Fabrication and characterization of monodispersed Mn0.8Ni0.2Co2O4 mesoporous microspheres for supercapacitor application

The monodispersed Ni doped MnCo₂O₄ mesoporous microspheres were synthesized through a simple ammonium bicarbonate-assisted solvothermal route. The spinel-type crystal structure with a lattice parameter of 8.199?Å for Mn_0.8Ni_0.2Co₂O₄ composition was obtained by using X-ray diffraction analysis. The Brunauer?Emmett?Teller (BET) specific surface area of the sample was found to be 75.78?m² g^?1 with an average pore diameter of 9.88?nm. Electron microscopy studies revealed that the stable mesoporous microspheres are constituted by well-connected aggregates of nanoparticles. The influence of Ni doping on the pseudo-capacitance of MnCo₂O₄ electrode was investigated by means of cyclic voltammetry in 6?M KOH electrolyte. We found that the spinel-type Mn_0.8Ni_0.2Co₂O₄ mesoporous microspheres exhibit specific capacitances of 1822 F g^?1 at a scan rate of 5?mV/s. Furthermore, the electrochemical impedance spectroscopy analysis revealed the low resistance and good electrochemical stability of the sample.     

Synthesis and magnetic properties of monodisperse CoFe2O4 nanoparticles coated by SiO2

The monodisperse CoFe₂O₄ nanoparticles were synthesized by a modified chemical coprecipitation method. Coating SiO₂ on the surface of the CoFe₂O₄ nanoparticles was carried out to keep single domain particles non-interacting with cubic magnetocrystalline anisotropy. The Curie temperatures (T_c) of the monodisperse CoFe₂O₄ nanoparticles can be accurately measured because the SiO₂ shells prevented the aggregation and growth of nanoparticles at high temperature. The magnetic properties of the CoFe₂O₄@SiO₂ nanoparticles with core-shell structure in a wide temperature range (300～950?K) were investigated. It is remarkable that the coercive field (H_c) of CoFe₂O₄ nanoparticles increased from about 760?Oe to 1806?Oe after being coated with SiO₂, which increased by 137.6% compared to the uncoated samples at 300?K. The saturation magnetization (M_s) of the CoFe₂O₄@SiO₂ nanoparticles is 34.59?emu/g, which is about 52% of the naked CoFe₂O₄ nanoparticles value (66.51?emu/g) at 300?K. The hysteresis loops of the CoFe₂O₄@SiO₂ nanoparticles showed an orderly magnetic behavior at high temperature, such as the M_s, remanence magnetization (M_r) and H_c decreased as temperature increasing, being equal to zero near T_c. This is a good indication that the CoFe₂O₄@SiO₂ nanoparticles are suitable for a wide variety of technological applications at high temperature.     

Rapid microwave-assisted synthesis of graphene nanosheet/Co3O4 composite for supercapacitors

Graphene nanosheet (GNS)/Co₃O₄ composite has been rapidly synthesized by microwave-assisted method. Field emission scanning electron microscopy and transmission electron microscopy observation reveals the homogeneous distribution of Co₃O₄ nanoparticles (3-5 nm in size) on graphene sheets. Electrochemical properties are characterized by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy. A maximum specific capacitance of 243.2 F g⁻¹ has been obtained at a scan rate of 10 mV s⁻¹ in 6 M KOH aqueous solution for GNS/Co₃O₄ composite. Furthermore, the composite exhibits excellent long cycle life along with ∼95.6% specific capacitance retained after 2000 cycle tests.     

Structure and magnetic properties of multi-morphological CoFe2O4/CoFe nanocomposites by one-step hydrothermal synthesis

Multi-morphological CoFe₂O₄/CoFe nanocomposites have been synthesized using a facile hydrothermal process. The effects of hydrazine hydrate amount during hydrothermal reaction on the structure and magnetic property of the specimens were studied. With increasing hydrazine hydrate amount, the CoFe₂O₄ transformed to CoFe and the morphology of the specimen changed from granular particles to faceted particles. The saturation magnetization monotonically increased and the coercivity monotonically decreased with increasing hydrazine hydrate amount. The magnetic interactions, determining the magnetic properties of the composites, result from the dominant dipole coupling and relative weak exchange coupling between CoFe₂O₄ and CoFe nanoparticles. The CoFe₂O₄/CoFe nanocomposite prepared with 2?mL hydrazine hydrate exhibited the optimal magnetic properties, with the saturation magnetization of 81?emu/g and coercivity of 636?Oe.     

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.     

High capacity three-dimensional ordered macroporous CoFe2O4 as anode material for lithium ion batteries

A three-dimensional ordered macroporous (3DOM) cobalt ferrite (CoFe₂O₄) was prepared using polystyrene (PS) colloidal crystal template. The scanning electron microscopy (SEM) and the transmission electron microscopy (TEM) micrographs showed that the as-prepared CoFe₂O₄ material had a typical 3DOM structure, which was constructed with about 130 nm-sized macropores and 10-20 nm-sized walls. The obtained CoFe₂O₄ material had a specific surface area of 66.67 m² g⁻¹, and could deliver a relatively high capacity of 702 mAh g⁻¹ (about double that of graphite) at a current density of 0.2 mA cm⁻² after 30 cycles. Owing to the 3DOM nanoarchitecture, the as-prepared CoFe₂O₄ electrode exhibited a good rate performance. The results suggest a promising application of the 3DOM CoFe₂O₄ as anode material for lithium ion batteries.     

MnCo2O4 nanospheres for improved lithium storage performance

Mesoporous MnCo₂O₄ nanospheres with an average diameter of approximately 480?nm have been synthesized by a polyvinyl pyrrolidone (PVP)-assisted solvothermal method followed by thermal annealing. MnCo₂O₄ nanospheres consist of many nanoparticles having sizes in range of 20–50?nm, the specific area of the sample being 24.4?m² g^?1. When used as the anode material for lithium ion batteries, the mesoporous MnCo₂O₄ nanospheres show not only an excellent cycling stability, but also an outstanding rate capability. More specially, the discharge capacities of 749.1 and 629.6?mA?h?g^?1 can be retained at current densities of 200 and 400?mA?g^?1 after 50 cycles, respectively. In addition, the average discharge capacities of 1013.8, 827.1, 770.6, 733.3, 697.3, 651.4 and 522.4?mA?h?g^?1 could be observed at current densities of 100, 200, 400, 600, 800, 1000 and 2000?mA?g^?1, respectively. The improved cycling stability and rate capability can be ascribed to two unique structural features of mesoporous MnCo₂O₄ nanospheres: namely, the mesoporous nature of electrode materials which can help to reduce the volume variation during repeated lithiation/delithiation processes, and the nanostructure which can provide a shortened Li⁺ transmission path. The current synthesis approach can be easily spread to prepare other binary metal oxides, including Co-free anode materials.     

Ordered mesoporous Co3O4 nanospheres / reduced graphene oxide composites for rutin detection

The ordered mesoporous Co₃O₄ nanospheres encapsulated with reduced graphene oxide (denoted as meso-Co₃O₄ / RGO) were synthesized via electrostatic interaction and firstly for the electrochemical detection of rutin with good sensing effects. The resultant meso-Co₃O₄ / RGO nanocatalyst not only possesses more active sites due to the high surface area deriving from the mesoporous structure, but also has benign conductibility due to the presence of RGO, both of which enhance the sensing properties for the electrochemical detection of rutin. The developed sensor displays low detection limit (0.03?μM) and large sensitivity (74.85?μA?μM^?1 cm^?2). Besides, the rutin sensor possesses good selectivity, stability and reproducibility.     

Template-free synthesis of rGO decorated hollow Co3O4 nano/microspheres for ethanol gas sensor

A series of the rGO decorated hollow Co₃O₄ spheres were fabricated via a solvothermal-combination-calcination process with no template. The morphological and crystal structure analysis were carried out through several characterization techniques, including SEM, TEM, XRD and XPS. The results indicate that the hollow Co₃O₄ microspheres were assembled by nanoparticles with an average diameter of 20?nm and adhered uniformly on rGO nanosheets. According to the gas sensing test, 3?wt% rGO-Co₃O₄ hollow spheres showed a higher substantial response to 100?ppm ethanol reaching up to 13.5, which is 3.7 times than the pristine Co₃O₄ at 180?°C. In addition, it also exhibited short response-recovery time and good reproducibility. The enhanced sensing properties probably come from the synergy between rGO and Co₃O₄, mesoporous structure, and its high specific surface area (108.2?m²/g). This facile method could be used for the fabrication of many advanced materials for sensors, capacitors and electrodes.     

Hydrothermal synthesis of nanostructured Co3O4 materials under pulsed magnetic field and with an aging technique, and their electrochemical performance as anode for lithium-ion battery

Co₃O₄ nanoparticle samples were prepared as anode materials for lithium-ion batteries by the hydrothermal synthesis method without magnetic field (Co₃O₄-0T), under pulsed magnetic field (Co₃O₄-4T), and by using an aging technique (Co₃O₄-Aging), respectively. The morphology and structural properties of the Co₃O₄ nanoparticles were investigated by field-emission scanning electron microscopy (FE-SEM), and X-ray diffraction (XRD). FE-SEM measurements demonstrated that the Co₃O₄ sample formed under a 4 T magnetic field consisted of large agglomerated spheres composed of numerous quasi-spherical nanoparticles with a typical diameter of ∼25 nm and had more compact and smoother surfaces compared to a reference sample prepared without magnetic field. After the aging process, large Co₃O₄ hollow spheres composed of numerous spherical nanoparticles with a typical diameter of ∼20 nm were formed. Electrochemical measurements showed that Co₃O₄ materials prepared by the aging technique (Co₃O₄-Aging) yielded the best electrochemical performance compared with the other samples. Capacities were maintained at 274, 348, and 407 mAh g⁻¹ up to 100 cycles for the Co₃O₄-0T, Co₃O₄-4T, and Co₃O₄-Aging materials, which are about 26, 27, and 30% of initial discharge capacities, respectively. The capacity loss is in the order of Co₃O₄-Aging < Co₃O₄-4T < Co₃O₄-0T. Thus, the morphology affects not only the discharge capacity, but also the cycling stability of Li-ion batteries.     

Formation of CoFe2O4/PVA-SiO2 nanocomposites: Effect of diol chain length on the structure and magnetic properties

The paper presents the influence of diol (1,2-ethanediol, 1,2-propanediol, 1,3-propanediol and 1,4-butanediol) on the formation of magnetic crystalline cobalt ferrite embedded in polyvinyl alcohol-silica hybrid matrix at 200?°C. Formation of crystalline oxides (CoFe₂O₄, Co₃O₄ and Co₂SiO₄) was studied by X-ray diffraction and Fourier transformed infrared spectroscopy. The effect of annealing temperature and diol chain length on the cobalt ferrite nanocrystallites size was investigated. Using transmission electron microscopy, the size and shape of particles obtained at 200?°C were recorded and compared to those obtained by annealing at 500, 800 and 1100?°C. The saturation magnetization (M_s) and coercive field were calculated from the magnetic hysteresis loops of nanocomposites. The M_s was influenced by the particle size and crystallinity only for nanocomposites annealed at 800 and 1100?°C, when the magnetic domains started to form and to be larger than the critical particle size. The diols used in the synthesis influence both the oxidic phase formation and its properties.     

Hydrothermal synthesis of Co3O4 microspheres as anode material for lithium-ion batteries

Co₃O₄ microspheres were synthesized in mass production by a simple hydrothermal treatment. One micrometer-sized spherical particles with well-crystallization could be obtained by XRD and SEM. Higher specific surface area (93.4 m² g⁻¹) and larger pore volume (78.4 cm³ g⁻¹) by BET measurements offered more interfacial bondings for extra sites of Li⁺ insertion, which resulted in the anomalous large initial irreversible capacity and capacity cycling loss due to SEI film formation. The capacity retention of Co₃O₄ microspheres involved first forming acted as Li-ion anode material is almost above 90% from 12th cycle and it retain lithium storage capacity of 550.2 mAh g⁻¹ after 25 cycles, which show good long-life stability. The electrochemical impedance spectroscopy (EIS) tests before and after cyclic voltammetry measurements and charge-discharge experiments were carried out and the corresponding D_Li values were also calculated. The relationship of the ac impedance spectra and the cycling behaviors was discussed. It is found that the decrease of capacity results from the larger Li⁺ charge-transfer impedance and the lower lithium-diffusion processes on cycling, which is in very good agreement with the electrochemical behaviors of Co₃O₄ electrode.     

Ordered CoFe2O4 nanowire arrays with preferred crystal orientation and magnetic anisotropy

CoFe₂O₄ nanowire arrays were fabricated by electrodeposition of Fe²⁺ and Co²⁺ into anodic aluminum oxide (AAO) templates and further oxidization. The phase structure of the nanowires is cubic spinel-type, and the XRD result exhibits perfect preferred crystallite orientation along the nanowire axes. Compared with CoFe₂O₄ nanowire arrays synthesized by other methods, the magnetic hysteresis loops demonstrate that the arrays of nanowires exhibit uniaxial magnetic anisotropy with easy magnetization direction along the nanowire axes owing to the large shape anisotropy. This approach provides a facile technology to fabricate oxide nanowires with uniaxial magnetic anisotropy.     

Microwave assisted hydrothermal synthesis of (Fe,Co)3O4 nanoparticles in the presence of surfactants and effects of Co/Fe ratio on microstructure and magnetism

Microstructure and magnetic properties of nanoparticles can be tailored by optimising the synthesis procedure and changing chemical composition. In this study, a two-step procedure, i.e., coprecipitation in the presence of PEG 300 followed by microwave assisted (MW) hydrothermal synthesis, was introduced to obtain Co_xFe_3-xO₄ (x?=?0, 0.1 and 0.2) nanoparticles. It was found that with the increase of Co content, particle/crystallite size increased, with significant change of coercivity (H_c). The mixed samples of Co_xFe_3-xO₄ (x?=?0.1 and 0.2) were magnetically harder in comparison with Fe₃O₄. Тhe H_c of Fe₃O₄ was 91?Oe, while for Co_0.10Fe_2.90O₄ and Co_0.20Fe_2.80O₄, H_c was 256?Oe and 1070?Oe, respectively. Saturation magnetisation (M_s) of mixed samples also increased up to 6% compared to Fe₃O₄. A special effort was devoted to study the effects of introducing different surfactants (PEG 300, PEG 4000 or SDS) during the synthesis procedure in order to improve morphological and microstructural properties of CoFe₂O₄ nanoparticles. The influence of surfactants on physical/chemical properties of nanoparticles is discussed.     

Achieving ultra-high electromagnetic wave absorption by anchoring Co0.33Ni0.33Mn0.33Fe2O4 nanoparticles on graphene sheets using microwave-assisted polyol method

The Co_0.33Ni_0.33Mn_0.33Fe₂O₄/graphene nanocomposite for electromagnetic wave absorption was successfully synthesized from metal chlorides solutions and graphite powder by a simple and rapid microwave-assisted polyol method via anchoring the Co_0.33Ni_0.33Mn_0.33Fe₂O₄ nanoparticles on the layered graphene sheets. The Fe³⁺, Co²⁺, Ni²⁺ and Mn²⁺ ions in the solutions were attracted by graphene oxide obtained from graphite and converted to the precursors Fe(OH)₃, Co(OH)₂, Ni(OH)₂, and Mn(OH)₂ under slightly alkaline conditions. After the transformations of the precursors to Co-Ni-Mn ferrites and conversion of graphene oxide to graphene under microwave irradiation at 170?°C in just 25?min, the Co_0.33Ni_0.33Mn_0.33Fe₂O₄/graphene nanocomposite was prepared. The composition and structure of the nanocomposite were characterized by X-ray diffraction (XRD), inductive coupled plasma emission spectroscopy (ICP), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy (RS), transmission electron microscopy (TEM), etc. It was found that with the filling ratio of only 20?wt% and the thickness of 2.3?mm, the nanocomposite showed an ultra-wide effective absorption bandwidth (less than ?10?dB) of 8.48?GHz (from 9.52 to 18.00?GHz) with the minimum reflection loss of ??24.29?dB. Compared to pure graphene sheets, Co_0.33Ni_0.33Mn_0.33Fe₂O₄ nanoparticles and the counterparts reported in literature, the nanocomposite exhibited much better electromagnetic wave absorption, mainly attributed to strong wave attenuation, as a result of synergistic effects of dielectric loss, conductive loss and magnetic loss, and to good impedance matching. In view of its thin thickness, light weight and outstanding electromagnetic wave absorption property, the nanocomposite could be used as a very promising electromagnetic wave absorber.     

Ultrathin CeO2 coating for improved cycling and rate performance of Ni-rich layered LiNi0.7Co0.2Mn0.1O2 cathode materials

In this study, we have successfully coated the CeO₂ nanoparticles (CeONPs) layer onto the surface of the Ni-rich layered LiNi_0.7Co_0.2Mn_0.1O₂ cathode materials by a wet chemical method, which can effectively improve the structural stability of electrode. The X-ray powder diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS) are used to determine the structure, morphology, elemental composition and electronic state of pristine and surface modified LiNi_0.7Co_0.2Mn_0.1O₂. The electrochemical testing indicates that the 0.3?mol% CeO₂-coated LiNi_0.7Co_0.2Mn_0.1O₂ demonstrates excellent cycling capability and rate performance, the discharge specific capacity is 161.7?mA?h?g^?1 with the capacity retention of 86.42% after 100 cycles at a current rate of 0.5?C, compared to 135.7?mA?h?g^?1 and 70.64% for bare LiNi_0.7Co_0.2Mn_0.1O₂, respectively. Even at 5?C, the discharge specific capacity is still up to 137.1?mA?h?g^?1 with the capacity retention of 69.0%, while the NCM only delivers 95.5?mA?h?g^?1 with the capacity retention of 46.6%. The outstanding electrochemical performance is assigned to the excellent oxidation capacity of CeO₂ which can oxidize Ni²⁺ to Ni³⁺ and Mn³⁺ to Mn⁴⁺ with the result that suppress the occurrence of Li⁺/Ni²⁺ mixing and phase transmission. Furthermore, CeO₂ coating layer can protect the structure to avoid the occurrence of side reaction. The CeO₂-coated composite with enhanced structural stability, cycling capability and rate performance is a promising cathode material candidate for lithium-ion battery.     

Ag@CoFe2O4/Fe2O3 nanorod arrays on carbon fiber cloth as SERS substrate and photo-Fenton catalyst for detection and degradation of R6G

In this study, Ag nanoparticles loaded CoFe₂O₄/Fe₂O₃ nanorod arrays on carbon fiber cloth have been successfully fabricated by a hydrothermal route followed by a calcination treatment and photochemical reduction process. The as-prepared composite has been characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS). The obtained Ag@CoFe₂O₄/Fe₂O₃ nanorod arrays show excellent SERS performance, which provides enhancement factors (EF) as high as about 1.2 × 10⁸ for Rhodamine 6G (R6G). The SERS signals collected over a 20?µm × 20?µm area show relative standard deviation lower than 12%, suggesting good SERS signal uniformity. In addition, the Ag@CoFe₂O₄/Fe₂O₃ nanorod arrays can be used as an effective photo-Fenton catalyst photocatalytical degradation of R6G. It was found that 99.15% of R6G can be degraded in an hour. This bifunctional composite that can act both as SERS substrates and as photo-Fenton catalyst would facilitate the cleaning and recycling of SERS substrates for reusing through a photocatalytic process, as well as facilitate the integration of rapid detection and effective degradation of organic pollutants.     

Highly reversible Co3O4/graphene hybrid anode for lithium rechargeable batteries

A Co₃O₄/graphene hybrid material was fabricated using a simple in situ reduction process and demonstrated as a highly reversible anode for lithium rechargeable batteries. The hybrid is composed of 5 nm size Co₃O₄ particles uniformly dispersed on graphene, as observed by transmission electron microscopy, atomic force microscopy, Raman spectroscopy and X-ray diffraction analysis. The Co₃O₄/graphene anode can deliver a capacity of more than 800 mA h g⁻¹ reversibly at a 200 mA g⁻¹ rate in the voltage range between 3.0 and 0.001 V. The high reversible capacity is retained at elevated current densities. At a current rate as high as 1000 mA g⁻¹, the Co₃O₄/graphene anode can deliver more than 550 mA h g ⁻¹, which is significantly higher than the capacity of current commercial graphite anodes. The superior electrochemical performance of the Co₃O₄/graphene is attributed to its unique nanostructure, which intimately combines the conductive graphene network with uniformly dispersed nano Co₃O₄ particles.     

Study of crystal structure,dielectric, magnetic and magnetoelecrtic properties of xCoFe2O4-(1-x)Na0.5Bi0.5TiO3 composites

Multiferroic composites of spinel ferrite and ferroelectric xCoFe₂O₄ – (1-x)Na_0.5Bi_0.5TiO₃ (with x = 0.10,0.30,0.50) were efficiently prepared by standard solid state reaction mechanism. X-ray diffractometer was used to analyze crystal structure of the prepared composites. The observed XRD patterns of the composites comprise peaks of both the phases i.e. ferrite and ferroelectric, with no sign of secondary peaks. Rietveld refinement of XRD data further confirms the coexistence of these two phases with cubic (Fd3m) and rhombohedral (R3c) symmetry corresponding to ferrite and ferroelectric phase respectively. The 3-dimensional overview of crystal structure of pure CoFe₂O₄ and Na_0.5Bi_0.5TiO₃ and of composite 0.50CoFe₂O₄?0.50Na_0.5Bi_0.5TiO₃ is generated by using refined parameters. The dielectric constant (ε´) and dielectric loss (tanδ) values were recorded as a function of frequency ranging from 100?Hz to 7?MHz and at different temperatures. Both ε´ and tanδ follow dispersion pattern at lower frequencies while show frequency independent behavior at higher frequencies. The magnetic evaluation carried by analyzing M-H hysteresis loop reveals the ferrimagnetic characteristics of these composites. The highest value of magnetic moment is 1.12μ_B observed for composite 0.50CoFe₂O₄ – 0.50Na_0.5Bi_0.5TiO_3. Magnetoelectric (ME) voltage coefficient (α) was also demonstrated to observe the interaction between ferrite and ferroelectric phases. The highest value of α (72.72μV/Oe cm) is obtained for low ferrite composition 0.10CoFe₂O₄ – 0.90Na_0.5Bi_0.5TiO₃, which suggests the dependence of magnetoelectric response on the resistivity of the composites.     

Effect of surface-modified Al2O3 on the thermomechanical properties of polybutylene succinate/Al2O3 composites

This study investigates the effect of the incorporation of alumina particles on the thermomechanical properties of polybutylene succinate (PBS)/Al₂O₃ composites. The alumina surface was modified with the carboxylic groups of maleic acid through simple acid-base and in situ polymerization reactions. Scanning electron microscope (SEM) results revealed the introduction of maleic acid treated alumina significantly affect the morphology of the PBS/Al₂O₃ composites as compared to the neat PBS. The thermal conductivity of the composite (0.411?W?m^?1 K^?1) was more than twice that of neat PBS. The composite containing polymerization-modified alumina showed a 50% increase in storage modulus compared with that of neat PBS. In addition, universal testing machine (UTM) and differential scanning calorimetry (DSC) measurements indicated an increase in the tensile strength and degree of crystallinity after the incorporation of modified alumina in the PBS/Al₂O₃ composite.