Hybrid manganese oxide films for supercapacitor application prepared by sol-gel technique

Hybrid films were prepared by adding various concentrations of meso-carbon microbeads (MCMB) during sol-gel processing of manganese oxide films. The heat-treated films were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). In addition, electrochemical performance of the MCMB-added Mn-oxide hybrid coatings was evaluated by cyclic voltammetry (CV) and compared with its unadded counterpart. Experimental results showed that Mn-oxide films exhibited a mixture of Mn₂O₃ and Mn₃O₄ phases. The higher the heat-treatment temperature, the more Mn₂O₃ can be observed. The specific capacitance of the unadded Mn-oxide electrodes is 209 F/g. Because the MCMB particles provide more interfacial surface area for electrochemical reactions, a significant improvement can be noticed by adding MCMB in Mn-oxide coatings. The 300 °C heat-treated hybrid Mn-oxide coating with a Mn/MCMB ratio of 10/1 exhibits the highest value of 350 F/g, showing a ~ 170% increase in specific capacitance.     

Fabrication horizontal aligned MoO2/single-walled carbon nanotube nanowires for electrochemical supercapacitor

The horizontally aligned MoO₂/single-walled carbon nanotube (MoO₂/SWNT) composite has been prepared by electrochemically induced deposition method which utilizes the good electronic conductivity of SWNTs as supporting material to deposit MoO₂. The morphology and crystal structure of the composite were investigated by X-ray photoelectron spectroscopy and scanning electron microscopy, respectively. The capacitive properties of the MoO₂/SWNT composites have been investigated by cyclic voltammetry (CV). A specific capacitance (based on MoO₂) as high as 597 F g^− 1 is obtained at a scan rate of 10 mV s^− 1 in 0.1 M Na₂SO₄ aqueous solution. Additionally, the MoO₂/SWNT composites electrode shows excellent long-term cycle stability (only 2.5% decrease of the specific capacitance is observed after 600 CV cycles).     

Potentiodynamical co-deposited manganese oxide/carbon composite for high capacitance electrochemical capacitors

Manganese oxide/carbon composite materials were prepared by introducing the carbon powders into the potentiodynamical anodic co-deposited manganese oxide in 0.5 mol L^− 1 MnSO₄ and 0.5 mol L^− 1 H₂SO₄ mixed solution at 40 °C. The surface morphology and structure of the composite material were examined by scanning electron microscope and X-ray diffraction. Cyclic voltammetry tests and electrochemical impedance measurements were applied to investigate the performance of the composite electrodes with different ratios of manganese oxide and carbon. These composite materials with rough surface, which consisted of approximately amorphous manganese oxide, were confirmed to possess the ideal capacitive property. The highest specific capacitance of manganese oxide/carbon composite electrode was up to 410 F g^− 1 in 1.0 mol L^− 1 Na₂SO₄ electrolyte at the scan rate 10 mV s^− 1. The synthesized composite materials exhibited ideal capacitive behavior indicating a promising electrode material for electrochemical supercapacitors.     

Preparation and thermoelectric properties of nc-Si:(Al2O3 + SiO2) composite film

A composite film of nanocrystalline Si (nc-Si) embedded in (Al₂O₃ + SiO₂) has been prepared on a quartz substrate by thermally evaporating a 400 nm thick Al film on a quartz substrate and annealing in air at 580 °C for 1 h. During annealing, the Al reacts with the SiO₂ of the quartz substrate and produces nc-Si, which is embedded in the (Al₂O₃ + SiO₂) film. The average size of nc-Si is ~ 22 nm and the thickness of the nc-Si:(Al₂O₃ + SiO₂) composite film is ~ 810 nm. It is found that the prepared film is thermoelectric with a Seebeck coefficient of − 624 μV/K at 293 K and − 225 μV/K at 413 K.     

Rapid synthesis of homogeneous MnO2/multi-wall carbon nanotubes nanostructure and its electrochemical capacitive behavior

A homogeneous composite of MnO₂/multi-wall carbon nanotubes (MnO₂/MWCNTs) was rapidly and efficiently synthesized by a redox reaction of MnO₄⁻ and Mn²⁺ on the MWCNTs under ultrasonic irradiation. The structure and morphology of the obtained MnO₂ and MnO₂/MWCNTs composite were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and transmission electron microscopy. Electrochemical investigation indicated that the maximum specific capacitance of the MnO₂/MWCNTs composite, measured by galvanostatic charge-discharge test, was 315 F g^− 1, compared to the pristine MnO₂ (192 F g^− 1) and MWCNTs electrode (25 F g^− 1), showing the synergistic effect of MWCNTs and MnO₂. The homogeneous hybrid nanostructure and the good conductivity of MWCNTs were considered to be responsible for its preferable electrochemical performances.     

Facile synthesis and electrochemical properties of Mn3O4 nanoparticles with a large surface area

Mn₃O₄ nanoparticles were prepared by a novel oxidation-precipitation method at a low temperature. The crystal phase, microstructure, surface area and electrochemical properties of the products were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), N₂ adsorption-desorption isotherms and cyclic voltammetry (CV). The results indicate that the addition of citric acid and tartaric acid remarkably reduced the particle size and increased the specific surface area of Mn₃O₄ nanoparticles. The samples prepared by the addition of citric acid and tartaric acid have a narrow particle size distribution of 5-10 nm, a surface area of 119 and 122 m²/g, and a capacitance of 171 and 172 F g⁻¹, respectively.     

Preparation and characterization of nanostructured NiO/MnO2 composite electrode for electrochemical supercapacitors

Nanostructured nickel-manganese oxides composite was prepared by the sol-gel and the chemistry deposition combination new route. The surface morphology and structure of the composite were characterized by scanning electron microscope and X-ray diffraction. The as-synthesized NiO/MnO₂ samples exhibit higher surface area of 130-190 m² g⁻¹. Cyclic voltammetry and galvanostatic charge/discharge measurements were applied to investigate the electrochemical performance of the composite electrodes with different ratios of NiO/MnO₂. When the mass ratio of MnO₂ and NiO in composite material is 80:20, the specific capacitance value of NiO/MnO₂ calculated from the cyclic voltammetry curves is 453 F g⁻¹, for pure NiO and MnO₂ are 209, 330 F g⁻¹ in 6 mol L⁻¹ KOH electrolyte and at scan rate of 10 mV s⁻¹, respectively. The specific capacitance of NiO/MnO₂ electrode is much larger than that of each pristine component. Moreover, the composite electrodes showed high power density and stable electrochemical properties.     

Self-assembled manganese dioxide nanowires as electrode materials for electrochemical capacitors

The microstructure and morphology of sol-gel derived manganese dioxide (MnO₂) xerogels were affected by the synthesis conditions and post synthesis heat treatment. Manganese dioxide nanoparticles in sol that were dialyzed to more acidic pH (pH 5.7) value were observed to self-assemble into nanowires, whereas non-dialyzed sols remained nanoparticulate in nature. MnO₂ xerogels of disordered nanowire network exhibited comparatively higher porosity and BET surface areas. The electrochemical properties of both MnO₂ nanowire and nanoparticle thin-film electrodes were evaluated using cyclic voltammetry in a mild aqueous electrolyte (0.1 M Na₂SO₄). The charge capacities of MnO₂ nanowire-based thin-film electrodes were substantially higher (~ 800 F/g) than those of nanoparticulate thin-film electrodes (~ 700 F/g).     

Solution-combustion synthesis of ε-MnO2 for supercapacitors

ε-MnO₂ nanoparticles were synthesized through a single step solution combustion process without using any template or surfactants. Plate-like ε-MnO₂ materials, 50-150 nm in diameter and 20-25 nm in thickness, were obtained at a higher Mn(NO₃)₂:C₂H₅NO₂ molar ratio (i.e., 2:1), whereas spherical ε-MnO₂ particles (about 60 nm in diameter) were obtained as the Mn(NO₃)₂:C₂H₅NO₂ ratio is lower (e.g., 1:2). Electrochemical performance of the as-prepared ε-MnO₂ nanoparticles was examined. The spherical ε-MnO₂ nanoparticle sample shows a relatively higher specific capacitance of 123 F g^− 1 at the current density of 1 A g^− 1 in 1 M NaSO₄ electrolyte solution, probably due to its porous structures and higher surface areas in comparison with the plate-like counterparties.     

Photocatalytic properties of BiFeO3 nanoparticles with different sizes

BiFeO₃ nanoparticles with different average grain sizes have been prepared through a polyacrylamide gel route. In the present synthesis route, the grain size is tailored by varying the ratio of bis-acrylamide to acrylamide. The photocatalytic activity of the as-prepared BiFeO₃ nanoparticles has been investigated by the degradation of methyl orange (MO), a typical azo dye. It is revealed that the products exhibit a pronounced photocatalytic activity under ultraviolet as well as visible-light irradiation. With decrease in particle size, the photocatalytic activity exhibits a rising trend. The influences of catalyst dosage and initial dye concentration on the photocatalytic efficiency have been also investigated. In the present experiments, the optimum loading of BiFeO₃ nanoparticles and initial concentration of MO are obtained to be ~ 2.5 g L⁻¹ and ~ 10 mg L⁻¹, respectively.     

Pore size control and electrochemical capacitor behavior of chemically activated polyacrylonitrile – Carbon nanotube composite films

Activated polyacrylonitrile (PAN)/carbon nanotube (CNT) composite film based electrodes have been prepared by chemical activation with potassium hydroxide for electrochemical capacitors. This paper analyses the following aspects of specific capacitance, pore size distribution and surface area: influence of activation temperature, molarity of activating agent, composition of PAN/carbon nanotube precursor films and electrolytes. A maximum value of specific capacitance of ∼302 Fg⁻¹ was achieved for the samples activated at 800 °C. Energy density for PAN/CNT 80/20 sample when tested with ionic liquid/organic electrolyte system was as high as ∼22 W h kg⁻¹. Pore size control predominantly below 5 nm was observed in these activated PAN samples. Data analysis showed that micropores make a significant contribution to the capacitance performance of these materials in both 6 M KOH as well as in BMIMBF₄/acetonitrile electrolytes.     

Growth and spectral properties of Cr:KAl(MoO4)2 crystal

The Cr³⁺:KAl(MoO₄)₂ single crystal was grown by top seeding solution growth method (TSSG). Based on the absorption and emission spectra, the crystal field strength Dq, the Racah parameters B and C, the effective phonon energy ?ω and the Huang-Rhys factor S were calculated: Dq = 1494.8 cm^− 1, B = 585.5 cm^− 1 and C = 3049 cm^− 1, ?ω = 373.8 cm^− 1 and the Huang-Rhys factor S = 3.74, respectively. The value Dq/B = 2.55 indicates that Cr³⁺ ion occupies the strong crystal field site in KAl(MoO₄)₂ crystal. A comparison of crystal field parameters for Cr³⁺:KAl(MoO₄)₂ with other Cr³⁺-doped crystals was presented. The results of spectral measurement show that Cr³⁺:KAl(MoO₄)₂ may be a potential candidate for broadband laser applications.     

A new asymmetric supercapacitor based on λ-MnO2 and activated carbon electrodes

Lithium-ion intercalated compound λ-MnO₂ was used as positive electrode in asymmetric supercapacitor with activated carbon used as negative electrode in 1 mol L^− 1 Li₂SO₄ aqueous electrolyte solution. Phase composition, morphology and particle sizes of λ-MnO₂ were studied by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). Electrochemical capacitive performance of the asymmetric supercapacitor was tested by cyclic voltammetry and galvanostatic charge-discharge tests. The results show that the asymmetric supercapacitor has electrochemical capacitance performance within wide potential range of 0-2.2 V. The specific capacitance is 53 F g^− 1 at a constant current density of 10 mA cm^− 2. The energy density is 36 W h kg^− 1 with a power density of 314 W kg^− 1. It is obvious that λ-MnO₂ is a potential electrode material for asymmetric supercapacitor.     

Effects of Fe2O3 doping on the microstructure and piezoelectric properties of 0.55Pb(Ni1/3Nb2/3)O3-0.45Pb(Zr0.3Ti0.7)O3 ceramics

0.55Pb(Ni_1/3Nb_2/3)O₃-0.45Pb(Zr_0.3Ti_0.7)O₃(PNN-PZT) ceramics with different concentration of xFe₂O₃ doping (where x = 0.0, 0.8, 1.2, 1.6 mol%) were synthesized by the conventional solid state sintering technique. X-ray diffraction analysis reveals that all specimens are a pure perovskite phase without pyrochlore phase. The density and grain size of Fe-doped ceramics tend to increase slightly with increasing concentration of Fe₂O₃. Comparing with the undoped ceramics, the piezoelectric, ferroelectric and dielectric properties of the Fe-doped PNN-PZT specimens are significantly improved. Properties of the piezoelectric constant as high as d₃₃ ~ 956 pC/N, the electromechanical coupling factor k_p ~ 0.74, and the dielectric constant ε_r ~ 6095 are achieved for the specimen with 1.2 mol% Fe₂O₃ doping sintered at 1200 °C for 2 h.     

Hydrothermal synthesis of carbon nanotube/cubic Fe3O4 nanocomposite for enhanced performance supercapacitor electrode material

Carbon nanotube/Fe₃O₄ (CNT/Fe₃O₄) nanocomposite with well-dispersed Fe₃O₄ nano-cubes inlaid on the surfaces of carbon nanotubes, was synthesized through an easy and efficient hydrothermal method. The electrochemical behaviors of the nanocomposite were analyzed by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and chronopotentiometry in 6 M KOH electrolyte. Results demonstrated that CNT as the supporting material could significantly improve the supercapacitor (SC) performance of the CNT/Fe₃O₄ composite. Comparing with pure Fe₃O₄, the resulting composite exhibited improved specific capacitances of 117.2 F/g at 10 mA/cm² (3 times than that of pure Fe₃O₄), excellent cyclic stability and a maximum energy density of 16.2 Wh/kg. The much improved electrochemical performances could be attributed to the good conductivity of CNTs as well as the anchored Fe₃O₄ particles on the CNTs.     

Nickel-cobalt oxides/carbon nanoflakes as anode materials for lithium-ion batteries

Novel nickel-cobalt oxides/carbon nanoflakes with Ni/Co molar ratio = 1:1 and 1:2 have been synthesized by a convenient hydrothermal method followed by a simple calcination process. X-ray diffraction results showed that the composites were composed of NiO, Co₃O₄, and carbon. Scanning electron microscope measurements demonstrated that the composites were flakes less than 100 nm in thickness, and the corresponding energy dispersive spectroscopy mapping showed that the carbon was distributed homogeneously in the composites. The electrochemical results showed that the composite electrodes exhibited low initial coulombic efficiency and excellent charge-discharge cycling stability. Additionally, the effect of different Ni/Co molar ratios on the electrochemical properties of the composites was investigated, and better performance was obtained for the sample with a Ni/Co molar ratio of 1:2.     

Temperature-dependent high-resolution X-ray photoelectron spectroscopic study on Ge1Sb2Te4

Oxygen-free and amorphous Ge₁Sb₂Te₄ thin film was obtained in an ultra-high vacuum and then annealed in situ to the stable-phase temperature. High-resolution X-ray photoelectron spectroscopy using synchrotron radiation was performed on the film at the different annealing temperatures of 100, 130, 150, 180, and 250 °C. The Te 4d, Sb 4d, and Ge 3d shallow core levels as well as the valence-band spectra were acquired. In the shallow core-level spectra, we observed distinguishable changes in the Sb 4d and Ge 3d levels as the film phase changed. As the temperature increased, a higher binding-energy (BE) component appeared at the Sb 4d level, the intensity of the component increased, and the spin-orbit split feature was enhanced at the Ge 3d level. In the valence-band spectra, a slight increase was observed at 0-1, ~ 3, ~ 9, and ~ 12 eV BE, and a decrease, at ~ 1.5 and ~ 4.5 eV BE. The energy resolution employed in this study was about 150 meV.     

Preparation and electrochemical performance of LiFePO4/C composite with network connections of nano-carbon wires

LiFePO₄/C composite with network connections of nano-carbon wires was successfully prepared by using polyvinyl alcohol as carbon source. The composite was characterized by X-ray diffraction and transmission electron microscopic, and its electrochemical performance was investigated by galvanostatic charge and discharge tests. The experimental results show that LiFePO₄ grains are tightly connected by the network of nano-carbon wires. Moreover LiFePO₄/C composite exhibits high capacity of 168 mAh g⁻¹ applied 15 mA g⁻¹ current density (C/10), excellent cyclic ability and rate capability. When 1500 mA g⁻¹ current density (10C) was applied, the high discharge capacity of 129 mAh g⁻¹ has been obtained at room temperature.     

Preparation and characterization of composite microspheres for brachytherapy and hyperthermia treatment of cancer

Composite microspheres were prepared by coating yttrium-aluminum-silicate (YAS) glass microspheres (20-30 μm) with a layer of Fe₃O₄ nanoparticles and evaluated for potential use in brachytherapy and hyperthermia treatment of cancer. After neutron activation to form the β-emitting ⁹⁰Y radionuclide, the composite microspheres can be injected into a patient to destroy cancerous tumors; at the same time, the composite microspheres can generate heat upon application of a magnetic field to also destroy the tumors. The results showed that the composite microspheres were chemically durable when immersed in a simulated body fluid (SBF), with ~ 0.25% weight loss and ~ 3.2% yttrium dissolved into the SBF after 30 days at 37 °C. The composite microspheres also showed ferromagnetic properties as a result of the Fe₃O₄ coating; when immersed in water at 20 °C (20 mg in 1 mL of water), the application of an alternating magnetic field produced a temperature increase from 20 °C to 38−46 °C depending on the thickness of the Fe₃O₄ coating. The results indicate that these composite microspheres have promising potential in combined brachytherapy and hyperthermia treatment of cancerous tumors.