Facile synthesis and characterization of conducting polymer-metal oxide based core-shell PANI-Pr2O–NiO–Co3O4 nanocomposite: As electrode material for supercapacitor

Metal oxide nanoparticles and their composites with conducting polymers, specifically Polyaniline (PANI) were utilized for fabricating nanoscale supercapacitor (SC) electrode materials. In the present study, we have synthesized pristine Pr₂O₃, NiO, Co₃O₄ nanoparticles, binary PANI-Pr₂O₃, PANI-NiO, PANI-Co₃O₄, ternary Pr₂O₃–NiO–Co₃O₄, and quaternary PANI-Pr₂O₃–NiO–Co₃O₄ spherical core-shell nanocomposite using co-precipitation and ultra-sonication methods. The grown samples were characterized with different analytical techniques. The XRD pattern revealed that the as-synthesized products were crystalline with Pr₂O₃ hexagonal phase, NiO cubic phase, and Co₃O₄ cubic phase in pure and nanocomposites. The Williamson-Hall, Scherrer, and size-strain plot methods were employed to study the crystalline development and contribution of micro-strain. FTIR pattern exhibited the metal-oxygen and PANI bond vibrations. FE-SEM images shown the spherical core-shell shape morphology of quaternary nanocomposite. EDX evident the presence of praseodymium, cobalt, and nickel in synthesized samples. UV–vis spectroscopy confirmed the absorption in the visible region. The IV graphs showed a higher conductivity of quaternary nanocomposite. The cyclic voltammetry results revealed that the quaternary nanocomposite has a higher specific capacitance 500 Fg^-1 as compared to binary nanocomposites 134 F g^?1 (PANI-Pr₂O₃), 143 F g^?1 (PANI-Co₃O₄), 256 F g^?1 (PANI-NiO), and PANI (90.8 F g^?1) at a scan rate of 5 m Vs^?1. The GCD results also showed that the quaternary nanocomposite has a higher specific capacitance of 905 F g^?1 at current density 1 A g^?1 with maximum energy density and power density of 87.99 kWhkg^-1 and 2.6 k W kg^?1_, respectively. The EIS curve also confirmed that the quaternary nanocomposite has a lower polarization resistance (R_p) and solution resistance (R_s). The higher capacitance of quaternary nanocomposite can facilitate ion transfer, and the formation of its core-shell structure flourish to enhance surface-dependent electrochemical properties. Furthermore, this study gives a novel research idea to manufacture electrode materials for supercapacitors.     

Solution growth of NiO nanosheets supported on Ni foam as high-performance electrodes for supercapacitors

Well-aligned nickel oxide (NiO) nanosheets with the thickness of a few nanometers supported on a flexible substrate (Ni foam) have been fabricated by a hydrothermal approach together with a post-annealing treatment. The three-dimensional NiO nanosheets were further used as electrode materials to fabricate supercapacitors, with high specific capacitance of 943.5, 791.2, 613.5, 480, and 457.5 F g^-1 at current densities of 5, 10, 15, 20, and 25 A g^-1, respectively. The NiO nanosheets combined well with the substrate. When the electrode material was bended, it can still retain 91.1% of the initial capacitance after 1,200 charging/discharging cycles. Compared with Co₃O₄ and NiO nanostructures, the specific capacitance of NiO nanosheets is much better. These characteristics suggest that NiO nanosheet electrodes are promising for energy storage application with high power demands.     

Comparison of lithium nickel cobalt oxides synthesized from NiO,Co3O4, and LiOH·H2O or Li2CO3 by solid-state reaction method

LiNi_1?yCo_yO₂ (y = 0.1, 0.3 and 0.5) cathode materials were synthesized by the solid-state reaction method at different temperatures from LiOH·H₂O, NiO and Co₃O₄ and from Li₂CO₃, NiO and Co₃O₄ as the starting materials. The physical and electrochemical properties of the synthesized samples were then compared. Among LiNi_1?yCo_yO₂ (y = 0.1, 0.3 and 0.5) synthesized for 40 h from LiOH·H₂O, NiO and Co₃O₄, and from Li₂CO₃, NiO and Co₃O₄, LiNi_0.5Co_0.5O₂ synthesized from Li₂CO₃, NiO and Co₃O₄ at 800 °C has relatively large first discharge capacity and relatively good cycling performance. This sample is considered the best one with relatively good electrochemical properties.     

Carbon nanotubes branch on cobalt oxide nanowires core as enhanced high-rate cathodes of alkaline batteries

Directional synthesis of carbon/metal oxide core-branch arrays is of great importance for development of advanced high-rate alkaline batteries. In this work, we report a facile hydrothermal-chemical vapor deposition (CVD) method for controllable fabrication of Co₃O₄ @CNTs core-branch arrays. Interestingly, free-standing Co₃O₄ core nanowires are intimately decorated by cocoon-like branch CNTs with diameters of 20–30?nm, which act as a highly conductive network and structure stabilizer. The electrochemical performance of the designed Co₃O₄ @CNTs core-branch arrays are tested as cathodes of alkaline batteries. Arising from enhanced electrical conductivity, larger surface area and improved structural stability, the Co₃O₄ @CNTs arrays show superior high-rate electrochemical performance with a higher capacity (116 mAh g^?1 at 2.5?A?g^?1), lower polarization and better cycling stability than the pure Co₃O₄ nanowires arrays (76 mAh g^?1 at 2.5?A?g^?1). Our directional composite strategy can be extended to preparation of other carbon-based core-branch arrays for applications in electrochemical batteries and catalysis.     

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.     

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.     

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.     

Facile synthesis of In2O3 nanoparticles with high response to formaldehyde at low temperature

In₂O₃ nanoparticles with uniform particle size (10-25 nm) were obtained using the facile precipitation strategy at room temperature with following calcined treatment. The gas-sensing performance of In₂O₃ nanoparticles with different calcined temperatures was investigated. The results demonstrated that the In₂O₃ nanoparticles calcined at 500°C exhibited highest sensing response (R_a/R_g = 68.1) to 10 ppm HCHO at 100°C with good selectivity, stability, reproducibility, and ultra-low limit of detection (1 ppm). The results of XPS, UV, and other characterizations indicated that In₂O₃-500 possessed the most absorbed oxygen species, the highest carrier mobility, and lowest band gap energies. Our work offers new insights into the development of sensing materials to the detection of volatile organic compounds (VOCs).     

Fabrication of carbon encapsulated Co3O4 nanoparticles embedded in porous graphitic carbon nanosheets for microwave absorber

Carbon-encapsulated Co₃O₄ nanoparticles homogeneously embedded 2D (two-dimensional) porous graphitic carbon (PGC) nanosheets were prepared by a facile and scalable synthesis method. With assistance of sodium chloride, the Co₃O₄ nanoparticles (10–20 nm) with magnetic loss were well encapsulated by onion-like carbon shells homogeneously embedded porous graphitic carbon nanosheets (thickness of less than 50 nm) with dielectric loss. In the architecture, the well impedance matching for microwave absorption can be obtained by the synergetic effect between Co₃O₄ nanoparticles and encapsulated porous carbon nanosheets. The minimum reflection loss value of −32.3 dB was observed at 11.4 GHz with a matching thickness of 2.3 mm for 2D Co₃O₄@C@PGC nanosheets. The 2D Co₃O₄@C@PGC nanosheets can be used as a kind of candidate for microwave absorbing materials.     

Constructing bilayer sensors with Co-MOF-derived Co3O4 porous sensing films and SnO2 catalytic overlayers to enhance room-temperature triethylamine sensing performance

Gas sensors with good repeatability and controllable fabrication method are extremely desired for practical applications. Co-MOF-derived Co₃O₄ is a promising gas-sensing material candidate because of its large surface area, ultrahigh porosities, and abundant oxygen defects. However, the advantages of Co-MOF precursor were limited by the traditional sensor fabrication methods. Moreover, the high resistance and poor surface activity of Co₃O₄ resulted in low gas-sensing performance at room temperature (RT). To overcome these challenges, in-situ sensors based on Co₃O₄ porous films with controlled nanoscale thickness were directly prepared on ceramic substrates by using Co-MOF films as precursors. To further improve the conductivity, SnO₂ catalytic overlayers were introduced on top of Co₃O₄ sensors to construct SnO₂/Co₃O₄ bilayer sensors, which were promising for triethylamine (TEA) detection at RT. As a result, the optimized SnO₂/Co₃O₄ sensor exhibited a fast response/recovery rate (11 s/16 s), high selectivity, and a satisfactory sensitivity (150%) to TEA at RT. The enhanced gas-sensing performance could be attributed to the unique bilayer structures, improved conductivity, and synergistic effects of the SnO₂ catalytic overlayers and Co₃O₄ sensing layers.     

Preparation of scale-like nickel cobaltite nanosheets assembled on nitrogen-doped reduced graphene oxide for high-performance supercapacitors

Ultrathin scale-like nickel cobaltite (NiCo₂O₄) nanosheets supported on nitrogen-doped reduced graphene oxide (N-rGO) are successfully synthesized through a facile co-precipitation of Ni²⁺ and Co²⁺ in the presence of sodium citrate and hexamethylenetetramine and subsequent calcination treatment. The composition and morphology of NiCo₂O₄ nanosheets@nitrogen-doped reduced graphene oxide (denoted as NiCo₂O₄ NSs@N-rGO) were characterized by Scanning electron microscope, Transmission electron microscope, X-ray diffraction, Raman spectra, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller and thermogravimetric analysis. The thickness of NiCo₂O₄ nanosheets anchored on the reduced graphene oxide is around 4 nm. The capacitance of NiCo₂O₄ NSs@N-rGO is evaluated by cyclic voltammogram and galvanostatic charge/discharge with the result that the NiCo₂O₄ NSs@N-rGO could deliver a specific capacitance of 1540 F g⁻¹ after 1000 cycles at 10 A g⁻¹.     

Magnetic reduced graphene oxide nanocomposite as an effective electromagnetic wave absorber and its absorbing mechanism

A magnetic reduced graphene oxide (MRGO) composite consisting of graphene oxide and Fe₃O₄ particles in the range of 5–20 nm has been prepared by the one-pot hydrothermal process. RGO nanosheets provide flexible substrates for nanoparticle decoration, while Fe₃O₄ nanoparticles can also effectively prevent nanosheets to restack each other. Compared with previously literature, the synthesized RGO-Fe₃O₄ composite exhibits excellent electromagnetic wave absorption. The minimum reflection loss (R_L) value of −49.05 dB has been observed at 14.16 GHz with a thickness of 2.08 mm. The absorption bandwidth (R_L<−10 dB) corresponding to the minimum R_L is 4.60 GHz. The electromagnetic wave absorption properties of the RGO-Fe₃O₄ composite have been interpreted through the quarter-wavelength matching model.     

Facile synthesis of NiMn2O4 nanosheet arrays grown on nickel foam as novel electrode materials for high-performance supercapacitors

Nanostructured spinel NiMn₂O₄ arrays have been fabricated by a facile hydrothermal approach and further investigated as binder-free electrode for high-performance supercapacitors. Compared with Mn₃O₄, NiMn₂O₄ exhibited higher specific capacitances (662.5 F g⁻¹ and 370.5 F g⁻¹ in different electrolytes at the current density of 1 A g⁻¹) and excellent cycling stability (~96% capacitance retention after 1000 cycles) in a three-electrode system. Such a novel microstructure grown directly on the conductive substrate provided sufficient active sites for redox reaction resulting in their enhanced electrochemical behaviors. Their improved performances suggested that ultrathin sheet-like NiMn₂O₄ arrays on Ni foam substrate were a promising electrode material for supercapacitors.     

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.     

Electrochemical properties of cathode materials LiNi1−y Co y O2 synthesized using various starting materials

LiNi_1−y Co _y O₂ samples were synthesized at 800 °C and 850 °C, by the solid-state reaction method, using the starting materials LiOH·H₂O, Li₂CO₃, NiO, NiCO₃, Co₃O₄ and CoCO₃. The LiNi_1−y Co _y O₂ synthesized using Li₂CO₃, NiO and Co₃O₄ exhibited the α-NaFeO₂ structure of the rhombohedral system (space group ). As the Co content increased, the lattice parameters a and c decreased. The reason is that the radius of the Co ion is smaller than that of the Ni ion. The increase in c/a shows that a two-dimensional structure develops better as the Co content increases. The LiNi_0.7Co_0.3O₂ synthesized at 800 °C using LiOH · H₂O, NiO and Co₃O₄ exhibited a larger first discharge capacity of 162 mAh g⁻¹ than the other samples. The cycling performances of the samples with the first discharge capacity larger than 150 mAh g⁻¹ were investigated. LiNi_0.9Co_0.1O₂ synthesized at 850 °C using Li₂CO₃, NiO and Co₃O₄ showed excellent cycling performance. Samples with larger first discharge capacity will have a greater tendency for lattice destruction due to expansion and contraction during intercalation and deintercalation, than samples with smaller first discharge capacity. As the first discharge capacity increases, the capacity fading rate thus increases.     

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.     

Preparation and capacitance performance of nitrided lithium titanate nanoarrays

Nitrided lithium titanate (N-Li₄Ti₅O₁₂) nanoarrays with nanowire and nanotube structures were designed as the electrode materials of lithium-ion supercapacitor for electrochemical energy storage. Two types of TiO₂ nanoarrays were used as the precursor which involved TiO₂ nanowire array prepared by hydrothermal process and TiO₂ nanotube array prepared by anodization process. Li₄Ti₅O₁₂ nanoarrays were formed through hydrothermal reaction or sonochemical reaction of TiO₂ nanoarrays with lithium hydroxide and then calcination treatment process. Finally, N-Li₄Ti₅O₁₂ nanoarrays were formed through nitriding treatment of Li₄Ti₅O₁₂ using ammonia as nitrogen source. The electroactive N-Li₄Ti₅O₁₂ nanowire array and nanotube array exhibited the specific capacitance of 607.2 F g⁻¹ and 814.4 F g⁻¹ at a current density of 1 A g⁻¹, respectively. The corresponding capacitance retention was determined to be 92.1% and 94.2% after 1000 cycles at high current density of 5 A g⁻¹. The corresponding capacitance still kept 182.9 and 352.1 F g⁻¹ at much higher current density of 20 A g⁻¹, presenting reasonable rate capability for N-Li₄Ti₅O₁₂ nanoarrays. The improved capacitance performance of N-Li₄Ti₅O₁₂ nanotube array was ascribed to the more amount of TiN and more accessible nanotube surface area, which contributed to the improved conductivity and fast diffusion of electrolyte ions on the surface of electrode. Both N-Li₄Ti₅O₁₂ nanowire array and nanotube array with well-aligned integrative structure exhibited an excellent cycling stability during continuous charge/discharge process. Well-designed N-Li₄Ti₅O₁₂ nanoarrays with high capacitance, good cycling stability and rate capability presented the promising application as feasible electrode materials of lithium-ion supercapacitors for the energy storage.     

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.     

In-situ synthesis of reduced graphene oxide wrapped Mn3O4 nanocomposite as anode materials for high-performance lithium-ion batteries

We report a novel in-situ symbiosis method to prepare reduced graphene oxide wrapped Mn₃O₄ nanoparticles (rGO/Mn₃O₄) with uniform size about 50 nm as anodes for lithium-ion batteries (LIBs), which can simplify the preparation process and effectively reduce pollution. The rGO/Mn₃O₄ nanocomposite exhibited a reversible specific capacity of 795.5 mAh g^?1 at 100 mA g^?1 after 200 cycles (capacity retention: 87.4%), which benefits from the unique structural advantages and the synergistic effect of rGO and Mn₃O₄. The Mn₃O₄ nanoparticles encapsulated among the rGO nanosheets exhibited good electrochemical activity, and the multilayer wrinkled rGO sheets provided a stable 3D conduction channel for Li⁺/e^? transport. The rGO/Mn₃O₄ nanocomposite is a promising anode candidate for advanced LIBs with excellent cycling performance and rate performance. Furthermore, this new preparation method can be extended to green and economical synthesis of advanced graphene/manganese-based nanocomposites.     

Effective hydrolysis of sodium borohydride driven by self-supported cobalt oxide nanorod array for on-demand hydrogen generation

Hydrogen storage, distribution and controlled release are of important concerns for hydrogen based economy. Sodium borohydride (NaBH₄) is one of the mostly studied chemical hydrides used for hydrogen storage and generation. However, it requires efficient catalysts to accelerate its dehydrogenation for controllable hydrogen production. In this paper, we demonstrate that the dehydrogenation of NaBH₄ in alkaline solutions can be driven by self-supported cobalt oxide nanorod array on Ti sheet (Co₃O₄ NA/Ti). Such Co₃O₄ NA/Ti shows high catalytic performance with a maximum hydrogen generation rate of 1940 mL/min/g_Co3O4 and an activation energy of 59.84 kJ/mol under ambient condition. Moreover, this catalyst exhibits no mass or activity loss even after 5 cycles with an obvious advantage of easy separation from the fuel solution. This development offers us a cost-effective and recyclable catalytic material toward hydrolytic hydrogen production for applications.