhibits a maximum energy density of 30.6 W h/kg at 498 W/kg, along with exceptional long-term cycling stability of up to 10,000 cycles. This performance exceeds that of the majority of recently published MOF-based HSC devices in aqueous electrolyte systems. This study demonstrates the capability to design and fabricate novel MOF-based hybrid arrays for the development of highly efficient and durable flexible energy storage devices. Declarations Author Contribution Dr. P. Malarkodi : Analysis and wriiting the manuscript.Dr. J.C kannan: Editting the manuscript Acknowledgment No funds, grants, or other support was received. References Lu, X.; Yu, M.; Wang, G.; Tong, Y.; Li, Y. Flexible Solid-State Supercapacitors: Design, Fabrication and Applications. Energy Environ. Sci. 2014, 7, 2160−2181. Choi, S.; Lee, H.; Ghaffari, R.; Hyeon, T.; Kim, D.-H. Recent Advances in Flexible and Stretchable Bio-Electronic Devices Integrated with Nanomaterials. Adv. Mater. 2016, 28, 4203−4218. Khan, Y.; Ostfeld, A. E.; Lochner, C. M.; Pierre, A.; Arias, A. C. Monitoring of Vital Signs with Flexible and Wearable Medical Devices. Adv. Mater. 2016, 28, 4373−4395. Miao, Z.; Huang, Y.; Xin, J.; Su, X.; Sang, Y.; Liu, H.; Wang, J.-J. 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Formation of Bimetallic Metal-Organic Framework Nano sheets and their Derived Porous Nickel-Cobalt Sulfides for Super capacitors. Dalton Trans. 2018, 47, 5639−5645. Additional Declarations No competing interests reported. Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8780253","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Short Report","associatedPublications":[],"authors":[{"id":594101020,"identity":"87dba954-a491-4e3c-9ed7-e8b416802cd7","order_by":0,"name":"P. Malarkodi","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA90lEQVRIiWNgGAWjYFAC5gYGhgMMjG0MzAcffADy2dgJamGEaWFLNpwB0sJMrJYGBh4zaR6wtQQ06LYfbPxcccZGtk+6x0Da5tc2eT5mBsYPH3NwazE7k9gseeZGmnGbzLEC49y+24ZtzAzMkjO34dFyILFBsuHD4cQ2ieQNybk9txmBWtiYefFpOf+w+SdES4LBYcue2/aEtdxIbJNsuAHSkmLYzPDjdiIRWh62WTacAfslmbG34XZyGzNjM36/nE8+fLPhmI3s/NnNx3/8+HPbdn5788EPH/FoQQAJIAZGKAMkpogCIC0Mf4hUPApGwSgYBSMKAAByBVp0WCXRlwAAAABJRU5ErkJggg==","orcid":"","institution":"Shri Venkateshwara Hi-tech Engineering College.","correspondingAuthor":true,"prefix":"","firstName":"P.","middleName":"","lastName":"Malarkodi","suffix":""},{"id":594101021,"identity":"a2e812a2-1abc-4228-8d7c-bee4a045fe54","order_by":1,"name":"J. C. Kannan","email":"","orcid":"","institution":"KSR Institute of Engineering and Technology.","correspondingAuthor":false,"prefix":"","firstName":"J.","middleName":"C.","lastName":"Kannan","suffix":""}],"badges":[],"createdAt":"2026-02-03 23:08:16","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-8780253/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-8780253/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":103504044,"identity":"eddaaa6d-2f21-44a1-a8dd-d674c3dbd5b0","added_by":"auto","created_at":"2026-02-26 13:11:02","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":122921,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSchematic representation of preparing NiCo\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e and NiCo\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e@Ni-MOF via hydrothermal method\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8780253/v1/00561d0e8d73f595567d9fad.jpeg"},{"id":103112408,"identity":"008a7afe-768e-42d3-8db6-fef538531b9c","added_by":"auto","created_at":"2026-02-21 04:31:35","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":201949,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eFESEM analysis (a,b) NCO nanorods; (c,d) NCO@MOF; (e-g) Elemental Mapping\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8780253/v1/04b16a5b5e1965b5a05319d3.jpeg"},{"id":103504859,"identity":"d498172b-ed57-4626-b7ce-3fe8d0229c41","added_by":"auto","created_at":"2026-02-26 13:21:48","extension":"jpeg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":108368,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a) XRD analysis; (b) raman analysis of NCO and NCO@MOF samples\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage3.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8780253/v1/7ea2f0cc720f8c05c15e0c38.jpeg"},{"id":103504631,"identity":"c50c2587-94ad-4ed9-8298-975a27539a39","added_by":"auto","created_at":"2026-02-26 13:20:50","extension":"jpeg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":96687,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eXPS: (a) Survey spectra; (b) Ni 2p ;(c) Co 2P; (d) O1s\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage4.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8780253/v1/42796c5f9742f88689f2e6a4.jpeg"},{"id":103112410,"identity":"6f8883d6-5543-4308-a5cf-ffa82817c41a","added_by":"auto","created_at":"2026-02-21 04:31:35","extension":"jpeg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":105647,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eBet analysis (a) NCO; (b) NCO@MOF (inserted pore size distribution)\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage5.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8780253/v1/b7ea30230c0a729d3c049ffe.jpeg"},{"id":103112414,"identity":"24f9efeb-420f-453a-ba94-5de87e0783ca","added_by":"auto","created_at":"2026-02-21 04:31:35","extension":"jpeg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":189333,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eThree electrode configuration (a-b) CV analysis; (b) Square root vs. scan rate;(d-e) GCD pattern; (f) Current density vs specific capacitance; (g) Cyclic stability;( h) EIS analysis.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage6.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8780253/v1/73231bb7c8708b87b8649598.jpeg"},{"id":103112413,"identity":"ca25aadb-ac17-4af3-b227-ff264ba5e328","added_by":"auto","created_at":"2026-02-21 04:31:35","extension":"jpeg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":228062,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a) Fabrication of Asymmetric capacitor; (b) CV analysis of NCO@MOF//AC; (c) GCD pattern of\u0026nbsp; NCO@MOF//AC; (d) Current density Ag\u003c/strong\u003e\u003csup\u003e\u003cstrong\u003e-1 \u003c/strong\u003e\u003c/sup\u003e\u003cstrong\u003eVs specific capacitance Fg\u003c/strong\u003e\u003csup\u003e\u003cstrong\u003e-1\u003c/strong\u003e\u003c/sup\u003e\u003cstrong\u003e;(e) cycle test; (f) Ragone plot.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage7.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8780253/v1/4779cfd202eb7c0c1331d1db.jpeg"},{"id":106113965,"identity":"dfa43dcd-4cbf-4148-b55a-424bf5821ddd","added_by":"auto","created_at":"2026-04-03 15:41:36","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1769830,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8780253/v1/75877752-a8e5-4c41-a1c9-e67f36a972ba.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Metal organic frame work inserted NiCo 2 O 4 for asymmetric supercapacitor applications","fulltext":[{"header":"Introduction","content":"\u003cp\u003eIn the last ten years, there has been rapid progress in next-generation flexible electronics, including wearable and portable appliances, rollable monitors, and electronic skins. In order to meet the increasing needs, it is crucial to develop new energy storage systems that are sustainable, efficient, and very flexible [\u003cspan additionalcitationids=\"CR2 CR3 CR4 CR5 CR6 CR7 CR8\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. The various advantages of hybrid supercapacitors (HSCs)\u0026mdash;including extended cycle life, lower maintenance expenses, enhanced safety, quick charge/discharge capabilities, elevated energy and power densities, and swift charge/discharge\u0026mdash;have recently garnered significant interest as a potential alternative or complement to lithium-ion batteries[\u003cspan additionalcitationids=\"CR11\" citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]. The energy and power sources of HSC devices comprise a battery-type Faradaic cathode featuring transition metal oxides, hydroxides, sulphides, and phosphides, alongside an electrochemical double layer capacitance (EDLC)-type anode constructed from carbonaceous materials. The type of battery cathode significantly influences the overall performance of HSC devices. As a result, the primary objective of the current investigation into HSC devices is to identify novel battery-type materials that exhibit exceptional electrochemical properties.\u003c/p\u003e \u003cp\u003eA new class of porous crystalline materials called metal-organic frameworks (MOFs) has recently attracted a lot of attention because of its many different topologies, configurable functions, and widespread porosity [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]. Metal-organic frameworks (MOFs) have recently attracted significant attention as a novel category of porous crystalline materials, owing to their extensive porosity, adjustable functionalities, and diverse range of topologies [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. Multiple research teams have demonstrated that MOFs can serve as adaptable sacrificial templates for the synthesis of diverse forms of porous carbon, metal oxides, metal hydroxides, or composite materials comprising these components. Unfortunately, the process that involves heating the material to a high temperature is not only energy-intensive but also somewhat complicated. Additionally, the precursor MOFs' delicate porous interior structures are generally degraded to some extent, which limits how well they can be used for energy storage.\u003c/p\u003e \u003cp\u003eA lot of people have been interested in using MOFs as supercapacitor electrode materials recently. Because of its excellent stability in alkaline electrolytes and relatively high specific capacity, a layered structure of nickel-based MOF has been widely chosen and used as electrode materials for supercapacitors among various metal-organic frameworks [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. Using a solvothermal approach, Wei and colleagues successfully synthesized a two-dimensional (2D) layered Ni-MOF structure. This structure showed a rate capability of 60% and a specific capacity of 109.6 mA h/g [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. The production of multi-nanosheet Ni-MOF microspheres was described in detail by Pei et al. utilizing a similar solvothermal method. According to the research, the specific capacity and rate capability of Ni-MOF were significantly enhanced when partially substituted with Co\u003csup\u003e2+\u003c/sup\u003e or Zn\u003csup\u003e2+\u003c/sup\u003e ions [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. In a recent study, Pang's group detailed how bulk Ni-MOF can be ultrasonically treated into thin nanosheets, creating an accordion-like superstructure. This structure has impressive cycling stability, maintaining 96.5% of its initial capacity over 5000 cycles, and a specific capacity of 123.5 mA h/g [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. Several electroactive materials with improved conductivity have been employed due to the fact that pure MOFs typically have a low electrical conductivity, which restricts their use in electrochemical applications. Graphene and carbon nanotubes are examples of carbonaceous compounds; polyaniline and polypyrrole are examples of conductive polymers. To improve the electrochemical characteristics of MOF-based composite materials, these components are being added. A recent demonstration by Lai and colleagues demonstrated the use of an in situ self-transformation technique to incorporate metal oxides into the MOF system. The outcome of this method was an increased rate capability and a specific capacity that was three times higher for the MOF\u0026minus;MnOx composite [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. The direct use of MOFs as electrode materials still presents difficulties, despite considerable advancements in this field. Since these MOFs have a strong propensity to aggregate when mixed with water, they are often manufactured in powder form [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. In addition, the electrode's electrochemical performance will be negatively affected because of the conductive additives and polymer binders that must be included during electrode preparation. These additives reduce the electrode's flexibility, decrease the effective surface area, and prevent the efficient penetration of electrolyte ions within the electrode.\u003c/p\u003e \u003cp\u003eWe propose a simple two-step solution-based process for fabricating hierarchical NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Ni-MOF hybrid arrays, which are advanced electrodes for HSC devices, taking into account the previously mentioned factors. Few articles have addressed the production of well-aligned MOF arrays on conductive three-dimensional (3D) matrices and their direct application in electrochemical energy storage, as far as we are aware [\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. This research details the methods used to methodically construct arrays of Ni-MOFs on NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanorodss by precisely controlling the MOF formation reaction. Anchored firmly on NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e are the Ni-MOF nanorodss, which include linked layers with a high surface area and abundant porosity. Not only does this arrangement improve the electrochemical characteristics in a synergistic way, but it also allows for more favorable kinetics of ion diffusion and electron transport inside the hybrid electrode. The optimized NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Ni-MOF hybrid electrode can reach a rate capability of 89% at a current density ten times higher and an impressive specific capacity of 506 Fg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at 1 Ag\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. A flexible and durable solid-state HSC device is constructed using activated carbon (AC) as the anode and NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Ni-MOF as the cathode. The adaptive NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Ni-MOF//AC HSC device has a peak energy density of 30.6 W h/kg at a power density of 498 W/kg, indicating exceptional mechanical stability. The exceptional cycling stability\u0026mdash;approximately 82% retention after 10,000 cycles\u0026mdash;positions MOF-based hybrid arrays as a viable option for high-performance battery-type electrodes in HSC devices.\u003c/p\u003e"},{"header":"Experimental Section","content":"\u003cp\u003e \u003cb\u003eSynthesis of NiCo\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eO\u003c/b\u003e \u003csub\u003e \u003cb\u003e4\u003c/b\u003e \u003c/sub\u003e \u003cb\u003enanoparticles through hydrothermal method.\u003c/b\u003e\u003c/p\u003e \u003cp\u003eThe analytical grade chemicals were sourced from Aladin and utilised precisely as specified. In the standard procedure for synthesising NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanorods arrays, a mixture was prepared by combining 0.1 mmol of Ni(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO, 0.15 mmol of Co(NO\u003csub\u003e3)2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO, and 0.10 mmol of CO(NH\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e with 50 mL of deionised (DI) water, followed by stirring. Subsequently, the mixture was moved to a stainless steel autoclave lined with Teflon. A temperature of 140\u0026deg;C was maintained for 6 hours in the sealed autoclave. After cooling down to room temperature, the sample was washed with water and ethanol to remove the unwanted impurities. After washing the sample was dried at oven at 100˚C and sintered at 350 ˚C for 3h. A simple solvothermal method was used to create the hierarchical NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Ni-MOF hybrid arrays by growing Ni-MOF nanosheets on NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanorodss. The standard procedure involved dissolving 0.1mmol of Ni(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO and 0.05 mmol p-benzenedicarboxylic acid (PTA) in 20 mL of N,N-dimethylformamide (DMF) in separate solutions. Carefully, the nickel nitrate solution was added to the PTA solution dropwise at a controlled rate of 0.3 mL/min while stirring continuously, and the 0.12 g NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e was added to the mixed solution were then kept in the reaction autoclave, which was kept at 120\u0026deg;C for the duration of the reaction. After cooling down the sample was washed with ethanol and DMF rinses, the samples were dried for an entire night at 80\u0026deg;C. NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Ni-MOF hybrid arrays are then created and utilized for additional analysis. The prepared samples were named as NCO (NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e) and NCO@MOF (NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Ni-MOF).\u003c/p\u003e \u003cp\u003e \u003cb\u003eMaterials Characterization.\u003c/b\u003e \u003c/p\u003e \u003cp\u003eX-ray diffraction (XRD, Bruker) was used to characterize the structure of the as-prepared samples. Field emission scanning electron microscopy (Zeiss Ultra 55) were used to acquire the microstructure and detailed morphology, respectively. The chemical compositions were examined with the help of a X-ray photoelectron spectroscope (XPS, MKLAB).\u003c/p\u003e \u003cp\u003e \u003cb\u003eFabrication of Solid-State HSCs.\u003c/b\u003e \u003c/p\u003e \u003cp\u003eFull-cell devices, designated as NCO@MOF//AC, were constructed utilising the optimised NCO@MOF for the cathode and AC for the anode, with cellulose paper serving as the separator. To prepare the gel electrolyte, combine the appropriate quantities of polyvinyl alcohol (PVA) and potassium hydroxide (KOH) in deionised water, stirring continuously while heating to 90\u0026deg;C until the mixture becomes clear. In addition, for the anode's construction, N-methyl-2-pyrrolidinone was mixed with 80% activated carbon, 10% polyvinylidene fluoride, and 10% acetylene black. The carbon fabric was evenly coated with the resulting slurry, and then it was vacuum-dried at 80\u0026deg;C for 12 hours. A two-electrode system was used to assess the electrochemical performance of the constructed HSC device, which was then sealed with PET films to avoid electrolyte leakage.\u003c/p\u003e"},{"header":"Results and Discussion","content":"\u003cp\u003eIn Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e we can see the simplified version of the synthesis procedure for NCO@MOF core/shell hybrid arrays provided by this research. A post-annealing procedure successfully establishes a framework for the subsequent development of MOF shells from self-supported NCO nanorods arrays, which are initially produced via the hydrothermal reaction of Ni2\u0026thinsp;+\u0026thinsp;and Co2\u0026thinsp;+\u0026thinsp;ions with the hydrolysis product of urea. After that, NCO nanorodss are methodically coated with interconnected Ni-MOF nanosheets using a simple solvothermal technique. The intended NCO@MOF hybrid is eventually formed as a result of this method. With a NCO core and a Ni-MOF shell, these unique three-dimensional hierarchical nanostructures are expected to provide favorable kinetics for quick electron transport and ion diffusion. Furthermore, it is anticipated that the components will show notable synergistic effects, leading to significantly enhanced electrochemical characteristics.\u003c/p\u003e\n\u003cp\u003eFirst, scanning electron microscopy (SEM) is used to analyze the surface morphologies of the NCO arrays synthesized and the NCO@MOF arrays. The nearly uniformly manufactured pure NCO composite has an average diameter of 18\u0026ndash;20 nm, as shown in Figs. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ea and \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003eb. Figure \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ec, d shows a hybrid electrode that has been hydrothermally modified to cover the NCO structure with multiple layers of Ni-MOF nanosheets. The ability to regulate the ratios and hence the creation of Ni-MOF shells is crucial. This is because the Ni-MOF shells thicken with increasing ratio, leading to a marked increase in mass loading. At the same time, the interstitial space among the NCO nanorodss is substantially occupied by the Ni-MOF shells. Figure \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e(e-g) shows the elemental mapping of NCO@MOF samples which cleary shows that pure phase of sample was achieved with no impurities [\u003cspan class=\"CitationRef\"\u003e23\u003c/span\u003e].\u003c/p\u003e\n\u003cp\u003eAs shown in Figs. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e, XPS characterization is used to investigate the surface states and chemical composition of the samples. Comparison of the standard survey spectra of pure NCO and NCO@MOF composite arrays synthesized by hydrothermal method is shown in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ea. Figure \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003eb shows the Ni 2p core-level spectra that were fitted with a Gaussian distribution. According to NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, Ni\u003csup\u003e2+\u003c/sup\u003e is responsible for the peaks at 854 and 871 eV, while Ni3\u0026thinsp;+\u0026thinsp;is responsible for the peaks at 855 and 873 eV, with their respective satellite peaks at 861 and 879 eV. In the Co 2p spectrum (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ec), a single shifted satellite and two distinct spin-orbit doublets were observed. Co\u003csup\u003e3+\u003c/sup\u003e is indicated by the initial doublet at 778 eV in Co 2p\u003csub\u003e3/2\u003c/sub\u003e and 793 eV in Co 2p\u003csub\u003e1/2\u003c/sub\u003e, whereas Co\u003csup\u003e2+\u003c/sup\u003e is indicated by the subsequent doublet at 779 eV in Co 2p\u003csub\u003e3/2\u003c/sub\u003e and 796.7 eV in Co 2p\u003csub\u003e1/2\u003c/sub\u003e. Three distinct peaks at 529 to 532 eV are observed in the O 1s spectrum of NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, as shown in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ed. These peaks correspond to oxygen at defect sites, surface-adsorbed H\u003csub\u003e2\u003c/sub\u003eO, and lattice oxygen, respectively the other hand, the large O 1s peaks located at 531 and 532 eV, respectively, in NCO@MOF are thought to be O\u0026thinsp;\u0026minus;\u0026thinsp;C\u0026thinsp;=\u0026thinsp;O links in Ni-MOF and metal\u0026minus;oxygen bonds in Ni-MOF. Further evidence that the Ni-MOF shell completely covers NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e is the fact that the hybrid arrays of NCO@MOF do not show the lattice oxygen peak (529 eV) from NCO [\u003cspan class=\"CitationRef\"\u003e26\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e28\u003c/span\u003e]. Figure \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e shows the surface area analysis and pore size distribution of NCO and NCO@MOF samples respectively. Compare of NCO (Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ea), the NCO@MOF (Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003eb) delivers higher surface area of about 228 m\u003csup\u003e2\u003c/sup\u003e g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e with pore diameter of 2\u0026ndash;4 nm. This clearly shows that NCO@MOF sample possess the larger surface area with mesopores nature which greatly enhances the electrochemical performance of NCO@MOF sample during cycling.\u003c/p\u003e\n\u003cp\u003eInitially, electrochemical assessments were performed using a three-electrode setup with a 2 M KOH electrolyte to showcase the enhanced electrochemical characteristics of the NCO and NCO-MOF hybrid electrodes for supercapacitor applications. In Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e, we can see that the NCO-MOF hybrid electrode has the best electrochemical performance when compared to the NCO. This is based on a comparison of the CV and GCD curves, as well as the rate capabilities of the two electrodes. An appropriate reaction time for deposition of Ni-MOF shells on NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e arrays is required, as an excess of Ni-MOF shells may compromise electrochemical characteristics by preventing electrolyte ions from entering the underlying materials. Additionally, each CV curve displays a pair of redox peaks linked to the Faradaic redox reaction of transition-metal ions with the electrolyte, confirming their battery-type distinguishing characteristics. The hybrid electrode made of Ni-MOF shows a significantly larger CV enclosed area and peak current density when compared to pure NCO. Based on these findings, it can be concluded that the hybrid arrays\u0026apos; Ni-MOF nanosheets offer much more capacity compared to pure materials, even if the mass loading is almost the same. This discovery underscores the unique synergistic interaction between the core and shell nanostructures [29]. The CV curves were shown in Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e(a, b)\u003c/p\u003e\n\u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003ec illustrates the logarithmic connection between peak current and scan rates of NCO@MOF derived from CV analysis at various scan rates. Diffusion-controlled battery behavior is demonstrated by the NCO@MOF hybrid electrode, as indicated by the calculated b values for the cathodic and anodic reaction processes of 0.55 and 0.65, respectively. The GCD curves for NCO and NCO@MOF at various current densities are displayed in Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003ed, e. Additionally, as shown in Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003ef,g this outstanding value is among the highest that have been recorded for NCO@MOF -based electrodes thus far. Compared to the pristine NCO, which exhibits a rate capability of 78.5%, the optimized NCO@MOF electrode exhibits a notable improvement in rate capability, reaching 87%. The Nyquist plots depicting the electrochemical impedance spectroscopy (EIS) spectra for the three electrodes are presented in Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003eh. In the high-frequency regions, these plots will exhibit a semicircle that indicates the charge-transfer resistance (Rct) at the electrode/electrolyte interface. Conversely, in the low-frequency regions, a sloped straight line will represent the Warburg impedance (Zw) within the electrode [\u003cspan class=\"CitationRef\"\u003e30\u003c/span\u003e]. The equivalent series resistance (Rs) will be indicated by the intercept with the real axis. According to the figures, NCO@MOF, the Rs is slightly lower at 0.38 Ω compared to pure Ni-MOF\u0026apos;s 0.38 Ω, and the Rct is much lower at 4.0 Ω compared to Ni-MOF\u0026apos;s 7.8 Ω. The ion diffusion dynamics of NCO are also comparable. Therefore, the enhanced electrochemical performance of the NCO@MOF hybrid electrode may be well explained by the combined benefits of fast electron conduction and ionic diffusion kinetics [\u003cspan class=\"CitationRef\"\u003e31\u003c/span\u003e].\u003c/p\u003e\n\u003cp\u003eWe have developed all-solid-state HSC devices to evaluate their practicality, leveraging the exceptional electrochemical properties of the NCO@MOF hybrid arrays. The solid-state HSC device incorporates activated carbon for the anode and utilises optimised NCO@MOF for the cathode.The electrolyte is PVA/KOH gel, as shown in Fig. \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003ea. According to Fig. \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003e, which shows the individual cyclic voltammetry curves of the two electrodes in a separate three-electrode setup, the HSC device appears to be capable of producing a consistent working voltage of 1.2 V. The device\u0026apos;s CV curves, acquired at scan speeds ranging from 5 to 50 mV/s, are shown in Fig. \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003eb. Both the EDLC and battery types of electrodes have an impact on the total capacity, as shown by the similarly distorted rectangular shape of the CV curves. To estimate the device\u0026apos;s specific capacity values, Fig.\u0026nbsp;8c shows the discharge curves of the HSC device across a range of current densities from 1 to 10 Ag\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The HSC apparatus demonstrates a notable specific capacity of 180 Ag\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at 1 Ag\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, resulting in a retention rate of 85% (Fig. \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003ed, e). This decline may be attributed to restricted ion mobility within the gel electrolyte, especially at higher current densities [\u003cspan class=\"CitationRef\"\u003e32\u003c/span\u003e].\u003c/p\u003e\n\u003cp\u003eAt a current density of 1 Ag\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e shows the HSC device\u0026apos;s effectiveness in sustained cycling. It is remarkable that, even after 10,000 cycles, nearly all of the initial capacity can be maintained. This further proves the device\u0026apos;s remarkable long-term cycling stability. Similar to other solid-state full-cell devices that use the improved NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Ni-MOF, we have observed an improvement in capacity during the device\u0026apos;s cycling process. We studied the morphological change of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Ni-MOF hybrid electrode after cycling using various techniques. The calculated specific capacitance of solid state device was shown in Figure d Although the Ni-MOF shell\u0026apos;s morphology has changed, showing many pores probably caused by the repeated intercalation and deintercalation of electrolyte ions, the hierarchical structure of the integrated electrode stays intact after 10 000 cycles, as shown in Fig. \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003ee [\u003cspan class=\"CitationRef\"\u003e33\u003c/span\u003e].\u003c/p\u003e\n\u003cp\u003eEnergy density and power density serve as critical metrics for evaluating the performance of energy storage devices in real-world applications. Figure \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003ef illustrates the Ragone plots of our NCO@MOF//AC hybrid supercapacitor device [\u003cspan class=\"CitationRef\"\u003e34\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e40\u003c/span\u003e], in conjunction with other previously reported MOF-based hybrid supercapacitor devices for comparative evaluation. The multifunctional solid-state NCO@MOF//AC HSC device achieves a remarkable energy density of 30.6 W h/kg at 498 W/kg, while maintaining 12.6 W h/kg with a power density of 3846 W/kg. The energy density achieved by our flexible solid-state HSC device is equivalent to, or may exceed, that of other previously documented MOF-based HSC devices in an aqueous electrolyte. This further highlights the significant potential of MOF-based hybrid arrays as advanced battery-type electrodes for flexible energy storage solutions.\u003c/p\u003e"},{"header":"Conclusions","content":"\u003cp\u003eIn conclusion, we have developed a two-step synthetic approach to facilitate the controlled assembly of hierarchical NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Ni-MOF hybrid arrays directly on carbon cloth, which function as advanced electrodes for flexible all-solid-state HSC devices. The integration of NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e and Ni-MOF in a unique 3D hierarchical structure offers significant benefits, enabling the optimised NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Ni-MOF hybrid electrode to attain an extraordinarily high specific capacity and impressive rate capability. The HSC device, incorporating the optimised NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Ni-MOF and AC, exhibits a maximum energy density of 30.6 W h/kg at 498 W/kg, along with exceptional long-term cycling stability of up to 10,000 cycles. This performance exceeds that of the majority of recently published MOF-based HSC devices in aqueous electrolyte systems. This study demonstrates the capability to design and fabricate novel MOF-based hybrid arrays for the development of highly efficient and durable flexible energy storage devices.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eDr. P. Malarkodi : Analysis and wriiting the manuscript.Dr. J.C kannan: Editting the manuscript\u003c/p\u003e\u003ch2\u003eAcknowledgment\u003c/h2\u003e \u003cp\u003eNo funds, grants, or other support was received.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eLu, X.; Yu, M.; Wang, G.; Tong, Y.; Li, Y. Flexible Solid-State Supercapacitors: Design, Fabrication and Applications. Energy Environ. Sci. 2014, 7, 2160\u0026minus;2181.\u003c/li\u003e\n\u003cli\u003eChoi, S.; Lee, H.; Ghaffari, R.; Hyeon, T.; Kim, D.-H. Recent Advances in Flexible and Stretchable Bio-Electronic Devices Integrated with Nanomaterials. Adv. Mater. 2016, 28, 4203\u0026minus;4218. \u003c/li\u003e\n\u003cli\u003eKhan, Y.; Ostfeld, A. E.; Lochner, C. M.; Pierre, A.; Arias, A. C. Monitoring of Vital Signs with Flexible and Wearable Medical Devices. Adv. Mater. 2016, 28, 4373\u0026minus;4395. \u003c/li\u003e\n\u003cli\u003eMiao, Z.; Huang, Y.; Xin, J.; Su, X.; Sang, Y.; Liu, H.; Wang, J.-J. 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Dalton Trans. 2018, 47, 5639\u0026minus;5645.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-8780253/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8780253/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003ePorous metal-organic frameworks, or MOFs, hold great promise as elements for a wide range of functional materials with the potential to store and convert electrochemical energy with exceptional performance. For use in high-performance supercapacitors, this article introduces bimetallic oxide (NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-MOF) electrode materials made from metal-organic frameworks (MOFs). The optimal Ni-MOF@NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (NCO@MOF) electrode achieves a maximum specific capacity of 560 Fg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at 1 Ag\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and an outstanding rate capability of 87% after 5000 cycles, significantly exceeding that of its separate components. The constructed asymmetric device (ASC) utilising NiCo2O4-MOF as the positive electrode and activated carbon as the negative electrode demonstrated an exceptional energy density of 30.6 Wh kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at a power density of 480 W kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, with 84% capacitance retention after 10,000 cycles. This paper presents a novel method for the synthesis and fabrication of metal oxides originating from MOFs, recognised for their elevated porosity, advantageous for electrochemical energy storage applications.\u003c/p\u003e","manuscriptTitle":"Metal organic frame work inserted NiCo 2 O 4 for asymmetric supercapacitor applications","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-02-21 04:31:30","doi":"10.21203/rs.3.rs-8780253/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"d1186cfc-a599-4ab0-afa8-46426b88dd4b","owner":[],"postedDate":"February 21st, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2026-04-03T15:40:44+00:00","versionOfRecord":[],"versionCreatedAt":"2026-02-21 04:31:30","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8780253","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8780253","identity":"rs-8780253","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}