MWCNTs-GONRs/Co3O4 electrode with needle-like arrays for outstanding supercapacitors

Multiwalled carbon nanotubes-graphene oxide nanoribbons (MWCNTs-GONRs) exhibit high specific surface area and good electroconductivity because of their unique three-dimensional cross-linking structure with the properties of both CNTs and GONRs. In this study, a hydrothermal method was employed to anchor MWCNTs–GONRs onto a Ni foam (NF) to obtain a precursor substrate. Subsequently, Co₃O₄ arrays were grown on the NF substrate to synthesize a MWCNTs–GONR/Co₃O₄ electrode. The electrode showed a capacitance of 846.2 F g⁻¹ at 1 A g⁻¹ and a capacitance retention of 90.1% after 3000 cycles. Furthermore, MWCNTs–GONRs/Co₃O₄ and active carbon (AC) were used as the positive and negative electrodes, respectively, to assemble a supercapacitor, which delivered a maximum energy density of 38.23 W h kg⁻¹ and a high power density of 6.80 kW kg⁻¹. In addition, the specific capacitance of the device reached a maximum of 91.5% after 9000 cycles. Thus, the MWCNTs–GONRs/Co₃O₄ electrode showed huge potential for supercapacitor applications.     

Holey graphene interpenetrating networks for boosting high-capacitive Co3O4 electrodes via an electrophoretic deposition process

A composite of Co₃O₄/holey graphene (Co₃O₄/HG) was prepared via a facile hydrothermal route, and was then processed into an electrode by an electrophoretic deposition process. Holey graphene (HG) wrapped Co₃O₄ to form a 3D skeleton network, thereby providing high electrical conductivity, and the holes in HG could further shorten the electrolyte ion diffusion pathway. Therefore, by adjusting the mass ratio of Co₃O₄ to HG, the Co₃O₄/HG composite afforded an enhanced capacitance of 2714 F g⁻¹ (at a current density of 1 A g⁻¹), which is 20 times higher than that of pure Co₃O₄. To further explore the practical applications of Co₃O₄/HG, a symmetric supercapacitor employing Co₃O₄/HG was fabricated. The supercapacitor functioned stably at potentials up to 1.2 V, with an enhanced energy density of 165 Wh kg⁻¹ and a high power density of 0.6 kW kg⁻¹ at 1 A g⁻¹.     

Waste catkins-derived graphitic carbon/Co3O4 composites as long-life and high-rate anodes for lithium-ion battery

Upgrading waste re-utilization has been regarded as an important concept to promote the sustainable development of social economy. Herein, waste catkins were used as carbon source and template to prepare graphitic carbon/Co₃O₄ composites through cobalt salt immersion, in-situ carbonization and calcination. The obtained Co₃O₄/C composites inherit the microtubular structure of catkins with ultra-thin tube wall and large tube cavity. Particularly, the sample (Co₃O₄/C-280) calcined at 280 °C in air shows a morphology of the hollow Co₃O₄ spheres (av. 50 nm) evenly embedded on the biocarbon tube. As an anode for lithium-ion battery, such unique structure is more conductive to alleviate volume expansion. As expected, Co₃O₄/C-280 electrode has excellent rate capability at 5 A g⁻¹ and stable long-cycle performance (647.3 mA h g⁻¹, 1800 cycles, 1 A g⁻¹). The presence of pseudo-capacitance behavior plays an important role in improving the capacity of material. The good electrochemical properties of Co₃O₄/C-280 can be ascribed to the synergistic effect of hollow tubular structure and graphitic carbon. Therefore, the strategy of making waste profitable is in line with the theme of green and sustainable development, and provides a reference for improving lithium storage performance of Co₃O₄-based anode materials.     

Facile synthesis of three dimensional flower-like Co3O4@MnO2 core-shell microspheres as high-performance electrode materials for supercapacitors

In this work, we reported the synthesis of three dimensional flower-like Co₃O₄@MnO₂ core-shell microspheres by a controllable two-step reaction. Flower-like Co₃O₄ microspheres cores were firstly built from the self-assembly of Co₃O₄ nanosheets, on which MnO₂ nanosheets shells were subsequently grown through the hydrothermal decomposition of KMnO₄. The MnO₂ nanosheets shells were found to increase the electrochemical active sites and allow faster redox reaction kinetics. Based on these advantages, when used as an electrode for supercapacitors, the prepared flower-like Co₃O₄@MnO₂ core-shell composite electrode demonstrated a significantly enhanced specific capacitance (671 F g⁻¹ at 1 A g⁻¹) as well as improved rate capability (84% retention at 10 A g⁻¹) compared with the pristine flower-like Co₃O₄ electrode. Moreover, the optimized asymmetric supercapacitor device based on the flower-like Co₃O₄@MnO₂//active carbon exhibited a high energy density of 34.1 W h kg⁻¹ at a power density of 750 W kg⁻¹, meaning its great potential application for energy storage devices.     

One-step hydrothermal synthesis of hybrid core-shell Co3O4@SnO2–SnO for supercapacitor electrodes

We successfully synthesized a novel core-shell hybrid metal oxide via a simple one-step hydrothermal method without annealing. This composite of Co₃O₄ particles covered with SnO₂–SnO (Co₃O₄@SnO₂–SnO) predicted better performance compared to pure Co₃O₄, which strongly depends on the synthetic temperature. The Co₃O₄@SnO₂–SnO prepared at a temperature of 250 °C (labeled Co₃O₄@SnO₂–SnO-250) exhibited an outstanding specific capacitance of 325 F g⁻¹ under the current density of 1 A g⁻¹, which was much higher than those of Co₃O₄ (12.6 F g⁻¹) and other composites. Additionally, the sample also exhibited good cycle stability performance with a retention rate of 100% after 5000 cycles at a current density of 5 A g⁻¹. Through X-ray photoelectron spectroscopy analysis, the presumed mechanism was that Sn-O_x decreases the surface electron densities of Co₃O₄, which is beneficial to OH⁻ adsorption and specific capacitance improvement, and the synthetic temperature had a strong impact on the microstructure and thus on the surface electron densities. The most.obvious finding to emerge from this study is that the specific capacitance can be improved through adjusting the surface electron densities of transition metal oxides.     

Straightforward synthesis of hierarchical Co3O4@CoWO4/rGO core–shell arrays on Ni as hybrid electrodes for asymmetric supercapacitors

Hierarchical Co₃O₄@CoWO₄/rGO core/shell nanoneedles arrays are successfully grown on 3D nickel foam using a simple, effective method. By virtue of its unique structure, Co₃O₄@CoWO₄/rGO demonstrates an enhanced specific capacitance of 386 F g⁻¹ at 0.5 A g⁻¹ current density. It can be used as an integrated, additive-free electrode for supercapacitors that boasts excellent performance. As illustration, we assemble an asymmetric supercapacitor (ASC) using the as-prepared Co₃O₄@CoWO₄/rGO as the positive electrode and activated carbon as the negative electrode. The optimized ASC displays a maximum energy density of 19.99 Wh kg⁻¹ at a power density of 321 W kg⁻¹. Furthermore, the ASC also presents a remarkably long cycle life along with 88.8% specific capacitance retention after 5000 cycles.     

Hierarchical Co3O4@ZnWO4 core/shell nanostructures on nickel foam: Synthesis and electrochemical performance for supercapacitors

To improve the electrochemical properties of Co₃O₄ for supercapacitors application, a hierarchical Co₃O₄@ZnWO₄ core/shell nanowire arrays (NWAs) material is designed and synthesized successfully via a facile two-step hydrothermal method followed by the heat treatment. Co₃O₄@ZnWO₄ NWAs exhibits excellent electrochemical performances with areal capacitance of 4.1 F cm⁻² (1020.1 F g⁻¹) at a current density of 2 mA cm⁻² and extremely good cycling stability (99.7% of the initial capacitance remained even after 3000 cycles). Compared with pure Co₃O₄ electrodes, the results prove that this unique hierarchical hybrid nanostructure and reasonable assembling of two electrochemical pseudocapacitor materials are more advantageous to enhance the electrochemical performance. Considering these remarkable capacitive behaviors, the hierarchical Co₃O₄@ZnWO₄ core/shell NWAs nanostructure electrode can be revealed promising for high-performance supercapacitors.     

Enhancing the performance and stability of NiCo2O4 nanoneedle coated on Ni foam electrodes with Ni seed layer for supercapacitor applications

We introduce a facile way to improve the performance of NiCo₂O₄ electrode by including a Ni seed layer. The seed layer deposited on Ni foam electrode (NiCo₂O₄/Ni@NF) shows the superior specific capacity of 1142 C g⁻¹ at 1 A g⁻¹ with the excellent cycle stability of ∼96% even after 5000 cycles at a higher current density of 5 A g⁻¹. These values are about 3.7 times higher than that of the electrode (NiCo₂O₄@NF) without a seed layer, which shows the specific capacity of 305 C g⁻¹@1 A g⁻¹ with cycle stability of 84% even at a lower current density of 1 A g⁻¹. The enhanced performance of the NiCo₂O₄/Ni@NF electrode may be attributed to lower interface resistance, fast redox reversible reaction, and improved surface active sites. Further, the asymmetric solid-state supercapacitor device is fabricated by using the NiCo₂O₄/Ni@NF electrode as a positive and reduced graphene oxide (rGO)-Fe₂O₃ nanograin as a negative electrode with PVA-KOH gel electrolyte, and the NiCo₂O₄/Ni20@NF//rGO-Fe₂O₃@NF asymmetric solid state device delivers an areal capacitance of 446 mF cm⁻² with a low capacitance loss of 18% even after 10000 cycles. Further, the fabricated asymmetric solid state device shows a maximum energy density of 124.3 Wh cm⁻² (at 3.58 kW cm⁻²) and power density of 14.88 kW cm⁻² (at 31.41 Wh cm⁻²).     

3D network-like porous MnCo2O4 by the sucrose-assisted combustion method for high-performance supercapacitors

3D network-like porous MnCo₂O₄ nanostructures have been successfully fabricated through a facile and scalable sucrose-assisted combustion route followed by calcination treatment. Benefiting from its advantages of the unique 3D network-like architectures with large specific surface area (216.15 m² g⁻¹), abundant mesoporosity (2–50 nm) and high electronic conductivity, the as-prepared MnCo₂O₄ electrode displays a high specific capacitance of 647.42 F g⁻¹ at a current density of 1 A g⁻¹, remarkable capacitance retention rate of 70.67% at current density of 10 A g⁻¹ compared with 1 A g⁻¹, and excellent cycle stability (only 6.32% loss after 3000 cycles). The excellent electrochemical performances coupled with facile and cost effective method will render the as-fabricated 3D network-like porous MnCo₂O₄ as a promising electrode material for supercapacitors.     

Template-free synthesis of novel Co3O4 micro-bundles assembled with flakes for high-performance hybrid supercapacitors

In this paper, a novel Co₃O₄ micro-bundles structure (Co₃O₄ MBs) was obtained at 120 °C after a hydrothermal reaction for 24 h and followed by an annealing treatment at 300 °C in air. The unique Co₃O₄ MBs are constructed by many adjacent flakes with 0.4 μm in thickness, and exhibit a large surface area of 81.2 m² g^?1 and a mean pore diameter of 6.14 nm, which may facilitate a sufficient contact with electrolyte and then shorten the diffusion pathway of ions. A remarkable electrochemical behavior including specific capacity of 282.3 C g^?1 at 1 A g^?1 and 205.9 C g^?1 at 10 A g^?1, and an excellent cycling performance with 74.6% capacity retention after 4000 charge-discharge process at 5 A g^?1 are achieved when the test of Co₃O₄ MBs-modified electrode is performed using three-electrode configuration. Additionally, a hybrid supercapacitor (HSC) was fabricated with the obtained Co₃O₄ MBs as positive electrode and commercial activated carbon (AC) as negative electrode. The HSC exhibits a specific capacity of 144.1 C g^?1 at 1 A g^?1 and 126.4% capacity retention after 5000 cycles at 5 A g^?1. An energy density of 38.5 W h kg^?1 can be obtained at a power density of 962.0 W kg^?1, and 29.5 W h kg^?1 is still retained at 8532.5 W kg^?1. The simple synthetic strategy can be applicable to the synthesis of other transition metal oxides with superior electrochemical performance.     

Design and self-assembly of metal-organic framework-derived porous Co3O4 hierarchical structures for lithium-ion batteries

Porous metal oxides hierarchical structures with controlled morphologies have received great attention because of their promising applications in catalysis, energy storage, gas sensing, etc. Porous Co₃O₄ hierarchical structures with controlled morphologies were synthesized on the basis of a pyrolytic conversion of Co-based metal-organic frameworks (Co-MOFs), which were initially grown in solutions containing Co(NO₃)₂·6H₂O, 1,3,5-Benzentricarboxylic acid and pyrazine as solute and N,N-dimethylformamide (DMF) as solvent under a solvothermal condition. Porous Co₃O₄ with twin hemispherical and flower-like structures were obtained with the assistance of PVP by adjusting the amount of pyrazine. The results of nitrogen adsorption–desorption indicate the BET surface area (22.6 m² g⁻¹) of twin hemispherical Co₃O₄ structures is lower than that (33.3 m² g⁻¹) of flower-like Co₃O₄ structures. However, the pore size of twin hemispherical Co₃O₄ structures is smaller, which is centered at about 2.5, 4.0 and 20.0 nm. The Co₃O₄ with twin hemispherical structures exhibit more excellent electrochemical performance as anode materials for lithium ion batteries than that of flower-like Co₃O₄ structures, which may be attributed to the smaller particle size and compact porous structures with suitable pore size.     

Facile synthesis of porous hollow Co3O4 microfibers derived-from metal-organic frameworks as an advanced anode for lithium ion batteries

Co₃O₄, as a promising anode material for the next generation lithium ion batteries to replace graphite, displays high theoretical capacity (890 mAh g⁻¹) and excellent electrochemical properties. However, the drawbacks of its poor cycle performance caused by large volume changes during charge-discharge process and low initial coulombic efficiency due to large irreversible reaction impede its practical application. Herein, we have developed a porous hollow Co₃O₄ microfiber with 500 nm diameter and 60 nm wall thickness synthesized via a facile chemical precipitation method with subsequent thermal decomposition. As an advanced anode for lithium ion batteries, the porous hollow Co₃O₄ microfibers deliver an obviously enhanced electrochemical property in terms of lithium storage capacity (1177.4 mA h g⁻¹ at 100 mA g⁻¹), initial coulombic efficiency (82.9%) and cycle performance (76.6% capacity retention at 200th cycle). This enhancement could be attributed to the well-designed microstructure of porous hollow Co₃O₄ microfibers, which could increase the contact surface area between electrolyte and active materials and accommodate the volume variations via additional void space during cycling.     

Hierarchical microstructure of CNTs interwoven ultrathin Co3S4 nanosheets as a high performance anode for sodium-ion battery

In this work, Co₃S₄/CNTs three-dimensional hierarchical microstructure has been synthesized through a facile sulfidation method with Co₃O₄/CNTs as precursor. Particularly, by controlling hydrothermal time, the optimized Co₃S₄/CNTs-9 composite consists of ultrathin and rich mesoporous Co₃S₄ nanosheets (<?10?nm) with CNTs firmly intertwined inside microstructures. Benefitting from the porous and robust secondary-structure, as well as the intertwined CNTs among ultrathin active materials Co₃S₄ nanosheets, Co₃S₄/CNTs-9 electrode provides fast efficient ways of ion and electron transportation. As a result, it exhibits an excellent rate performance. Charge capacity retention at 1?A?g^?1 is up to 80% compared with 0.1?A?g^?1. The enhanced extrinsic pseudocapacitive contribution is confirmed at higher rate through the cyclic voltammetry analysis at different scan rates of Co₃S₄/CNTs-9 electrode. Importantly, Co₃S₄ electrode also exhibits a high initial coulombic efficiency of 82.89%, which suggests that Co₃S₄ is a promising anode candidate for sodium-ion batteries.     

Porous Co3O4 nanorods as superior electrode material for supercapacitors and rechargeable Li-ion batteries

Porous aggregated nanorods of Co₃O₄ with a surface area of ~100 m² g^?1 synthesized without using any templates or surfactants give very high specific capacitance of ~780 F g^?1 when used as electrode in a faradaic supercapacitor, with a cycle life of more than 1,000 cycles. Further, in Li-ion batteries when used as an anode, the Co₃O₄ nanorods achieved a capacity of 1155 mA h g^?1 in the first cycle and upon further cycling it is stabilized at 820 mA h g^?1 for more than 25 cycles. Detailed characterization indicated the stability of the material and the improved performance is attributed to the shorter Li-insertion/desertion pathways offered by the highly porous nanostructures. The environmentally benign and easily scalable method of synthesis of the porous Co₃O₄ nanorods coupled with the superior electrode characteristics in supercapacitors and Li-ion batteries provide efficient energy storage capabilities with promising applications.     

Anchoring mesoporous Fe3O4 nanospheres onto N-doped carbon nanotubes toward high-performance composite electrodes for supercapacitors

Fe-based oxide electrodes for practical applications in supercapacitors (SCs) suffer from low conductivity and poor structural stability. To settle these issues, we report on the design and synthesis of Fe₃O₄/carbon nanocomposites via firmly anchoring mesoporous Fe₃O₄ nanospheres onto N-doped carbon nanotubes (N-CNTs) via C–O–Fe bonds. Mesoporous Fe₃O₄ nanospheres are featured by rich electroactive sites and short ion diffusion pathways. The N-CNTs, on the other hand, serve as the scaffolds, which not only provide conductive networks but also suppress the accumulation between mesoporous Fe₃O₄ nanospheres as well as alleviate volume changes during charge/discharge cycles. Accordingly, the constructed Fe₃O₄/N-CNTs nanocomposite electrode demonstrates improved specific capacity values of up to 314 C g⁻¹ at 1 A g⁻¹, with 92% retention of the initial capacity after 5000 cycles at 10 A g⁻¹. In addition, the assembled Fe₃O₄/N-CNTs//active carbon (AC) asymmetric supercapacitor (ASC) device possesses an energy density of 25.3 Wh kg⁻¹, suggesting that the prepared Fe₃O₄/N-CNTs nanocomposites are promising electrode materials for use in SCs.     

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.     

Simple solvothermal synthesis of magnesium cobaltite microflowers as a battery grade material with high electrochemical performances

In this paper, a simple solvothermal method accompanied with a post annealing process was used to synthesize porous and hierarchical MgCo₂O₄ microflowers (MFs), which were composed of many tightly connected nanosheets. The entire synthesis process was accomplished without any surfactant or template participation. The specific surface area of MgCo₂O₄ MFs with mean pore size of 29.6 nm was as high as 71.58 m² g⁻¹. A typical three-electrode system was used to investigate the electrochemical properties of MgCo₂O₄ MFs-based electrode in 2 M of potassium hydroxide aqueous solution as electrolyte. The results demonstrated that such working electrode delivered a specific capacity of 313.3 C g⁻¹ at 1 A g⁻¹, and still remained 189.4 C g⁻¹ even at the current density increasing to 16 A g⁻¹. In addition, the capacity retention reached 74.5% after 5000 cycles at 5 A/g, suggesting its excellent long-term stability. MgCo₂O₄ MFs with highly specific surface area as well as mesoporous microstructures are significantly beneficial to rapid Faradic reaction, in that it ensures sufficient contact of electrolyte/electrode materials and shortens diffusion paths for ions/electrons, as well as maximizes the number of active sites. The synthesis procedure of MgCo₂O₄ MFs proposed in this work is simple and cheap, and is expected to be employed for the preparation of other binary metal cobaltite as well.     

Co3O4 thin film prepared by a chemical bath deposition for electrochemical capacitors

Co₃O₄ thin film is synthesized on ITO by a chemical bath deposition. The prepared Co₃O₄ thin film is characterized by X-ray diffraction, and scanning electron microscopy. Electrochemical capacitive behavior of synthesized Co₃O₄ thin film is investigated by cyclic voltammetry, constant current charge/discharge and electrochemical impedance spectroscopy. Scanning electron microscopy images show that Co₃O₄ thin film is composed of spherical-like coarse particles, together with some pores among particles. Electrochemical studies reveal that capacitive characteristic of Co₃O₄ thin film mainly results from pseudocapacitance. Co₃O₄ thin film exhibits a maximum specific capacitance of 227 F g⁻¹ at the specific current of 0.2 A g⁻¹. The specific capacitance reduces to 152 F g⁻¹ when the specific current increases to 1.4 A g⁻¹. The specific capacitance retention ratio is 67% at the specific current range from 0.2 to 1.4 A g⁻¹.     

Pseudocapacitive properties of electrodeposited porous nanowall Co3O4 film

A porous nanowall Co₃O₄ film is prepared by a facile cathodic electrodeposition. The as-prepared porous nanowall Co₃O₄ film shows a net-like porous structure with huge porosity. The porous network is made up of free standing interconnected Co₃O₄ nanoflakes with a thickness of 20 nm. As cathode material for pseudocapacitors, porous nanowall Co₃O₄ film exhibits weaker polarization, higher electrochemical reactivity and better cycling performance as compared to the dense Co₃O₄ film. The specific capacitance of porous nanowall Co₃O₄ film is 325 F g⁻¹ at 2 A g⁻¹ and 247 F g⁻¹ at 40 A g⁻¹, respectively, much higher than that of the dense Co₃O₄ film (230 F g⁻¹ at 2 A g⁻¹ and 167 F g⁻¹ at 40 A g⁻¹). The better pseudocapacitive performances of the porous nanowall Co₃O₄ film are attributed to its highly porous morphology, which provides large reaction surface and short ion diffusion paths, and relaxes the volume change caused by the reaction during the cycling process.     

Preparation of LiNi1/3Co1/3Mn1/3O2/polytriphenylamine cathode composites with enhanced electrochemical performances towards reversible lithium storage

A series of LiNi_1/3Co_1/3Mn_1/3O₂/polytriphenylamine composites were successfully synthesized by ultrasound dispersion method. LiNi_1/3Co_1/3Mn_1/3O₂/polytriphenylamine (5.0?wt%) composite with small and homogeneous particle size exhibited excellent electrochemical performance, which delivered an initial discharge capacity of 223.7?mAh g^?1 with a capacity retention of 84.39% after 100 cycles in the voltage range of 2.5–4.5?V and at a current density of 0.2C. Moreover, an excellent specific discharge capacity of 127.3?mAh g^?1 at a current density 5C indicates a superior rate performance of the LiNi_1/3Co_1/3Mn_1/3O₂/polytriphenylamine (5.0?wt%) composite. The good electrochemical performances of the composite can be attributed to the introduction of polytriphenylamine, which increased electrical conductivity, decreased charge transfer resistance and increased Li⁺ ion diffusion ability. These noteworthy results demonstrated that LiNi_1/3Co_1/3Mn_1/3O₂/polytriphenylamine composites might be potential cathode materials for lithium ion batteries.