Diffusion Of Electrolyte Ions Research Articles

An aqueous ZnCl2/Fe(bpy)3Cl2 flow battery with mild electrolyte

The kinetics of electrode reaction was investigated by cyclic voltammetry, and cyclic voltammograms show that the reversibility of the Fe(bpy)32+/Fe(bpy)33+ electrode reaction is better than that of the Zn/Zn2+ electrode reaction on the graphite disc. However, the Fe(bpy)32+ ion diffusion in electrolyte is subject to greater resistance than that of the Zn2+ ion one. The stability of the Fe(bpy)3Cl2 solution was investigated by UV-vis spectroscopy, and the performance of a mild redox flow battery employing ZnCl2 and Fe(bpy)3Cl2 in the NaCl aqueous solution with various membranes as the separator was also investigated. It was found that the Celgard 3501 membrane cannot effectively prevent Fe(bpy)32+ ions from leaking into anolyte, leading to the rapid failure of the flow battery. Although the Nafion 115 membrane can be polluted by Fe(bpy)32+ ions, it is not invalidated. The Nafion 115 membrane shows good selectivity, which can avoid Fe(bpy)32+ ions from leakage into anolyte. The ZnCl2/Fe(bpy)3Cl2 flow battery with the Nafion 115 membrane exhibits the capacity retention of 80% after 200 cycles.

Redox active covalent organic framework-based conductive nanofibers for flexible energy storage device

Covalent organic frameworks (COFs) constitute a family of crystalline porous polymers that are being studied for electrochemical energy storage. However, their low electrical conductivity and poor processability have largely limited their electrochemical performances and practical applications. Here, we develop an interfacial synthesis method to grow few-layered 2D redox-active COFs (DAAQ-TFP COF) on the surface of carboxylated carbon nanotubes (c-CNTs) in order to fabricate core-shell c-CNT@COF nanofibers, for which the thickness and the morphology of the COF nanolayers can be finely controlled. When using the c-CNT@COFs as electrode material, the tailored nanostructure with high electrical conductivity allows efficient electron transfer, while the few-layered structure of the COF promotes fast electrolyte ion diffusion in the near-surface region, which results in an efficient utilization of the redox active sites in COF. More significantly, c-CNT@COFs with nanofibrous structure show good processability and can be assembled into freestanding and flexible nanopapers with the assistance of Cladophora cellulose. Given the good electrochemical performance and excellent flexibility, the nanopaper electrodes are assembled into flexible hybrid capacitors, showing high areal capacitance and extremely long lifetime. This study provides a new pathway for the development of next generation sustainable and flexible energy storage devices based on COFs and cellulose materials.

Three-dimensional carbon nanotubes/iron oxyhydroxide shell/core hybrid as a binder-free electrode for the flexible supercapacitor

Carbon nanotubes/iron oxyhydroxide (CNTs/FeOOH) three-dimensional hybrid with shell/core nanostructure is designed as a binder-free electrode for the flexible supercapacitor (SC) application. The coiled and dense CNT forest is preferentially fabricated on flexible carbon fiber cloth (CC) by chemical vapor deposition (CVD) and employed as a highly conductive carrier for electrodeposition growth of FeOOH. The average diameter and length of the single CNT are 30–60 nm and 2–3 μm. The shell/core structured CNTs/FeOOH three-dimensional hybrid maintains the consistent interconnecting network morphology, contributing to overcoming the problem of poor conductivity of FeOOH and the transmission of electron channels and the diffusion of electrolyte ions. The CNTs/FeOOH hybrid exhibits a high mass-specific capacitance of 824 F g−1 (or 0.59 F cm−2) in 1 M Na2SO4 electrolyte at 0.5 mA cm−2. By increasing the FeOOH deposition weight, the enhanced area-specific capacitance of 0.892 F cm−2 (or 564 F g−1) is obtained at 0.5 mA cm−2, and the enhanced capacitance retention can reach 96% after 3000 charge/discharge cycles. Besides, a flexible SC is fabricated using the CNTs/FeOOH hybrid electrode and carboxymethyl cellulose (CMC)/Na2SO4 gel electrolyte. The SC displays an energy density as high as 13.33 Wh kg−1 at a power density of 1000 W kg−1. The SC device shows large bending deformation, and these SC devices pack can drive a red diode to work. These results provide such a shell/core structured CNTs/FeOOH three-dimensional hybrid that can be used as potential and low-cost electrode material for flexible SC.

Effect of decorating cobalt ferrite spinel structures on pistachio vera shell –derived activated carbon on energy storage applications

In this work, a simple insitu chemical co-precipitation technique was adopted for the synthesis of CoFe2O4 (Cf) decorated Pistachio shell derived activated carbon (Cf@Pv-AC) composite to fabricate electrodes for supercapacitor (SC) application. Doping of Cf particles on the surface of the Pv-AC effectively enhanced the diffusion of electrolyte ions by facilitating a porous structural morphology which act as the reservoir of electrolyte ions during the electrochemical redox reactions. FT-IR spectrum of Cf@Pv-AC composite exhibited the strong absorption band at 608 cm−1, which was associated to M-O bonds (Where M=Co and Fe) in Cf structure. FE-SEM images of Cf@Pv-AC suggested that Co-ferrite particles have evenly covered the surface of porous Pv-AC rods. Further, Cyclic voltammetric analysis (CV) of Cf@Pv-AC coated Ni foil electrode proved the battery type behavior of Cf in Cf@Pv-AC sample and delivered the specific capacity of 1233 C/g in the potential range of 0–0.69 V at the scan rate of 5 mV/s. These results revealed that the specific capacity value increased two fold than that of pure Cf (434 C/g) at the same scan rate. Moreover, the obtained results were also substantiated by Galvanostatic charge-discharge (GCD) measurements. About 93% of specific capacity retention was achieved by Cf@Pv-AC electrode, even after 5000 GCD cycles at the current density of 4 A/g, which were evident for the better capacitive performance of Cf@Pv-AC electrode material.

Facile strategy of hollow polyaniline nanotubes supported on Ti3C2-MXene nanosheets for High-performance symmetric supercapacitors

Titanium carbide MXene (Ti3C2) has attracted significant research interest because of its extraordinary advantages as advanced electrode material for energy storage. In this work, we explored a facile strategy to construct Ti3C2-based hierarchical composite materials by surface modification using pseudocapacitive materials. The method involved the synthesis of the exfoliation of ultrathin Ti3C2 nanosheets, followed by one-pot in situ polymerization and surface decoration using polyaniline nanotubes (PANI-NTs). Herein, the self-aggregation of Ti3C2 layers had been effectively suppressed, resulting in an enhanced interlamellar spacing and enlarged ion contact area. Furthermore, the novel hierarchical structure of Ti3C2/PANI-NTs can facilitate the electrolyte ions diffusion, which also boosted more electrochemical active sites to become more accessible. In addition, the electrochemical test in the three-electrode system demonstrated that the specific capacitance of the Ti3C2/PANI-NTs-1 composite can be as high as 596.6F g−1 at 0.1 A g−1, remaining 94.7% retention of initial capacitance after 5000 cycles of charge/discharge. Moreover, the symmetric supercapacitor device based on Ti3C2/PANI-NTs-1 composite exhibited a maximum energy density of 25.6 Wh kg−1 (at 153.2 W kg−1) and an impressive power density of 1610.8 W kg−1 (at 13.2 Wh kg−1), as well as outstanding cycling stability (81.1% retention of the capacitance after 4000 cycles). These electrochemical measurements indicated that the performance of Ti3C2-based supercapacitors could be immensely improved by designing and constructing the hierarchical structure with abundant pseudocapacitive materials. Furthermore, this strategy could be extended to other MXenes composite materials as advanced electrodes by taking full advantage of their potentials for new symmetric supercapacitors.

MnO2 nanosheets grown on N and P co-doped hollow carbon microspheres for high performance asymmetric supercapacitor

The rapid development of supercapacitors has led to an increasing demand for the exploitation of stable and excellent electroactive electrode materials. Herein, a novel hybrid material of N, P co-doped hollow carbon microspheres (N/P-HCS) and ultrathin MnO2 nanosheets was facilely constructed for the electrode material of supercapacitors through a two-step synthetic strategy including the preparation of N/P-HCS and subsequent growth of MnO2 nanosheets on N/P-HCS. The N/P-HCS@MnO2 hybrid possesses a N/P-HCS core and a porous shell composed of ultrathin MnO2 nanosheets. Moreover, the morphology and content of MnO2 in the hybrid can be controlled by designing the stoichiometric chemical reaction between N/P-HCS and KMnO4. The hybrid electrode exhibits excellent electron transport, fast electrolyte ions diffusion, rapid and reversible Faradaic reaction, and good rate performance. Additionally, a green asymmetric supercapacitor was manufactured using typical hybrid N/P-HCS@MnO2-30 as positive electrode and N/P-HCS as negative electrode, which displayed a high energy density of 32.21 Wh kg−1 at a power density of 449.8 W kg−1 and excellent cycling stability (capacitance retention of 94.5% after 3000 cycles). These results show that the N/P-HCS@MnO2 might be an attractive electrode material for practical application in advanced supercapacitor.

Fe-based phosphate nanostructures for supercapacitors

Fe-based phosphates with excellent physical and chemical features are potential electrode materials for supercapacitors. In this work, we successfully synthesized Fe-based phosphates with different dimensions, morphologies, and compositions by one-step hydrothermal method. Influence factors on the chemical composition and morphology of the as-prepared materials were explored and the energy storage performance of the as-prepared samples were tested under the traditional three electrode system. Two-dimensional (2D) iron metaphosphate (Fe(PO3)3) showed the best electrochemical performance. For Fe(PO3)3 electrode materials, the layered structure can provide a larger specific surface area than the bulk structure, which is conducive to the diffusion and transport of electrolyte ions during charging-discharging and further improves the rate performance and cycle stability of supercapacitor. 2D Fe(PO3)3 and activated carbon were used as electrode materials to construct a 2D Fe(PO3)3//AC supercapacitor. The supercapacitor showed high energy density, high power density, and excellent cycling stability, which indicates 2D Fe(PO3)3 is a promising electrode material for supercapacitors.

Low-cost and novel preparation of porous NiS2/graphene heterojunctions photoanodes for high-efficiency dye-sensitized solar cells

It's critical and challenging to investigate cost-effective and strong electrocatalyst within the advancement of large scaled dye-sensitized solar cells (DSSCs). In this work, we develop a novel strategy to prepare NiS2 microspheres interface with 2D graphene nanosheets constructed through a facile hydrothermal technique. Na2S2O3·5H2O plays an important role as the reducing agent for GO as well as the sulfur source for NiS2. The microstructures, morphologies and optical properties of the NiS2/graphene hybrid composite samples were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and N2 adsorption–desorption isotherm, UV–Vis diffuse reflectance spectra and photoluminescence spectra analysis. A significant narrowing the band gap (2.69 eV–2.44 eV) and control the prevention of electron-hole pair recombination process was examined through UV and PL studies. The J-V characteristics of the fabricated sandwich type DSSC device was monitored and the results demonstrate that NiS2/graphene hybrid photoanode displayed an excellent electrocatalytic activity in the reduction of I3− showing a power conversion efficiency of 12.56%, which is 2.5 times better than bare NiS2 photoanode (5.02%). This is ascribed to the low resistance to diffusion and transfer of electrolyte ions. These results suggest that the NiS2/graphene prepared through a facile process is a promising substitute to Pt electrode.

Metal-organic framework derived directional growth of ultrathin amorphous NiCo hydroxide nanosheets on NiCo2O4 nanowire arrays for enhanced electrochemical properties

The rational design of hierarchical nanostructured electrode materials is critical for achieving high electrochemical property for supercapacitor (SC) applications. Herein, we report a facile method for fabricating hierarchical NiCoO@NiCo–OH core-shell nanowire array (NiCoO@NiCo–OH NWA) on flexible carbon fiber clothes by using a cobalt-based metal organic framework (Co-MOF) as an intermediate. The growth mechanism study shows the formation process is completed by a localized dissolution of Co-MOF followed by a directional growth of NiCo–OH nanosheets on NiCo2O4 nanowires. The unique hierarchical nanostructure endows the material a high surface area, rich active sites, fast electron transport, and efficient electrolyte ion diffusion. Consequently, the as-prepared material exhibited an over 3 times’ higher specific capacity than the pristine NiCo2O4 nanowire arrays and an excellent rate capability at 40 A g−1 for SCs. Moreover, the NiCoO@NiCo–OH NWA based hybrid supercapacitor (HSC) exhibited a considerably high energy density of 57.2 Wh kg−1, a high power density of 17.6 kW kg−1, and ultralong cycling stability of over 10 000 cycles (retention rate of 91.8%), outperforming most of the current state-of-the-art SCs. The directional growth strategy using MOFs as intermediates reported here provides a simple but effective way to fabricate hierarchical nanostructured electrode materials for advanced energy storage applications.

Two-Step Synthesis of CuS/C@PANI Nanocomposite as Advanced Electrode Materials for Supercapacitor Applications.

In this study, the dense cloud-like structured CuS nanoparticles were successfully prepared using a simple two-step hydrothermal method. The experimental temperature was the most important factor that affected the microstructure and surface functions of CuS/C. Therefore, the CuS/C electrodes were synthesized at different temperatures (80 °C, 120 °C, and 160 °C). Subsequently, their crystallographic phase and morphologies as well as the structure of the as-prepared electrodes were analyzed in detail. The electrode prepared at 120 °C (CuS/C-120) was determined to have a perfect microstructure, high specific capacitance, and good rate performance. To further improve the electrochemical performance of this electrode, it was combined with polyaniline (PANI) to obtain a CuS/C-120@PANI electrode via the cyclic voltammetric electrodeposition method. The CuS/C-120@PANI electrode exhibits a specific capacitance of 425.53 Fg−1 at a current density of 1 Ag−1 and a good cycling stability of 89.86% after 3000 cycles. The perfect architecture of CuS/C-120@PANI maximizes the synergistic effect between its different components and provides abundant electrochemically reactive sites, promoting the diffusion and transfer of electrolyte ions during the electrochemical reaction processes. Detailed analysis shows that the CuS/C-120@PANI electrode has great potential for use in high-performance energy storage devices.

Writing ink-promoted synthesis of electrodes with high energy storage performance: A review

As the low-cost commercial product, writing inks (pen ink and Chinese ink) have attracted great attention to fabricate electrochemical electrodes for supercapacitors (SCs) and batteries. Due to the conductive nature deriving from graphitic carbon nanoparticles in ink and strong adhesion, ink can be easily coated onto support to enhance the conductivity, form a porous layer facilitating electrolyte ion diffusion, increase the specific surface area and function as binder and dispersant for other active materials. In this review, the beneficial features of pen ink and Chinese ink are summarized and how these features favor the electrochemical performance is discussed in details. And then, ways to coat ink onto support are described, giving a clear understanding of recent process in this area. Finally, the current challenges and outlook of ink-based electrode are discussed, aiming to offer some basic knowledge and promote wide application and future study of pen ink and Chinese ink in electrochemistry.

Wettability improvement of vanadium nitride/carbon electrode nanomaterial by electrostatic absorption of hydrophilic poly (allylamine hydrochloride)

Transport of electrolyte ions in electrode material is considered to be an essential influence on the charging-discharging process, which affects the overall performance of the energy storage device. In this work, poly (allylamine hydrochloride) is introduced into the surface of vanadium nitride/carbon electrode by electrostatic self-assembly to improve the wettability of the materials. After adsorbing polyelectrolyte, the electrode nanomaterials of vanadium nitride disperse well in water, implying optimized wetting behavior of vanadium nitride electrode in aqueous electrolyte. In this case, electrolyte ions could transport efficiently in the bulk of electrode material of vanadium nitride. The fabricated electrolyte-philic electrode nanomaterials yield specific capacitance of 96.4 F/g at the current density of 0.5 A/g while the poly (allylamine hydrochloride)-free control materials only 62.1 F/g. This work provides an idea for improving wettability of electrode materials, for example, the anode electrode material of vanadium nitride, to favor more efficient electrolyte ions diffusion and charge transfer for energy storage and conversion.

Effect of bottleneck size on lithium migration in lithium garnets Li7La3Zr2O12 (LLZO)

Molecular dynamic simulations were performed on element-screened Li7La3Zr2O12 (LLZO)-equivalent doping system to reveal the effect of bottleneck (surface between the polyhedron of 24d and 96h site in cubic LLZO) size on lithium ion diffusion in this garnet-type solid electrolyte. The relationship between lithium ion diffusivity, lattice constant (volume), and bottleneck size were further studied. Herein, we found unneglectable discreteness between lattice constant (volume) and lithium ion diffusivity; beyond that, a quasi-linear relationship between bottleneck size and lithium ion diffusivity under high temperature (1000~1400 K) was unveiled. Our results show that by simply regulating the bottleneck size, the diffusion properties of lithium garnets can be further improved.

Ion Dynamics of Water‐in‐Salt Electrolyte with Organic Solvents in Nanoporous Supercapacitor Electrodes

AbstractWater‐in‐salt electrolytes blended with organics solvents, that is, organic solvent/water mixed electrolytes, are promising for applications in next‐generation energy storage devices vitally needed for industrial electrification and decarbonization. However, the electrolyte ion diffusion behaviors within nanoporous supercapacitor electrodes are poorly understood. Here a systematic investigation into supercapacitor resistances and ion kinetics is carried out experimentally and with numerical simulations. The electrochemical results on the nanoporous electrodes reveal a nonmonotonic (decreasing, increasing, and then decreasing) trend of supercapacitor resistances with increasing solvent mobility, challenging the long‐held views that supercapacitor resistances decrease with elevated mobility of organic solvent. The abnormal trend is examined by numerical molecular dynamics simulations of electrolyte ion diffusion within 0.95 nm nanochannels. The electrolyte conductivity is related to cation–anion interactions within nanochannels. We further confirm the crucial interplay of the van der Waals sizes of solvent molecules and channel width in determining electrolyte conductivity in nanoporous electrodes.

Electrochemical Sensing of Serotonin by a Modified MnO2-Graphene Electrode.

The development of MnO2-graphene (MnO2-GR) composite by microwave irradiation method and its application as an electrode material for the selective determination of serotonin (SE), popularly known as “happy chemical”, is reported. Anchoring MnO2 nanoparticles on graphene, yielded MnO2-GR composite with a large surface area, improved electron transport, high conductivity and numerous channels for rapid diffusion of electrolyte ions. The composite was characterized by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and scanning electron microscopy (SEM) for assessing the actual composition, structure and morphology. The MnO2-GR composite modified glassy carbon electrode (GCE) exhibited an excellent electrochemical activity towards the detection of SE in phosphate buffer saline (PBS) at physiological pH of 7.0. Under optimum conditions, the modified electrode could be applied to the quantification of serotonin by square wave voltammetry over a wide linear range of 0.1 to 800 µM with the lowest detection limit of 10 nM (S/N = 3). The newly fabricated sensor also exhibited attractive features such as good anti-interference ability, high reproducibility and long-term stability.

Porous Hybrid Nanosheets of g-C3N4/β-Ni(OH)2 for Asymmetric Supercapacitor with Enhanced Specific Capacitance

Porous hybrid nanosheets of g-C3N4/[Formula: see text]-Ni(OH)2(CN/[Formula: see text]-NiOH) were constructed via gas bubble method in the NiCl[Formula: see text]H2O-NH3[Formula: see text][Formula: see text][Formula: see text]H2O-C2H5OH-CN system at 140∘C for 6[Formula: see text]h. The resulting CN(5.3[Formula: see text]wt.%)/[Formula: see text]-NiOH nanosheets show a porous texture and a large interface contact area, which facilitates the electrolyte ion diffusion during reversible insertion/deinsertion processes. The fabricated CN(5.3[Formula: see text]wt.%)/[Formula: see text]-NiOH hybrid-based electrode displays an enhanced specific capacitance of 887[Formula: see text]F[Formula: see text]g[Formula: see text] at a current density of 0.5[Formula: see text]A[Formula: see text]g[Formula: see text] when compared with single phase [Formula: see text]-NiOH (480[Formula: see text]F[Formula: see text]g[Formula: see text]). Using CN(5.3[Formula: see text]wt.%)/[Formula: see text]-NiOH porous nanosheets and activated carbon (AC) as cathode and anode, an asymmetric supercapacitor (ASC) was assembled and the energy density achieves 28.3[Formula: see text]Wh[Formula: see text]kg[Formula: see text] and 10.9[Formula: see text]Wh[Formula: see text]kg[Formula: see text] at a power density of 798.4[Formula: see text]W[Formula: see text]kg[Formula: see text] and 7991.9[Formula: see text]W[Formula: see text]kg[Formula: see text], respectively.

Flexible 3D core–shell nanoforest arrays trimetal electrode for high capacitance supercapacitor

A supercapacitor electrode with high capacitance is mainly based on the careful design of nanostructures and the intelligent hybridization of custom active materials. Herein, we designed 3D core–shell nanoforest arrays with hierarchical structure which are directly grown on carbon cloth using a two-step bracket-hydrothermal method and electrodeposition process. Due to the advantages of large specific surface area, abundant pores and active sites, the structure of Mo–Co–Ni(nanotube)@Ni–Co(nanosheet) arrays can promote electrolyte penetration and ions diffusion, further improving the electrochemical performance. The 3D core–shell nanoforest arrays electrode shows outstanding electrochemical performance: a superb areal capacitance of 9.81 F cm−2 (1998.0 F g−1) at the current densities of 1 mA cm−2, as well as long cycle stability (after 3000 cycles maintains 85.4% of the highest capacitance value). This work may provide a promising method for design of flexible supercapacitor electrode materials.

O/N-co-doped hierarchically porous carbon from carboxymethyl cellulose ammonium for high-performance supercapacitors

Nowadays, it has become a trend to prepare porous carbon as electrode materials for supercapacitors by using biomass and its derivatives by virtue of its low cost, abundant source and environmental friendliness. Carboxymethyl cellulose ammonium (CMC-NH4), a kind of cellulose derivative, is used as a carbon precursor and O/N source to prepare carbon material through cross-linking with aluminum ions, lyophilization, carbonization and activation. The as-prepared O/N-co-doped carbon samples (ONAC-500, ONAC-600 and ONAC-700) exhibit hierarchically porous structure with different size pores in carbon framework, ensuring electrolyte ions effective transport and diffusion. Meanwhile, the ONAC-600 reveals a high specific surface area of 2658 m2 g−1, abundantly porous structure with pore volume of 1.32 cm3 g−1 and effective O/N-doping, which ensure a high capacitance of 465.0 F g−1 at 1 A g−1 in 3 M KOH three-electrode system. It also shows better rate capability and good stability after 10000 cycled under 10 A g−1. Besides, the assembled all-solid-state supercapacitor with ONAC-600 delivers an acceptable energy density of 7.8 Wh kg−1 at a power density of 124.2 W kg−1.

Mn3O4 nanoflakes/rGO composites with moderate pore size and (O=)C-O-Mn bond for enhanced supercapacitor performance

Moderate pore size and (O=)C-O-Mn bonds are designed in Mn3O4 nanoflakes/reduced graphene oxide composites to enhance the specific capacitance and cycling performance of electrodes for supercapacitors. Manganese oxide nanoflakes grow on the surface of graphene oxides via chemical precipitation. After annealing, (O=)C-O-Mn bonds are formed between Mn3O4 and graphene to enhance structural stability of electrode materials. Moreover, the pore size in Mn3O4 enlarges with the increased annealing temperature driven by phase transition and lattice reforming. The moderate pore size of 5–10 nm in Mn3O4 contributes to electrolyte ion diffusion and improves the capacitive-controlled energy storage. In three-electrode system, Mn3O4 nanoflakes/reduced graphene oxide composites with optimal pore size of 5–10 nm and (O=)C-O-Mn bond deliver high specific capacitance (351 F g−1 at 0.5 A g−1) and good cycling performance (80.1% of maximum capacitance after 10,000 cycles). To probe practical applications, Mn3O4 nanoflakes/reduced graphene oxide composites and active carbon are employed as positive electrode and negative electrode, respectively, to assemble asymmetrical supercapacitors. This asymmetrical supercapacitor demonstrates high energy density (36.76 Wh kg−1) and good cycling performance (93.5% after 5000 cycles).

Designing of ultra-long-life hybrid supercapacitor based on advanced battery-type electrochemical performance from porous nanostructured nickel-doped bimetallic spinel electrodes

Engineering novel hierarchical nanostructure-based electrode materials with higher surface area remains a great challenge in energy storage field to achieve higher energy density hybrid supercapacitor for portable electronic applications. Herein, mono or mixed/bimetallic Co3O4, ZnCo2O4 and nickel (Ni) ions incorporated ZnCo2O4 (Ni0·05Zn0·95Co2O4) spinels with porous nanostructures were prepared via a simple eco-benign novel wet-chemical approach, followed by calcination. The Ni0·05Zn0·95Co2O4 composite revealed the hierarchical hollow nanospindles with a high specific surface area, and it has the ability to supply more electroactive sites for the diffusion of aqueous electrolyte ions, further assisting the electron transportation in electrochemical analysis. In particular, the Ni0·05Zn0·95Co2O4@Ni foam (NF) electrode revealed a battery-like electrochemical feature and exhibited the specific capacity of ∼138 mA h g−1 which is dramatically higher than the ZnCo2O4@NF (∼56 mA h g−1) and Co3O4@NF (∼34 mA h g−1) electrodes at 1 A g−1 due to the strong synergistic effect of Ni and Co ions and rapid reaction kinetics. Additionally, a pouch-type Ni0·05Zn0·95Co2O4@NF//commercial activated carbon@NF hybrid supercapacitor device showed maximum energy and power densities of ∼54.9 W h kg−1 and ∼6105 W kg−1, respectively. Impressively, the fabricated device further exhibited an ultra-long cycling life (114% capacitance retention after 15000 cycles) and successfully demonstrated its real-time portable electronic applications.