Rechargeability improvement of δ-type chemical manganese dioxide with the co-doping of Bi and Ni in alkaline electrolyte

δ-MnO₂ with the doping of Ni and Bi was prepared through a simple chemical precipitation/oxidation method. Its structure was confirmed by the X-ray diffraction tests. The results of cyclic voltammetry and galvanostatic charge–discharge tests showed that both the doping of Bi and Ni benefited the electrochemical activity of the MnO₂ electrode. Compared to the un-doped electrode, the Bi-doped one showed larger discharge capacity and the Ni-doped one showed higher discharge potential and better cycleability. With the co-doping of 5 wt% Bi and 10 wt% Ni, the discharge capacity of the MnO₂ electrode reached 252 mA h g^?1 at a 0.2C rate and 116 mA h g^?1 at a 1C rate, respectively. Its capacity remained in 105 mA h g^?1 after 50 cycles at a 1C rate, but the capacity of a commercial electrolytic MnO₂ electrode was only 37 mA h g^?1.     

Ultrathin MnO2 nanosheets grown on hollow carbon spheres with enhanced capacitive performance

Ultrathin MnO₂ nanosheets grown on the surface of hollow carbon spheres (MnO₂/HCSs) were fabricated by the redox reaction between carbon spheres with KMnO₄ in aqueous solution. Due to the porous structure and large amounts of active sites, MnO₂/HCSs exhibit excellent capacitive performance with 227.5 F g⁻¹ at 1 A g⁻¹. After 5000 cycles, the capacity retention of MnO₂/HCSs remains 96%, indicating its good cycling stability. These results demonstrate that MnO₂/HCSs are promising supercapacitor electrode material and this work provide a facile method for growth of ultrathin MnO₂ nanosheets on carbon substrate.     

SnO2-decorated multiwalled carbon nanotubes and Vulcan carbon through a sonochemical approach for supercapacitor applications

Multiwalled carbon nanotubes (MWCNTs) and Vulcan carbon (VC) decorated with SnO₂ nanoparticles were synthesized using a facile and versatile sonochemical procedure. The as-prepared nanocomposites were characterized by means of transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Fourier transform infra red spectroscopy. It was evidenced that SnO₂ nanoparticles were uniformly distributed on both carbon surfaces, tightly decorating the MWCNTs and VC. The electrochemical performance of the nanocomposites was evaluated by cyclic voltammetry and galvanostatic charge/discharge cycling. The as-synthesized SnO₂/MWCNTs nanocomposites show a higher capacity than the SnO₂/VC nanocomposites. Concretely, the SnO₂/MWCNTs electrodes exhibit a specific capacitance of 133.33 F g⁻¹, whereas SnO₂/VC electrodes exhibit a specific capacitance of 112.14 F g⁻¹ measured at 0.5 mA cm⁻² in 1 M Na₂SO₄.     

Hydrophilic polyaniline nanofibrous architecture using electrosynthesis method for supercapacitor application

An electrosynthesis process of hydrophilic polyaniline nanofiber electrode for electrochemical supercapacitor is described. The TGA–DTA study showed polyaniline thermally stable up to 323 K. Polyaniline nanofibers exhibit amorphous nature as confirmed from XRD study. Smooth interconnected fibers having diameter between 120–125 nm and length typically ranges between 400–500 nm observed from SEM and TEM analysis. Contact angle measurement indicated hydrophilic nature of polyaniline fibers. Optical study revealed the presence of direct band gap with energy 2.52 eV. The Hall effect measurement showed room temperature resistivity ∼3 × 10⁻⁴ Ω cm and Hall mobility 549.35 cm⁻²V⁻¹ s⁻¹_. The supercapacitive performance of nanofibrous polyaniline film tested in 1 M H₂SO₄ electrolyte and showed highest specific capacitance of 861 F g⁻¹ at the voltage scan rate of 10 mV/s.     

Morphologically controlled preparation of CuO nanostructures under ultrasound irradiation and their evaluation as pseudocapacitor materials

Various morphologies of copper oxide (CuO) nanostructures have been synthesized by controlling the reaction parameters in a sonochemical assisted method without using any templates or surfactants. The effect of reaction parameters including molar ratio of the reactants, reaction temperature, ultrasound exposure time, and annealing temperature on the composition and morphology of the product(s) has been investigated. The prepared samples have been characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDAX), and thermogravimetric analysis (TGA). It has been found that Cu₂(OH)₃NO₃ nanoplatelets are achieved in mild conditions which can be then converted to various morphologies of CuO nanostructures by either using high concentrations of OH⁻ (formation of nanorods), prolonging sonication irradiation (nanoparticles), or thermal treatment (nanospheres). Application of the prepared CuO nanostructures was evaluated as supercapacitive material in 1 M Na₂SO₄ solution using cyclic voltammetry (CV) in different potential scan rates ranging from 5 to 100 mV s⁻¹. The specific capacitance has been calculated using CV curves. It has been found that the pseudocapacitor performance of CuO can be tuned via employing morphologically controlled samples. Accordingly, the prolonged sonicated sample (nanoparticles) showed the high specific capacitance of 158 F.g⁻¹.     

Effect of different modes of electrodeposition on supercapacitive properties of MnO2 thin films

In present investigation MnO₂ thin films have been prepared by potentiodynamic (PD), potentiostatic (PS) and galvanostatic (GS) modes of electrodeposition. The effects of different modes on structural, surface morphological and supercapacitive properties of MnO₂ thin films have been investigated. Formation of amorphous phase of MnO₂ by all three modes is confirmed from X-ray diffraction (XRD) patterns. Significant change in the surface morphologies of MnO₂ thin films due to different modes has been observed. The supercapacitive properties of MnO₂ thin films have been studied in 1 M Na₂SO₄ electrolyte. The maximum supercapacitance obtained for potentiodynamic, potentiostatic and galvanostatic modes is 237, 196 and 184 F g⁻¹, respectively. Additionally charge-discharge and impedance of MnO₂ thin films have been investigated.     

Conversion of ultraviolet and infrared to visible light in Er3+ and Dy3+ co-doped CsGd2F7

The CsGd₂F₇ crystal co-doped with 1 at% Er³⁺ and 0.2 at% Dy³⁺ ions was studied using the excitation of both synchrotron radiation and 355 nm laser. All the emission bands were assigned by using the Dieke diagram together with the conclusions from relaxation kinetics studies. The onset of the 4f–5d transition bands and the centers of charge transfer bands were also calculated for the lanthanide series CsLn₂F₇ and the results were used to assign the bands and peaks in the excitation spectra. The energy transfer and relaxation processes in CsGd₂F₇ were thoroughly analyzed. Quantum cutting downconversion of one vacuum ultraviolet to two visible photons was realized under 154 nm excitation. Upconverted green emission was observed under 980 nm excitation.     

Optical characteristics of Tb-doped InBO3 nanocrystals

InBO₃ nanocrystals doped with Tb³⁺ ions are prepared via the sol–gel method. The structure, morphology, and optical properties of the nanocrystals are characterized by X-ray diffraction, high-resolution transmission electron microscopy, field-emission scanning electron microscopy, and photoluminescence analysis. The results show that a hexagonal InBO₃ phase forms at above 650 °C. A second phase of In₂O₃ begins to appear with Tb doping of over 3 mol%. The ⁵D₄→⁷F₅ (553 nm) transitions of Tb³⁺ ions in the InBO₃ host are observed at 2 mol%. The decay time of Tb-doped InBO₃ nanocrystals is about 2.1 ms. For Tb-doped InBO₃ nanocrystals excited at 237 nm and 553 nm wavelengths, the 2 mol% doping level yields the highest saturation of green emission. The emission shifts from green to yellow when the doping concentration is increased from 1 to6 mol%, due to the ⁵D₄→⁷F₅ transition.     

Electrochemical properties of spinel-type manganese oxide/porous carbon nanocomposite powders in 1 M KOH aqueous solution

Spinel-type manganese oxide/porous carbon (Mn₃O₄/C) nanocomposite powders have been simply prepared by a thermal decomposition of manganese gluconate dihydrate under an Ar gas flow at above 600 °C. The structure and texture of the Mn₃O₄/C nanocomposite powders are investigated by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS) equipped scanning transmission electron microscopy (STEM), transmission electron microscopy (TEM), selected area-electron diffraction (SA-ED), thermogravimetric and differential thermal analysis (TG-DTA) and adsorption/desorption of N₂ gas at ?196 °C. The electrochemical properties of the nanocomposite powders in 1 M KOH aqueous solution are studied, focusing on the relationship between their structures and electrochemical capacitance.In the nanocomposite powders, Mn₃O₄ nano particles approximately 5 nm in size are dispersed in a porous carbon matrix. The nanocomposite powders prepared at 800 °C exhibit a high specific capacitance calculated from cyclic voltammogram of 350 and 600 F g^?1 at a sweep rate of 1 and 0.1 mV s^?1, respectively. The influence of the heating temperature on the structure and the electrochemical properties of nanocomposite powders is also discussed.     

Porous carbon-coated graphite electrodes for energy production from salinity gradient using reverse electrodialysis

Performance of graphite foil electrodes coated by porous carbon black (i.e., Vulcan) was investigated in comparison with metal electrodes for reverse electrodialysis (RED) application. The electrode slurry that was used for fabrication of the porous carbon-coated graphite foil is composed of 7.2 wt% of carbon black (Vulcan X-72), 0.8 wt% of a polymer binder (polyvinylidene fluoride, PVdF), and 92.0 wt% of a mixing solvent (dimethylacetamide, DMAc). Cyclic voltammograms of both the porous carbon (i.e., Vulcan)-coated graphite foil electrode and the graphite foil electrode without Vulcan showed good reversibility in the hexacyanoferrate(III) (i.e., Fe(CN)₆³⁻) and hexacyanoferrate(II) (i.e., Fe(CN)₆⁴⁻) redox couple and 1 M Na₂SO₄ at room temperature. However, anodic and cathodic current of the Vulcan-coated graphite foil electrode was much higher than those of the graphite foil electrode. Using a bench-scale RED stack, the current–voltage polarization curve of the Vulcan-coated graphite electrode was compared to that of metal electrodes such as iridium (Ir) and platinum (Pt). From the results, it was confirmed that resistance of four different electrodes increased with the following order: the Vulcan-coated graphite foil<the Ir-coated titanium (Ti) mesh<the Pt-coated Ti plate<the graphite foil. Moreover, the Vulcan-coated graphite foil showed 5–10% higher power density than the metal mesh electrodes. From the polarization curve of the Vulcan-coated graphite foil electrode, it was found that total resistance decreased as thickness and geometric surface area of the electrode increased.     

Maximum magnetic entropy change modulated toward room temperature in perovskite manganites La0.7−xNdx(Ca,Sr)0.3MnO3

With Nd³⁺ doping and Ca²⁺, Sr²⁺ modulating in the sol–gel technique, a series of polycrystalline perovskite samples La_0.7?xNd_x(Ca,Sr)_0.3MnO₃ (x = 0, 0.05, 0.1, 0.15, 0.20, 0.25) was prepared, their maximum magnetic entropy changes were tuned to room temperature (ΔS_H = ?1.47 J/kg K at 298 k for La_0.45Nd_0.25(Ca,Sr)_0.3MnO₃), an enhancement of the maximum magnetic entropy change (ΔS_H = ?1.89 J/kg K at 315 k) and its refrigerant capacity (about 45.3 J/kg) had also been obtained under 9 kOe magnetic field variation for La_0.55Nd_0.15(Ca,Sr)_0.3MnO₃ contrast to La_0.7(Ca,Sr)_0.3MnO₃.     

Preparation and electrochemical investigation of the cobalt hydroxide carbonate/activated carbon nanocomposite for supercapacitor applications

Cobalt hydroxide carbonate/activated carbon (AC) composite was successfully synthesized by hydrothermal method. Morphological characterizations of cobalt hydroxide carbonate/AC composite were carried out by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and the results show that the cobalt hydroxide carbonate nanorods are well dispersed on the AC. Due to the synergistic effects arising from cobalt hydroxide carbonate nanorods and AC, the electrochemical performances of pure cobalt hydroxide carbonate material is significantly improved by the addition of AC. The composite shows a specific capacitance of 301.44 F g⁻¹ at a current density of 1 A g⁻¹ in 6 M KOH electrolyte and exhibits good cycling stability. Based on the above results, the cobalt hydroxide carbonate/AC composite shows a considerable promise as electrode for electrochemical applications.     

Luminescence properties of green emission of SiO2/Zn2SiO4:Mn nanocomposite prepared by sol–gel method

Green light emitting Mn²⁺ doped Zn₂SiO₄ particles embedded in SiO₂ host matrix were synthesized by a sol–gel method. After the incorporation of ZnO:Mn nanoparticles in a silica monolith using sol–gel method with supercritical drying of ethyl alcohol in two steps, it was heat treated in air at 1200 °C for 2 h in order to obtain the SiO₂/α-Zn₂SiO₄:Mn nanocomposites. The microstructure of phosphor crystals was characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). XRD results indicate that the pure phase α-Zn₂SiO₄ with rhombohedral structure was obtained after thermal treatment at 1200 °C. The SiO₂/α-Zn₂SiO₄:Mn nanocomposites with a Mn doping concentration of 1.5 at% exhibit two broadband emissions in the visible range: a strong green emission at around 525 nm and a second one in the range between 560 and 608 nm. This nanocomposite with a Mn doping concentration of 0.05 shows the highest relative emission intensity. Upon 255 nm excitation, the luminescence decay time of the green emission of Zn₂SiO₄:Mn around 525 nm is 11 ms. The luminescence spectra at 525 nm (⁴T₁–⁶A₁) and lifetime of the excited state of Mn²⁺ ions-doped Zn₂SiO₄ nanocrystals are investigated.     

Sonochemically synthesized MnO2 nanoparticles as electrode material for supercapacitors

In this study, manganese oxide (MnO₂) nanoparticles were synthesized by sonochemical reduction of KMnO₄ using polyethylene glycol (PEG) as a reducing agent as well as structure directing agent under room temperature in short duration of time and characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscope (SEM), Transmission electron microscopy (TEM) and Brunauer–Emmett–Teller (BET) analysis. A supercapacitor device constructed using the ultrasonically-synthesized MnO₂ nanoparticles showed maximum specific capacitance (SC) of 282 Fg⁻¹ in the presence of 1 M Ca(NO₃)₂ as an electrolyte at a current density of 0.5 mA cm⁻² in the potential range from 0.0 to 1.0 V and about 78% of specific capacitance was retained even after 1000 cycles indicating its high electrochemical stability.     

Effect of growth time of hydrothermally grown cobalt hydroxide carbonate on its supercapacitive performance

We present the time-dependent synthesis of cobalt hydroxide carbonate nanorods by hydrothermal method with a systematic increase of different parameters such as specific surface area and specific capacitance as a function of different synthesis time. Morphological characterization of the cobalt hydroxide carbonate nanorods were carried out by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that variation of the time of reaction plays a crucial role in the transformation of samples’ morphology. Cobalt hydroxide carbonate nanorods synthesized with 12 h reaction time, which is the reaction just before the materials transforms into cobalt oxide under the same synthesis conditions exhibited the highest specific capacitance of 466 F g⁻¹ at a current density of 1 A g⁻¹ in 6 M KOH electrolyte and also showed excellent stability with ∼99% capacitance retention after 2000 cycles at a current density of 10 A g⁻¹. Based on the above results, the cobalt hydroxide carbonate nanorods show a considerable potential as electrodes materials for supercapacitor applications.     

Electrochemical supercapacitor studies of hierarchical structured Co2+-substituted SnO2 nanoparticles by a hydrothermal method

Hierarchical structured Co-doped SnO₂ nanoparticles are prepared by a low temperature hydrothermal process. The structural and surface morphologies of the SnO₂ and Sn_1?xCo_xO₂ nanoparticles are studied by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The Sn_1?xCo_xO₂ nanoparticles form with a tetragonal rutile structure during the hydrothermal process without further calcination. The pseudocapacitance behavior of the Sn_1?xCo_xO₂ nanoparticles is characterized by cyclic voltammetry (CV) in 1.0 M H₂SO₄ electrolyte. The specific capacitance (SC) is found to increase with an increase in cobalt content. A maximum SC of 840 F g^?1 is obtained for a Sn_0.96Co_0.04O₂ composite at a 10 mV s^?1 scan rate.     

The synthesis and properties of nanocrystalline electrode materials by mechanical alloying

In this work, we have experimentally studied the structure and electrochemical properties of nanocrystalline TiFe- and LaNi₅-type alloys. These materials were prepared by mechanical alloying (MA) followed by annealing. The properties of hydrogen host materials can be modified substantially by alloying to obtain the desired storage characteristics. It was found that the respective replacement of Fe in TiFe by Ni and/or by Cr, Co, Mo, Zr improved not only the discharge capacity but also the cycle life of these electrodes. In the nanocrystalline TiFe_0.25Ni_0.75, powder discharge capacity up to 155 mA h g⁻¹ was measured (at 40 mA g⁻¹ discharge current). On the other hand, a partial substitution of Ni by Al or Mn in LaNi_5−xM_x alloy leads to an increase in discharge capacity. The alloying elements such as Al, Mn and Co greatly improved the cycle life of LaNi₅ material. For example, in the nanocrystalline LaNi_3.75Mn_0.75Al_0.25Co_0.25 powder, discharge capacity up to 258 mA h g⁻¹ was measured (at 40 mA g⁻¹ discharge current). The studies show, that electrochemical properties of Ni–MH batteries are the function of the microstructure and the chemical composition of used electrode materials.     

Ferromagnetic spin-order in Mg-doped SnS2 nanoflowers prepared by hydrothermal method

Mg-doped SnS₂ nanoflowers were synthesized by hydrothermal method. The XRD and absorption spectra analyses reveal that the incorporated Mg atoms substitute for Sn atoms in SnS₂ lattice and red-shift the band-gap at low doping concentration (≤4 at%). With further doping, a transformation of Mg atoms from substitutional sites to interstitial sites occurs. The ferromagnetism of SnS₂ nanoflowers is enhanced non-monotonously with Mg doping and the largest saturation magnetization of 2.11×10⁻³ emu/g appears in 4 at% Mg-doped SnS₂. The holes created by Mg substituted incorporation may be the origin of the ferromagnetism. On the other hand, interstitial Mg atoms play a negative role in enhancing the ferromagnetism due to the holes compensation effect.     

Effect of doping concentration and annealing temperature on luminescence properties of Y2O3:Eu3+ nanophosphor prepared by colloidal precipitation method

Eu³⁺ doped Y₂O₃ nanophosphors have been synthesized using the simple colloidal precipitation method. Doping of Eu³⁺ ions in host yttria lattice has been achieved through slow re-crystallization process under wet-chemical conditions followed by annealing at high temperatures (300–1400 °C). The nanophosphors were characterized by using powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), atomic force microscopy (AFM) and spectrofluorometer techniques. XRD analysis reveals formation of pure cubic phase of Y₂O₃ in samples annealed at 700 °C or above. Further, the XRD data was successfully used to retrieve the crystallite size and size distribution from powder samples using the FW((1/5)/(4/5))M method. Crystallite size (11–50 nm) extracted from XRD has been found to be consistent with AFM measurements. The PL emission spectra of nanophosphors show bright red emission at 612 nm due to hypersensitive electric dipole (ED) ⁵D₀–⁷F₂ transition of Eu³⁺ ions in Y₂O₃ lattice. Further, photoluminescence studies indicate that optimum value of the Eu³⁺ to get best luminescence properties is 12 at%. Surface conjugations of these nanophosphors with water soluble dextran biomolecules have also been performed. Surface conjugated rare earth nanophosphors have great potential for bio-applications.     

SILAR deposited Bi2S3 thin film towards electrochemical supercapacitor

Bi₂S₃ thin film electrode has been synthesized by simple and low cost successive ionic layer adsorption and reaction (SILAR) method on stainless steel (SS) substrate at room temperature. The formation of interconnected nanoparticles with nanoporous surface morphology has been achieved and which is favourable to the supercapacitor applications. Electrochemical supercapacitive performance of Bi₂S₃ thin film electrode has been performed through cyclic voltammetry, charge-discharge and stability studies in aqueous Na₂SO₄ electrolyte. The Bi₂S₃ thin film electrode exhibits the specific capacitance of 289 Fg⁻¹ at 5 mVs⁻¹ scan rate in 1 M Na₂SO₄ electrolyte.