Preparation of Co3O4 nanoplate/graphene sheet composites and their synergistic electrochemical performance

Co₃O₄ nanoplate/graphene sheet composites were prepared through a two-step synthetic method. The composite material as prepared was characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. The platelet-like morphology of Co₃O₄ leads to a layer-by-layer-assembled structure of the composites and a good dispersion of Co₃O₄ nanoplates on the surface of graphene sheets. The electrochemical characteristics indicate that the specific capacitance of the composites is 337.8 F?g^?1 in comparison with the specific capacitance of 204.4 F?g^?1 without graphene sheets. Meanwhile, the composites have an excellent rate capability and cycle performance. The results show that the unique microstructure of the composites enhances the electrochemical capacitive performance of Co₃O₄ nanoplates due to the three-dimensional network of graphene sheets for electron transport increasing electric conductivity of the electrode and providing unobstructed pathways for ionic transport during the electrochemical reaction.     

Hierarchically Porous NaCoPO4–Co3O4 Hollow Microspheres for Flexible Asymmetric Solid‐State Supercapacitors

A template‐free hydrothermal method is developed to prepare hierarchical hollow precursors. An inside‐out Ostwald ripening mechanism is proposed to explain the formation of the hollow structure. After the calcination in the air, hierarchically meso/macroporous NaCoPO₄–Co₃O₄ hollow microspheres can easily be obtained. When being evaluated as electrode materials for a supercapacitor, the hierarchically porous NaCoPO₄–Co₃O₄ hollow microspheres electrode shows a specific capacitance of 268 F g^?1 at 0.8 A g^?1 and offers a good cycle life. More importantly, the obtained materials are successfully applied to fabricate flexible solid‐state asymmetric supercapacitors. The device exhibits a specific capacitance of 28.6 mF cm^?2 at 0.1 mA cm^?2, a good cycling stability with only 5.5% loss of capacitance after 5000 cycles, and good mechanical flexibility under different bending angles, which confirms that the hierarchically porous NaCoPO₄–Co₃O₄ hollow microspheres are promising active materials for the flexible supercapacitor.     

Free-standing 3D Co3O4@NF micro-flowers composed of porous ultra-long nanowires as an advanced cathode material for supercapacitor

The development of smart structured cathode materials for supercapacitors (SCs) has sparked tremendous interest. However, the appropriate design to achieve high capacitance and energy density-based cathode materials remains a major problem for energy storage systems. This article describes the effective synthesis of self-supported 3D micro-flowers composed of ultrathin nanowires array of Co₃O₄ on Ni foam (NF) using hydrothermal conditions (Co₃O₄@NF). The mesoporous Co₃O₄@NF with a high surface area, providing a rich active state for the Faraday redox reaction and increasing the diffusion rate of the electrolyte ions. The optimized Co₃O₄@NF-16h electrode exhibited supreme electrochemical performance by delivering a high specific capacitance of 1878, (1127) and 1200 (720 C g⁻¹) F g⁻¹ at 1.0 and 20 A g⁻¹, respectively. The Co₃O₄@NF electrode retained good capacitance stability of 91% over 10000 cycles at 20 A g⁻¹ with excellent rate-performance of 67% at 20 folded high current values. The obtained results for the Co₃O₄@NF electrode are presented the enhanced pseudocapacitive performance, indicating the substantial potential for high-performance supercapacitor applications.     

Carbon‐Encapsulated Tube‐Wire Co3O4/MnO2 Heterostructure Nanofibers as Anode Material for Sodium‐Ion Batteries

This study presents a general approach for the synthesis of carbon‐encapsulated wire‐in‐tube Co₃O₄/MnO₂ heterostructure nanofibers (Co₃O₄/MnO₂@C) via electrospinning followed by calcination. The as‐synthesized Co₃O₄/MnO₂@C is investigated as the sodium‐ion batteries anode material, which not only exhibits a high reversible capacity of 306 mAh g⁻¹ at 100 mA g⁻¹ over 200 cycles, but also shows a cycling stability of 126 mAh g⁻¹ after 1000 cycles at a high current density of 800 mA g⁻¹. The excellent electrochemical performance can be ascribed to the contribution from carbon‐encapsulated outer‐tube Co₃O₄ and inner‐wire MnO₂ heterostructures, which offer a large internal space and good electrical conductivity. The present work can be helpful in providing new insights into heterostructures for sodium‐ion batteries and other applications.     

Cobalt terephthalate MOF-templated synthesis of porous nano-crystalline Co3O4 by the new indirect solid state thermolysis as cathode material of asymmetric supercapacitor

In this work, two different types of Co₃O₄ nano-crystals were synthesized by (i) conventional direct solid state thermolysis of cobalt terephthalate metal-organic framework (MOF-71) and (ii) new indirect solid state thermolysis of Co(OH)₂ derived by alkaline aqueous treatment of MOF-71. The products were then characterized by X-ray diffraction technique (XRD), Fourier transforms infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Reflection electron energy loss spectroscopy (REELS), Brunauer, Emmett, and Teller (BET), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) techniques. By REELS analysis the energy band gap of MOF-71 was determined to be 3.7 eV. Further, electrochemical performance of each Co₃O₄ nanostructure was studied by the cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS) in a three-electrode system in KOH electrolyte. An asymmetric supercapacitor was fabricated using indirect Co₃O₄ nanoparticles as cathode and electrochemically reduced graphene oxide as anode, and the electrochemical properties were studied and showed a high energy density of 13.51 Wh kg⁻¹ along with a power density of 9775 W kg⁻¹ and good cycling stability with capacitance retention rate of 85% after 2000 cycles.     

Decorating reduced graphene oxide with Co3O4 hollow spheres and their application in supercapacitor materials

In this paper, a composite of reduced graphene oxide decorated by Co₃O₄ hollow spheres (Co₃O₄/RGO composite) has been synthesized by a one-pot solvothermal method. The samples are characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR), Raman spectra and so on. The results demonstrate that the Co₃O₄ hollow spheres with good purity and homogenous size are absorbed onto the reduced graphene oxide sheets as spacers to prevent the aggregation of the graphene oxide sheets. Furthermore, the well electrochemical properties demonstrate that the Co₃O₄/RGO composite might have potential applications as electrode materials for supercapacitors.     

Graphene oxides and carbon nanotubes embedded in polyacrylonitrile-based carbon nanofibers used as electrodes for supercapacitor

This study investigates the use of graphene oxides (GOs) and carbon nanotubes (CNTs) embedded in polyacrylonitrile-based carbon nanofibers (GO–CNT/CNF) as electrodes for the supercapacitor. GO–CNT/CNF was prepared by electrospinning, and was subsequently stabilized and activated. The specific capacitance of GO–CNT/CNF is 120.5 F g⁻¹ in 0.5 M Na₂SO₄ electrolyte, which is higher than or comparable to the specific capacitances of carbon-based materials in neutral aqueous electrolyte, as prepared in this study. GO–CNT/CNF also exhibits a superior cycling stability, and 109% of the initial specific capacitance after 5000 cycles. The high capacitance of GO–CNT/CNF could be attributed to the edge planes and the functional groups of GO, the highly electrical conductivity of CNT, and the network structure of the electrode.     

Flexible Ti‐Doped FeOOH Quantum Dots/Graphene/Bacterial Cellulose Anode for High‐Energy Asymmetric Supercapacitors

Ti‐doped FeOOH quantum dots (QD) decorated on graphene (GN) sheets are designed and fabricated by a facile and scalable synthesis route. Importantly, the Ti‐doped FeOOH QD/GN are successfully dispersed within bacterial cellulose (BC) substrate as bending anode with large loading mass for flexible supercapacitor. By virtue of its favorable architecture, this composite electrode exhibits a remarkable areal capacitance of 3322 mF cm^?2 at 2 mA cm^?2, outstanding cycle performance (94.7% capacitance retention after 6000 cycles), and excellent mechanical strength (68.7 MPa). To push the energy density of flexible supercapacitors, the optimized asymmetric supercapacitor using Mn₃O₄/GN/BC as positive electrode and Ti‐doped FeOOH QD/GN/BC as negative electrode can be cycled reversibly in the operating voltage range of 0–1.8 V and displays ultrahigh areal energy density of 0.541 mWh cm^?2, ultrahigh volumetric energy density of 9.02 mWh cm^?3, reasonable cycling performance (9.4% decay in specific capacitance after 5000 cycles), and good capacitive retention at bending state.     

Synergistic effect of Cr2O3 and Co3O4 nanocomposite electrode for high performance supercapacitor applications

The fabrication of high performance supercapacitor electrodes has been greatly investigated for future high power storage applications. In this present work, chromium oxide-cobalt oxide based nanocomposite (Cr₂O₃–Co₃O₄ NC) was synthesized using the hydrothermal approach. Moreover, the cyclic voltammetry (CV) study reveals the Cr₂O₃–Co₃O₄ NC delivers a high specific capacitance of 619.4 F/g at 10 mV/s. The electrochemical impedance spectra (EIS) of Cr₂O₃–Co₃O₄ NC possess the solution resistance (R_s) and charge transfer resistance (R_ct) of 0.68 Ω and 0.03 Ω respectively. The Galvanostatic charge-discharge (GCD) analysis demonstrated the prolonged charge-discharge time and good rate capability of the Cr₂O₃–Co₃O₄ NC. The cyclic stability of Cr₂O₃–Co₃O₄ NC delivers superior capacitive retention of 83% even after 2000 cycles. The asymmetric supercapacitor (ASC) device based on Cr₂O₃–Co₃O₄//AC yielded an energy density of 4.3 Wh/kg at the corresponding power density of 200 W/kg. Furthermore, the ASC delivers superior cyclic stability of 74.8% even after 1000 consecutive charge-discharge cycles.     

Ultrahigh supercapacitance in cobalt oxide nanorod film grown by oblique angle deposition technique

Nanorod films of cobalt oxide (Co₃O₄) have been grown by a unique oblique angle deposition (OAD) technique in an e-beam evaporator for supercapacitor electrode applications. This technique offers a non-chemical route to achieve large aspect ratio nanorods. The fabricated electrodes at OAD 80° exhibited a specific capacitance of 2875 F/g. The electrochemically active surface area was 1397 cm⁻², estimated from the non-Faradaic capacitive current region. Peak energy and power densities obtained for Co₃O₄ nanorods were 57.7 Wh/Kg and 9.5 kW/kg, respectively. The Co₃O₄ nanorod electrode showed a good endurance of 2000 charge-discharge cycles with 62% retention. The OAD approach for fabricating supercapacitor nanostructured electrodes can be exploited for the fabrication of a broad range of metal oxide materials.     

Nitrogen-Doped Porous Graphene Coated with Fe3O4 Nanoparticles for Advanced Supercapacitor Electrode Material with Improved Electrochemical Performance

With the increasing demand for high-performance energy storage devices, single materials of ordinary structures for electrode materials have become increasingly difficult to meet people's needs. Therefore, composites of inimitable structures have drawn considerable attention. In this work, nitrogen-doped porous graphene coated with Fe₃O₄ nanoparticles (NPGF) is prepared by an efficient and green pyrolysis method. Structural and compositional characterizations confirm that the NPGF nanohybrids possess uniformly distributed pore structure and quite pure composition which is free of any impurities. In addition, electrochemical characterization verifies the excellent electrochemical performance, such as high-specific capacitance (713 F g⁻¹ at 1 A g⁻¹), prominent rate capability (capacitance retention of 77.3% and 67.9% when the current density is increased respectively from 1 to 10 and 20 A g⁻¹), and outstanding cycling stability (capacitance retention of 94.3% after 3000 cycles). Such promising results suggest that the NPGF nanohybrids have great application prospects in future high-performance supercapacitors.     

Co3O4 Hollow Polyhedrons as Bifunctional Electrocatalysts for Reduction and Evolution Reactions of Oxygen

It is very important to exploit low‐cost and efficient oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalysts for the development of renewable‐energy conversion and storage techniques. Although much attention has been made to develop efficient catalysts for ORR and OER, it is still highly desired to create new bifunctional catalysts. In this study, Co₃O₄ hollow polyhedrons are synthesized as efficient bifunctional electrocatalysts for ORR and OER by simple one‐step annealing Co‐centered metal–organic frameworks (ZIF‐67). Due to the large specific surface areas and high porosity, the as‐prepared Co₃O₄ hollow polyhedrons exhibit excellent electrocatalytic activities for ORR and OER in alkaline media. Co₃O₄ hollow polyhedrons show higher peak current density (0.61 mA cm^?2) with four‐electron pathway than Co₃O₄ particles (0.39 mA cm^?2), better methanol tolerance and superior durability (82.6%) than commercial Pt/C electrocatalyst (58.6%) for ORR after 25 000 s. In addition, Co₃O₄ hollow polyhedrons also display excellent OER performances with smaller overpotential (536 mV) for 10 mA cm^?2 than Co₃O₄ particles (593 mV) and superior stability (86.5%) after 25 000 s. This facile one‐step strategy based on metal–organic frameworks self‐sacrificed templates can be used to develop the promising well‐defined porous hollow metal oxides electrode materials for energy conversion and storage technologies.     

Ultrasonic-assisted hydrothermal synthesis of cobalt oxide/nitrogen-doped graphene oxide hybrid as oxygen reduction reaction catalyst for Al-air battery

A persistent ultrasound-assisted hydrothermal method has been developed to prepare cobalt oxide incorporated nitrogen-doped graphene (Co₃O₄/N-GO) hybrids. The electrochemical behaviors and catalytic activity of the prepared hybrids have been systematically investigated as cathode materials for Al-air battery. The results show that ultrasonication can promote the yield ratio of Co₃O₄ from 63.1% to 70.6%. The prepared Co₃O₄/N-GO hybrid with ultrasonication exhibits better ORR activity over that without ultrasonication. The assembled Al-air battery using the ultrasonicated Co₃O₄/N-GO hybrid exhibited an average working voltage of 1.02 V in 4 M KOH electrolyte at 60 mA∙cm⁻², approximately 60 mV higher than that using hybrid without ultrasonication. This should be attributed to large number density of fine Co₃O₄ particles growing on the dispersed GO sheets under the persistent ultrasonication. The related ultrasonic mechanism has been discussed in details.     

Self-assembled 3D Co3O4-graphene frameworks with high lithium storage performance

Three-dimensional Co₃O₄-graphene frameworks (3D-CGFs) are prepared with a one-pot hydrothermal method. Co₃O₄ particles are in situ anchored on graphene sheets, and the resulting composite self-assembles into 3D architecture during the hydrothermal treatment. Scanning electron microscope, transmission electron microscope, powder X-ray powder diffraction, and Raman spectroscopy are employed to characterize the sample. When tested as anode materials for lithium-ion batteries, 3D-CGFs demonstrate remarkable electrochemical lithium storage properties, such as large and stable reversible capacity (>530 mAh g^?1 at 500 mA g^?1 over 300 cycles), good capacity retention (88 % retention after 300 cycles at 500 mA g^?1 compared with the 4th cycle), excellent high-rate performance (515 mAh g^?1 at 1 A g^?1), making it a promising candidate for high-performance anode materials, especially for high-rate lithium-ion batteries.     

Liquid precipitation synthesis of Co3O4 for high-performance electrochemical capacitors

The amorphous Co₃O₄ nanostructure, which adopted sodium hexametaphosphate as structure-directing agent, has been successfully synthesized in large scale via two steps: preparation of the precursor and the calcination process. The results of X-ray diffraction indicate that the prepared materials are mainly composed of Co₃O₄; the formless Co₃O₄ nanoplate with loose structures is observed by scanning electron microscopy. Cyclic voltammetry, chronopotentiometry, and electrochemical impedance measurements are applied in a mild aqueous electrolyte (2 mol L^?1 KOH) to investigate the performance of the Co₃O₄, which show a high specific capacitance (SC) of 482.61 F g^?1 at 5 mA cm^?2. Besides, the SC degradation is only 10.05 % after 250 continuous charge–discharge cycles at 5 mA cm^?2, indicating an excellent electrochemical stability. The improved performance is reasonably ascribed to their irregular structure for ionic transport during the electrochemical reaction, which presents as promising candidates for supercapacitors.     

High surface area monodispersed Fe3O4 nanoparticles alone and on physical exfoliated graphite for improved supercapacitors

Highly conductive, unsophisticated and easy to be obtained physical exfoliated graphite (PHG) supporting well dispersed magnetite, Fe₃O₄/PHG nanocomposite, has been prepared by a one-step chemical strategy and physico-chemical characterized. The nanocomposite, favoured by the a-polar nanoparticles (NPs) capping, results in a self-assembled monolayer of monodispersed Fe₃O₄, covering perfectly the hydrophobic surfaces of PHG. The nanocomposite as an electrode material was fabricated into a supercapacitor and characterized by cyclic voltammetry (CV) and galvanostatic charge–discharge measurements. It shows, after a suitable annealing, significant electrochemical properties (capacitance value of 787 F/g at 0.5 A g⁻¹ and a Fe₃O₄/PHG weight ratio of 0.31) and good cycling stability (retention 91% after 30,000 cycles). Highly monodispersed very fine Fe₃O₄ NPs, covered by organic chains, have been also synthesized. The high surface area Fe₃O₄ NPs, after washing to leave a low content of organic chains able to avoid aggregation without excessively affecting the electrical properties of the material, exhibit remarkable pseudocapacitive activities, including the highest specific capacitance over reported for Fe₃O₄ (300 F/g at 0.5 A g⁻¹).     

Converting of the 2D graphene to its 3D by chicken red blood cells as sheets separator for construction supercapacitor electrode

Here, we report on a facile green and scalable method for the fabrication of porous 3D graphene as a well-known carbon-based material used in many energy storage devices. Chicken red blood cells were used as sheets spacer and heteroatom sources in the construction of 3D graphene. First, the red blood cells were separated from the blood and mixed with graphene oxide. Then, the mixture was freeze-dried and carbonized at 700 °C. The resulted 3D graphene containing heteroatoms was used as a supercapacitor electrode modifier on a glassy carbon electrode and tested with various electrochemical techniques. The supercapacitor electrode showed a specific capacitance of 330 F g⁻¹ at a current density of 1 A g⁻¹, maximum power density of 1958 W kg⁻¹, and maximum energy density of 85 Wh kg⁻¹. Furthermore, the supercapacitive performances were tested in a two-electrode symmetrical system which exhibited a specific capacitance of 238 F g⁻¹ for 1 A g⁻¹. It also showed a power density of 2200 W kg⁻¹ and an appreciable energy density of 160 Wh kg⁻¹. The excellent electrochemical behavior of 3D graphene indicates the promising abilities of the composite for other applications such as biosensors, batteries, electrocatalysts, etc.     

Nanostructured transition metal oxides for aqueous hybrid electrochemical supercapacitors

In this paper, we wish to present an overview of the research carried out in our laboratories with low-cost transition metal oxides (manganese dioxide, iron oxide and vanadium oxide) as active electrode materials for aqueous electrochemical supercapacitors. More specifically, the paper focuses on the approaches that have been used to increase the capacitance of the metal oxides and the cell voltage of the supercapacitor. It is shown that the cell voltage of an electrochemical supercapacitor can be increased significantly with the use of hybrid systems. The most relevant associations are Fe₃O₄ or activated carbon as the negative electrode and MnO₂ as the positive. The cell voltage of the Fe₃O₄/MnO₂ device is 1.8 V and this value was increased to 2.2 V by using activated carbon instead of Fe₃O₄. These two systems have shown superior behavior compared to a symmetric MnO₂/MnO₂ device which only works within a 1 V potential window in aqueous K₂SO₄. Furthermore, the activated carbon/MnO₂ hybrid device exhibits a real power density of 605 W/kg (maximum power density =19.0 kW/kg) with an energy density of 17.3 Wh/kg. These values compete well with those of standard electrochemical double layer capacitors working in organic electrolytes. PACS 82.47.Uv; 82.45.Fk; 82.45.Yz     

Encapsulation of Co3O4 Nanoparticles Inside CeO2 Nanotubes: An Efficient Biocatalyst for the Ultrasensitive Detection of Ascorbic Acid

A quick and sensitive detection of ascorbic acid (AA) is essential in the fields of biosensing and disease diagnosis. In this work, an effective approach combined with electrospinning, chemical bath deposition, and calcination process is developed to encapsulate Co₃O₄ nanoparticle into CeO₂ nanotubes as efficient peroxidase mimics for the detection of AA. The peroxidase‐like catalytic activity of the as‐prepared Co₃O₄@CeO₂ nanotubes is much higher than that of individual Co₃O₄ nanofibers and CeO₂ nanotubes alone due to the synergistic effect between the two components. Owing to the superior catalytic efficiency of the prepared Co₃O₄@CeO₂ nanotubes, a colorimetric route for the rapid and accurate detection of AA with a detection limit of 0.73 × 10⁻⁹m with a wide linear range from 0 to 0.8 × 10⁻⁶m is demonstrated. This detection limit is much better than the previous reports based on the enzyme‐like catalytic systems. In addition, a good selectivity toward the detection of AA over amino acids, common ions, dopamine, and uric acid is achieved. This study offers a new approach for the fabrication of Co₃O₄@CeO₂ nanotubes as sensing platform toward the detection of AA, which presents promising potential applications in biosensing, environmental monitoring, and medical diagnostics.     

General Synthesis and Lithium Storage Properties of Metal Oxides/MnO2 Hierarchical Hollow Hybrid Spheres

Metal oxides/MnO₂ hierarchical hollow hybrid nanostructures have attracted significant attention because of their wide potential applications. However, the exploration of a general synthetic approach for fabricating hierarchical hollow hybrid nanostructures is still a great challenge. Herein, a “penetration‐carbonization and reduction‐coating–annealing” route is presented for the generalized synthesis of metal oxides/MnO₂ hierarchical hollow hybrid spheres, including NiO/MnO₂, Co₃O₄/MnO₂, and CuO/MnO₂. Because of the unique hierarchical hollow hybrid nanostructures, NiO/MnO₂ nanomaterials possess a desirable capacity (1520 mA h g⁻¹) and outstanding cyclic stability (909 mA h g⁻¹ at the 200th cycle) as Li‐ion battery anode materials. The work reported herein can not only pave the way for the generalized synthetic strategy of metal oxides/MnO₂ hierarchical hollow hybrid nanostructures, but also provide a promising application of NiO/MnO₂ nanomaterials for Li‐ion battery anode.