Growth of yolk-shell CuCo2S4 on NiO nanosheets for high-performance flexible supercapacitors

A poor electrical conductivity and short cycle life limits the wide application of transition metal oxides in energy storage applications. In this study, yolk-shell structured CuCo₂S₄ was grown on NiO nanosheets (NiO@CuCo₂S₄) via a hydrothermal method and vulcanization, which combined the synergistic interactions between Ni, Co, and Cu. The effect of varying the amount of the vulcanizing agent (thiourea) on the electrochemical performance of NiO@CuCo₂S₄ was also investigated. Moreover, the amount of thiourea not only tuned the morphology of the composite, but significantly influenced its electrochemical performance. When the Cu²⁺: Co²⁺: thiourea molar ratio in the precursor solution was 1:2:6, the obtained NiO@CuCo₂S₄ exhibited the best electrochemical performance of the various systems examined, with a specific capacitance of 1658 F g^?1 being achieved at 1 A g^?1. Density functional theory calculations further confirmed the excellent synergistic effect between NiO and CuCo₂S₄. In addition, the asymmetric supercapacitor composed of a NiO@CuCo₂S₄ positive electrode reached an ultrahigh energy density of 73 Wh kg^?1 at a power density of 802 W kg^?1, as well as excellent cycling stability (i.e., 91% capacitance retention after 5000 cycles). These results suggest that NiO@CuCo₂S₄ is a promising candidate for use in energy storage applications.     

Hydrothermally synthesized microrods and microballs of NiCo2O4 for supercapacitor application

The microrods and microballs of NiCo₂O₄ are successfully synthesized by the hydrothermal method. The effect of ammonium hydroxide and ammonium fluoride on the surface microstructure is observed. The prepared microrods and microballs of NiCo₂O₄ are analyzed by various analytical tools like powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), with energy dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). The electrochemical properties are studied by using cyclic voltammetry (CV), galvanostatic charge discharge (GCD), and electrochemical impedance spectroscopy (EIS), using the workstation Biologic SP-200. The maximum specific capacitance of the NiCo₂O₄ microrods electrode is 1671 F/g. The areal specific capacitance of the NiCo₂O₄ microrods electrode is 284 mF/g. The energy density and power density of microrods of NiCo₂O₄ electrode are 19 Wh/Kg and 282 W/kg, respectively. The equivalent series resistance (Rs) is 0.62 Ω for NiCo₂O₄ microrods.     

Materials and electrode designs of high-performance NiCo2S4/Reduced graphene oxide for supercapacitors

NiCo₂S₄ is one of the most promising bimetallic sulfides for use in energy-storage systems, but more studies are needed to endow NiCo₂S₄ with a high electrochemical reaction capability and reversibility. In this work, we present rationally materials design of an optimal NiCo₂S₄ nanoparticle in a reduced graphene oxide (RGO) matrix as a NiCo₂S₄/RGO nanocomposite. Furthermore, we report the improvements in the materials technology, demonstrating the NiCo₂S₄/RGO nanocomposite electrode with an excellent specific capacitance of 963–700 F g⁻¹ at 1–15 A g⁻¹, high capacitance retention of 70%, and long cycle life of 3000 cycles. The practical application is showcased in an asymmetric supercapacitor with a high active-material loading. The NiCo₂S₄/RGO nanocomposite shows a high energy density of 31 Wh kg⁻¹ at a power density of 987 W kg⁻¹ and maintains an excellent density of 23 Wh kg⁻¹ at a high power density of 7418 W kg⁻¹. The outstanding electrochemical utilization and stability of the NiCo₂S₄/RGO nanocomposite confirm that our systematic optimization in the materials science and technology in terms of the active-material synthesis, the electrode development, and the device design/fabrication would benefit the future development of high-performance supercapacitors.     

Hierarchical architecture of Ti3C2@PDA/NiCo2S4 composite electrode as high-performance supercapacitors

A novel Ti₃C₂@PDA/NiCo₂S₄ composites as high performance supercapacitor electrodes were synthesized by the hydrothermal treatment process. The chemical modification and uniformly coating of Ti₃C₂ surface by polydopamine (PDA) can prevent the structural collapse and over-oxidation of Ti₃C₂ during the hydrothermal synthesis of NiCo₂S₄. Furthermore, the confined-synthesis of smaller NiCo₂S₄ particles between the Ti₃C₂ layers, not only prevent the restacking of Ti₃C₂ that between the adjacent monolayers during cycling, but also afford high surface areas accessible to charge transfer and ion diffusion. Thereby, enhance the electrochemical cycling stability of the Ti₃C₂@PDA/NiCo₂S₄ composite. It is significant to explore how NiCo₂S₄ alters the microstructure, morphology as well as supercapacitors performance of Ti₃C₂ to tune the microstructure and performance of Ti₃C₂ by appropriate hydrothermal synthesis strategy. The experimental results exhibit a prominent improvement in the supercapacitor performance, the gravimetric capacitance of Ti₃C₂@PDA/NiCo₂S₄ composites achieve as high as 495 F g^-1 at 2 mV s^-1, which increase the 10 times as compared to the pristine Ti₃C₂. Furthermore, the cycling stability of the Ti₃C₂@PDA/NiCo₂S₄ composites electrode was enhanced significantly by the hierarchical architecture, and showed exceptional capacitance retention (81.16%) even after 3000 cycles. The dramatic improvement in the supercapacitors performance of Ti₃C₂@PDA/NiCo₂S₄ electrodes is attributed to impressive conductive matrix Ti₃C₂, the effective modification of small size Ni₂Co₂S₄, and the strong interfacial interaction between Ti₃C₂@PDA and NiCo₂S₄. This study demonstrating its attractive application prospect of Ti₃C₂ Mxenes modified with bimetallic sulfide as electrode materials for high-performance supercapacitors.     

Conformal coatings of NiCo2O4 nanoparticles and nanosheets on carbon nanotubes for supercapacitor electrodes

NiCo₂O₄ is a promising electrode material for supercapacitors and it has been widely investigated. However, its low conductivity restricts the reaction kinetics. Combining it with carbon materials can efficiently overcome the issue. But, very limited research about the homogenous coatings of NiCo₂O₄ nanocrystals on carbon nanotubes (CNTs) is reported. In this work, thin nanosheets and small nanoparticles of NiCo₂O₄ densely coated on CNTs are synthesized by tuning the annealing time with a hybrid of metal hydroxide@CNTs as a precursor. In the precursor, core−shell structures are formed by conformally coating 2D metal hydroxides on CNTs. After annealing it at 300 °C for different time, NiCo₂O₄ nanosheets or nanoparticles are then obtained and the core−shell structure is remained. Due to the reduced crystal size of NiCo₂O₄ and the high conductivity of CNTs, the composites have large specific capacitances, excellent rate performances, and good stability. The composite of NiCo₂O₄ nanoparticles on CNTs has a higher specific capacitance, about 1786 F g⁻¹ at 0.5 A g⁻¹, than the hybrid of NiCo₂O₄ nanosheets on CNTs due to their different morphologies. Using the composite as positive electrode and activated carbon as negative electrode, a hybrid capacitor cell can work in a voltage of 1.6 V, delivering an energy density of 32.5 Wh kg⁻¹ at 800 W kg⁻¹, showing a large potential for supercapacitors.     

Flower-like NiCo2O4/NiCo2S4 electrodes on Ni mesh for higher supercapacitor applications

In this research, we have effectively synthesized a novel NiCo₂O₄/NiCo₂S₄ powder by co-precipitation and thin films prepared using a screen-printing method on Ni mesh for supercapacitor applications. Herein, we report the effect of unique hierarchical nanostructures and the systematic effect of Ni and Co on the structural, morphological and electrical properties of the NiCo₂O₄/NiCo₂S₄ electrodes. The optimized NiCo₂O₄/NiCo₂S₄ electrode shows outstanding performance with a specific capacitance of 1966 F g⁻¹ at 5 mV s⁻¹. The cycling stability reports indicate the NiCo₂O₄/NiCo₂S₄ electrodes have an outstanding cyclic stability with 91% capacity retention. From the supercapacitor performance results, we confirmed that the NiCo₂O₄/NiCo₂S₄ electrode is useful for the fabrication of symmetric supercapacitors. These results reveal that the NiCo₂O₄/NiCo₂S₄ electrodes is a capable electrode material for supercapacitor applications in the future.     

Facile synthesis of a novel Fe3O4-rGO-MoO3 ternary nano-composite for high-performance hybrid energy storage applications

Supercapacitors (SCs) have been considered as inspiring energy storage devices due to the long cycle lifetime and high power densities. However, their energy density is limited due to the low capacitance of cathode materials and inferior cycling stability at practically useable potential windows >1.2 V. In this paper, we demonstrate the synthesis of a novel ternary Fe₃O₄-rGO-MoO₃ nano-composite (FGM) with nanoparticles-like morphology (NPs) by utilizing the fast and facile microwave hydrothermal process. The optimized composition of FGM nanocomposite is characterized by the XPS, EDS, Raman, SEM, TEM and HRTEM techniques. The FGM-NPs supported on the carbon cloth (FGM@CC) electrode is used to investigate the electrochemical charge storage properties in basic potassium hydroxide (KOH) electrolyte. The charge-storage properties of the FGM@CC electrode were studied by the CV, GCD and EIS techniques. The obtained results of FGM@CC electrode in aqueous electrolyte showed excellent electrochemical performance as compared with single metal oxides: maximum specific capacitance of 1666.50 F g⁻¹ (FGM@CC), 1075.26 F g⁻¹ (Fe₃O₄ NPs) and 952.38 F g⁻¹ (MoO₃ NPs) at a current density of 2.5 A g⁻¹. The capacitance retention was 95.01% (FGM@CC), 94.1% (Fe₃O₄ NPs) and 92.5% (MoO₃ NPs) after 5000 cycles. Further, the charge storage mechanism is analyzed in the light of power's law and systematical investigated the capacitive and diffusion controlled based stored charge in FGM@CC electrode. Thus FGM nano-composite showed best performance as the cathode material for the next generation flexible supercapacitors.     

Promising electrode material of Fe3O4 nanoparticles decorated on V2O5 nanobelts for high-performance symmetric supercapacitors

Bundled V₂O₅ nanobelts decorated with Fe₃O₄ nanoparticles (F3V nanostructures) were successfully synthesized to develop a low-cost electrode material for energy storage applications. The synthesized samples were subjected to structural, morphological and electrochemical studies. The Fe₃O₄ nanoparticles decorated over bundled V₂O₅ nanobelts exhibited better electrochemical properties than the pristine Fe₃O₄ nanoparticles and V₂O₅ nanobelts. The electrochemical behavior of the fabricated electrodes was investigated in an electrolyte of 3 M KOH, demonstrated an exceptional specific capacity values of 750.1, 660.3, and 1519 F g^–1 for V₂O₅, Fe₃O₄, and F3V respectively at a current density of 15 A g^–1. The assembled F3V symmetric supercapacitor (SSC) device exhibited an excellent specific capacitance of 93 F g^–1 at a current density of 0.5 A g^–1, delivering energy and power densities of 13 Wh.kg^–1 and 1530 W kg^–1, respectively, and superior long-term cycling stability of ～84% capacity retention over 5000 galvanostatic charge–discharge cycles. These findings demonstrate the extraordinary electrochemical characteristics of the F3V nanostructures, indicating their potential use in energy storage applications.     

Polypyrrole-wrapped NiCo2S4 nanoneedles as an electrode material for supercapacitor applications

In this study, dicobalt tetrasulfide (NiCo₂S₄) nanoneedles were successfully synthesized by a two-step hydrothermal method on nickel foam. A layer of polypyrrole (PPy) was further wrapped on the surface of the NiCo₂S₄ nanoneedles by in-situ polymerization. The obtained NiCo₂S₄@PPy composite was investigated for supercapacitor applications, which exhibited a capacitance of 1842.8 F g^?1 at 1 A g^?1. An asymmetric supercapacitor device fabricated with an activated carbon negative electrode and NiCo₂S₄@PPy positive electrodes exhibited an energy density of 41.2 Wh kg^?1 at 402.2 W kg^?1 with a high charge–discharge cycling stability (92.8% after 5000 cycles). These results demonstrate that NiCo₂S₄@PPy electrodes have broad application prospects as energy storage electrode materials.     

Construction of spherical NiO@MnO2 with core-shell structure obtained by depositing MnO2 nanoparticles on NiO nanosheets for high-performance supercapacitor

The 3D spherical NiO@MnO₂ composites grown on Ni foam with core-shell structure were prepared by a hydrothermal process followed by a chemical bath deposition process, and then the mechanism improving the electrochemical performance of NiO by MnO₂ modification were investigated by the first-principles calculations for the first time. This core-shell structure promotes an efficient contact between electrolyte and active materials, and the distinct architecture can offer fast transfer channels of ion and electrons. The initial capacitances of NiO, NiO@MnO₂ (deposition time of MnO₂ is 20 min), NiO@MnO₂ (deposition time of MnO₂ is 30 min) and NiO@MnO₂ (deposition time of MnO₂ is 60 min) at 10 A g⁻¹ are 931.6, 1064.4, 1227.2 and 766.8 F g⁻¹, respectively. After 10000 cycles, the reversible capacitances attenuate to 352.8, 661.0, 1089.4 and 616.6 F g⁻¹, respectively. NiO@MnO₂ (deposition time of MnO₂ is 30 min) shows the most excellent reversible capacitance at each cycle and the highest retention rates after 10000 cycles among all samples. The first-principles calculation confirms that a strong interfacial interaction between NiO and MnO₂ can be generated, and then the atomic relaxations at the interface are rather small due to the well-matched interface and epitaxial bonding, resulting in a relatively small interfacial polarization of NiO@MnO₂ composites during cycling. The outstanding rate capability and cycle performance of NiO@MnO₂ (deposition time of MnO₂ is 30 min) electrode are attributed to the synergistic effect and particular 3 D architectures.     

Factors influencing MnO2/multi-walled carbon nanotubes composite's electrochemical performance as supercapacitor electrode

Poor crystallined α-MnO₂ grown on multi-walled carbon nanotubes (MWCNTs) by reducing KMnO₄ in ethanol are characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and Brunauer-Emmett-Telle (BET) surface area measurement, which indicate that MWCNTs are wrapped up by poor crystalline MnO₂ and BET areas of the composites maintain the same level of 200 m² g⁻¹ as the content of MWCNTs in the range of 0-30%. The electrochemical performances of the MnO₂/MWCNTs composites as electrode materials for supercapacitor are evaluated by cyclic voltammetry (CV) and galvanostatic charge-discharge measurement in 1 M Na₂SO₄ solution. At a scan rate of 5 mV s⁻¹, rectangular shapes could only be observed for the composites with higher MWCNTs contents. The effect of additional conductive agent KS6 on the electrochemical behavior of the composites is also studied. With a fixed carbon content of 25% (MWCNTs included), MnO₂ with 20% MWCNTs and 5% KS6 has the highest specific capacitance, excellent cyclability and best rate capability, which gives the specific capacitance of 179 F g⁻¹ at a scan rate of 5 mV s⁻¹, and remains 114.6 F g⁻¹ at 100 mV s⁻¹.     

Anchoring 2D NiMoO4 nano-plates on flexible carbon cloth as a binder-free electrode for efficient energy storage devices

The energy security and mounting environmental issues compel the scientific community to allocate greatly efficient and economical energy renovation and storage systems. Among the energy storage devices, supercapacitors have become the forefront in energy storing systems in recent decades. The efficiency of supercapacitors mainly depend on the electrode's material and they usually suffer from a quick reduction in specific capacitance at higher current densities. Herein, we combined the nano-plates like bimetallic oxides (NiMiO₄) with mixed valence states on the surface of a conductive substrate (carbon cloth) without any binder and additives (denoted NMO@CC). The as-prepared electrode NMO@CC showed marvelous electrochemical properties in the aqueous basic electrolyte by achieving a high capacity of 1500 C g⁻¹ at current density of 5 A g⁻¹ with high degree of rate capability. More interestingly, the NMO@CC electrode demonstrated excellent cycling stability of 94.63% after 5000 cycles during charge-discharge process. Further, the charge storage mechanism of NMO@CC electrode is investigated by analyzing the surface capacitive and diffusion controlled processes and it shows high surface capacitive storage (71%). These admirable results are based on the highly open channels for efficient diffusion of electrolyte ions and electronic transmission through the NMO and backbone carbon cloth, respectively. Therefore, accurate morphology and surface manufacturing engineering are highly appreciated to enhance the active surface area and inherent conductivity of electrode materials.     

Novel binder-free electrode of NiCo2O4@NiMn2O4 core-shell arrays modified carbon fabric for enhanced electrochemical properties

There is still a great challenge to develop new-style battery-type electrode materials with low resistance, large surface area, and stable microstructures on carbon fabric, which limited the development of flexible devices. In this work, NiCo₂O₄ nanoneedle@NiMn₂O₄ nanosheet core-shell arrays are constructed on the carbon fabric as a high-capacitance and long-life supercapacitor electrode for the first time. Benefiting from this kind of binder-free core-shell microstructure, the CF@NiCo₂O₄@NiMn₂O₄ electrode displays extraordinary specific-capacitance of 539.2 F g⁻¹ at a current density of 2 A g⁻¹, and nearly 93.0% retention of total capacitance even after discharging 5000 cycles. The outstanding properties of the hybrid electrode demonstrate that it is of great potential for flexible supercapacitors and batteries the application.     

The additive-free electrode based on the layered MnO2 nanoflowers/reduced,graphene oxide film for high performance supercapacitor

The MnO₂ nanoflowers/reduced graphene oxide composite is coated on a nickel foam substrate (denoted as MnO₂ NF/RGO @ Ni foam) via the layer by layer (LBL) self-assembly technology without any polymer additive, following the soft chemical reduction. The layered MnO₂ NF/RGO composite is uniformly anchored on the Ni foam skeleton to form the 3D porous framework, and the interlayers have access to lots of ions channels to improve the electron transfer and diffusion. This special construction of 3D porous structure is beneficial to the enhancement of electrochemical property. The specific capacitance is up to 246 F g⁻¹ under the current density of 0.5 A g⁻¹. After 1000 cycles, it can retain about 93%, exhibiting excellent cycle stability. The electrochemical impedance spectroscopy measurements confirm that MnO₂ NF/RGO @ Ni foam electrode has lower R_ESR and R_CT values when compared to MnO₂ @ Ni foam and RGO @ Ni foam. This study opens a new door to the preparation of composite electrodes for high performance supercapacitor.     

Hydrothermal synthesis of Polypyrrole/MoS2 intercalation composites for supercapacitor electrodes

As a pseudocapacitive electrode materials for supercapacitor, Polypyrrole (PPy) exhibit excellent theoretical specific capacitance. However, it suffers from a poor cycling stability due to structural instability during charge-discharge process. In this work, a novel and facile hydrothermal method has been developed for the intercalation composites of PPy/MoS₂ with multilayer three-dimensional structure. The report result shows that the as-prepared electrode possess a outstanding electrochemical properties with significantly specific capacitance of 895.6 F g⁻¹ at current density of 1 A g⁻¹, higher energy density (3.774 Wh kg⁻¹) at power density of 252.8 kW kg⁻¹, furthermore, it also achieve remarkable cycling stability (~98% capacitance retention after 10,000 cycles) which is attributed to the synergistic effect of PPy and MoS₂. This synthetic strategy integrates performance enables the multilayer PPy/MoS₂ composites to be a promising electrode for energy storage applications.     

硫源对双壳层NiCo2S4超级电容性能影响

通过自模板法,选用硫代乙酰胺（TAA）、硫脲（TU）分别作硫源制备双壳层NiCo₂S₄纳米材料。其中以TAA为硫源制备的NiCo₂S₄表现出高的比电容（2064F/g,当电流密度为0.5A/g时）,优异的倍率性能（1291F/g,当电流密度为20A/g时）和较好循环稳定性。由动力学机制分析可知,NiCo₂S₄-TAA表面控制电容和扩散控制电容较NiCo₂S₄-TU均有提升。通过实验分析可知,TAA作为硫源合成的NiCo₂S₄是由较小的次级颗粒聚集而成,这有利于电化学过程中电解质离子的扩散。由于较好的导电性能和离子扩散速率,NiCo₂S₄-TAA表现出优异的电化学性能。上述结果表明,在本实验条件下,TAA是制备NiCo₂S₄电容器电极材料的最佳硫源。     

Construction of hierarchical NiMoO4@MnO2 nanosheet arrays on titanium mesh for supercapacitor electrodes

Hierarchical NiMoO₄@MnO₂ nanosheet arrays supported on titanium mesh are synthesized by cost effective hydrothermal methods for binder-free electrode. High specific area of porous MnO₂nanosheets and exceptionally high pseudocapacitive behavior of NiMoO₄nanosheets lead to a specific capacitance of 976 F g⁻¹at a current density of 1 A g⁻¹ with pleasurable rate characteristic in three electrode configuration. The excellent electrochemical performances of the integrated electrode can be ascribed to the unique core-shell nanostructure and synergic interaction. It is believed that the hierarchical NiMoO₄@MnO₂ nanosheet arrays supported on titanium mesh can provide great prospect for energy storage applications.     

Ni@NiCo2O4 core/shells composite as electrode material for supercapacitor

A novel Ni@NiCo₂O₄ core/shells structure consisting of the Ni microspheres skeletons and nanosheet-like NiCo₂O₄ skins was designed and investigated as the electrochemical electrode for supercapacitor. Due to the unique architecture with Ni microspheres as the highly conductive cores improving the electrical conductivity of electrode and external nanosheet-like NiCo₂O₄ shells as the efficient electrochemical active materials facilitating the contact between the electrode and electrolyte, the as-prepared Ni@NiCo₂O₄ exhibited excellent electrochemical performance with high specific capacity of 597 F g⁻¹ (1 A g⁻¹) as well as remarkable capacitance retention of 96% (3000 cycles). These impressive results pave the way to design high-performance electrode materials for energy storage.     

NiCo2O4 arrays nanostructures on nickel foam: Morphology control and application for pseudocapacitors

The design of electrode materials with desirable morphology is of great importance and challenge to fabricate high-performance supercapacitors. In this work, NiCo₂O₄ nanopetal, nanosheet, nanoneedle and nanorod arrays on nickel foam have been synthesized through a facile hydrothermal method. The morphologies of NiCo₂O₄ arrays can be easily controlled by adjusting the kinds of alkali source and the addition of NH₄F. The electrochemical results show that the NiCo₂O₄ nanoneedles electrode has the optimal electrochemical performance among four samples, demonstrating its promising application potential for high performance supercapacitors. This investigation about morphology control of NiCo₂O₄ electrode materials and the relationship between the morphologies and corresponding electrochemical performances provides strategies to enhance the performance of supercapacitor electrodes.     

Fabrication of CuFe2O4@g-C3N4@GNPs nanocomposites as anode material for supercapacitor applications

The aim of this study was to synthesize CuFe₂O₄ together with g-C₃N₄ and GNPs in various combinations on the surface of Ni foam for use as anode materials in supercapacitors. The fabricated electrodes were investigated by XRD, FTIR, XPS, BET, SEM and TEM for content and by CV, GCD and EIS analysis for electrochemistry. The characterization results showed that CuFe₂O₄ was successfully synthesized together with g-C₃N₄ and GNPs in a nanosponge-like geometry. The highest value of specific capacitance was found to be 989 mF/cm² at 2 mA measurement in the triple combination. Moreover, the stability of this electrode was measured to be 70% after 1500 cycles at 16 mA, while the energy and power densities were calculated to be 27.8 mWh/cm² and 300 mW/cm², respectively. The EIS results show that the carbon-based component increased the Cs value by decreasing the charge transfer and diffusion resistances of the electrodes. Compared to its counterparts in the literature, its Cs value is quite high, but its stability is low, so it can be used in low-cycle applications.