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.     

A redox-assisted supramolecular assembly of manganese oxide nanotube

In this paper, we report the hydrothermal synthesis of manganese oxide nanotube from an aqueous medium of pH 7, using KMnO₄ and MnCl₂ as inorganic precursors, polyoxyethylene (10) nonyl phenyl ether (TX-10) a surfactant and acetaldehyde an additive. The characterization of X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and N₂ adsorption at 77 K (BET) reveals that the synthesized manganese oxide nanotube has a mesopore size of ca. 3.65 nm and a wall thickness of ca. 12 nm, with the wall being composed of microporous crystals of monoclinic manganite. The X-ray photoelectron spectroscopy (XPS) result demonstrates a decrease of the binding energy of the Mn³⁺ in the manganese oxide nanotube, which may be related to both the nanotubular morphology and the crystalline pore wall. A mechanism of a redox-assisted supramolecular assembly, regulated by acetaldehyde, is postulated.     

Crystal structure and properties of the new complex vanadium oxide K2SrV3O9

The new complex vanadium oxide K₂SrV₃O₉ has been synthesized and investigated by means of X-ray powder diffraction (XPD), electron microscopy and magnetic susceptibility measurements. The oxide has an orthorhombic unit cell with lattice parameters a = 10.1922(2) Å, b = 5.4171(1) Å, c = 16.1425(3) Å, space group Pnma and Z = 4. The crystal structure of K₂SrV₃O₉ has been refined by Rietveld method using X-ray powder diffraction data. The structure contains infinite chains built by V⁴⁺O₅ square pyramids linked to each other via VO₄ tetrahedra. The chains form layers and potassium and strontium cations orderly occupy structural interstices between these layers. Electron diffraction as well as high resolution electron microscopy confirmed the structure solution. Magnetic susceptibility measurements revealed an antiferromagnetic interaction with J of the order of 100 K inside the chains and no long-range magnetic order above 2 K. The origin of the magnetic exchange is likely a result of super-exchange interaction through the two VO₄ tetrahedra linking the polyhedra with the magnetic V⁴⁺ cations.     

Potentiodynamical deposition of nanosized manganese oxides as high capacitance electrochemical capacitors

Nanosized manganese oxides powders were potentiodynamically deposition onto the Pb substrates by anodic oxidation in 0.5 mol L⁻¹ MnSO₄ and 0.5 mol L⁻¹ H₂SO₄ mixed solution at 40 °C. The chemical composition of the sample was determined by complex titration with ethylene diamine tetraacetic acid and redox titration. X-ray diffraction, scanning electron microscopy, cyclic voltammetry, and chronopotentiometry were employed to characterize the materials. The highest specific capacitance of the MnO_x composite electrode was up to 420 F g⁻¹ in 1.0 mol L⁻¹ Na₂SO₄ electrolyte at the scan rate 5 mV s⁻¹. The synthesized nanosized manganese oxide exhibited ideal capacitive behavior indicating a promising electrode material for electrochemical supercapacitors.     

Preparation and crystal structure of a new tin titanate containing Sn; Sn2TiO4

Single crystals of a new tin titanate containing Sn²⁺, Sn₂TiO₄ was prepared by high temperature reaction in an evacuated quartz tube and its crystal structure was determined by single crystal X-ray diffraction data. The tin titanate crystallizes in the tetragonal space group P4₂/mbc with a = 8.490(2) and c = 5.923(3) Å, Z = 4 and the final R factors are R = 0.0497 and R_w = 0.0676 for 354 unique reflections. This tin titanate is isostructural with the low temperature form of Pb₃O₄(Pb₂²⁺Pb⁴⁺O₄). This compound was oxidized above 600 °C accompanying the mass gain and finally changed to rutile-type solid solution (Sn,Ti)O₂.     

Influence of isovalent ion substitution on the electrochemical performance of LiCoPO4

LiCo_1−xM_xPO₄ (M = Mg²⁺, Mn²⁺ and Ni²⁺; 0 ≤ x ≤ 0.2) compounds have been synthesized by solid-state reaction method and studied as cathode materials for secondary lithium batteries. LiCoPO₄ exhibits a discharge plateau at ∼4.7 V with an initial discharge capacity of 125 mAh/g and on cycling capacity falls. Substitution of Co²⁺ with Mg²⁺/Mn²⁺/Ni²⁺ in LiCoPO₄ has an influence on the initial discharge capacity and on cycling behaviour. The capacity retention of LiCoPO₄ is improved by manganese substitution. Among the manganese substituted phases, LiCo_0.95Mn_0.05PO₄ shows good reversible capacity of ∼50 mAh/g.     

Influence of Er doping on microstructure of oxyfluoride glass-ceramics

Oxyfluoride glasses with composition of 45SiO₂·20Al₂O₃·30PbF₂·5ZnF₂ by molar ratio with a high stability against crystallization have been obtained by melt quenching. After doping with x (x = 1, 2, 4) mol% of Er³⁺ transparent or translucent glass-ceramics could be formed. The structural transformations of these materials were investigated by thermal analysis, X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS). Spherical polycrystalline aggregates comprised of many nanosized and randomly oriented β-PbF₂ grains were embedded separately among glassy matrix. On heating these nanosized grains merge with their neighbors to form bigger single crystals in a way like Ostwald ripening. The size modification of polycrystalline aggregates in the samples was found to be dependent on Er³⁺ doping.     

An electrochemical sensor based on Pt/g-C3N4/polyaniline nanocomposite for detection of Hg2+

The synthesis of Pt/g-C₃N₄/polyaniline nanocomposites (Pt/g-C₃N₄/PAn NCs) via the direct reduction of Pt (II) in the presence of L-cysteine as the reducing agent is presented in this study. X-ray diffraction analysis showed that the Pt cations were reduced to metallic Pt in the presence of L-cysteine. Field emission scanning electron microscope images confirmed a low agglomeration of metallic Pt when synthesized in the presence of g-C₃N₄. Electrochemical impedance spectroscopy results showed that the low conductivity of g-C₃N₄ is compensated with the presence of polyaniline (PAn). A glassy carbon electrode modified with the Pt/g-C₃N₄/PAn NCs showed high selectivity and sensitivity for the detection of Hg²⁺. The presence of active sites in the g-C₃N₄ and PAn enhanced the adsorption of Hg²⁺. The voltammetric response was linear in the concentration range of 1–500 nM Hg²⁺, with the detection limit of 0.014 nM (at S/N = 3).     

Fabrication and characterization of platinum black and mesoporous platinum electrodes for in-vivo and continuously monitoring electrochemical sensor applications

Most electrochemical biosensors are disposable due to enzymes that are living creatures. Thus, these are limited to use in in-vivo and continuously monitoring biosensor system applications. The mesoporous (pores with a size of 2-50 nm) platinum (Pt) structure formed on a rod-shaped Pt microelectrode was reported for developments glucose sensors without any enzymes. In this paper, plane Pt electrode (non-treated), Pt black electrode, and mesoporous Pt electrode are fabricated and characterized on a silicon substrate in order to check their usability as enzymeless sensing electrodes for in-vivo and continuously monitoring electrochemical biosensors integrated with silicon CMOS read-out circuitry. The Pt black electrode with rough surface was fabricated by using an electrodeposition technique with hexachloroplatinic acid hydrate (HCPA) solutions. The proposed mesoporous Pt electrode with approximately 3 nm in pore diameter was fabricated by using an electrodeposition technique with nonionic surfactant octaethylene glycol monohexadecyl ether (C₁₆EO₈) and HCPA. The measured current responses at 40 mM glucose solution of the fabricated plane Pt, Pt black, and mesoporous Pt electrodes are approximately 12.4 nA/mm², 2.1 μA/mm², and 2.8 μA/mm², respectively. These data indicate that the mesoporous Pt electrode is much more sensitive than the other Pt electrodes and has strong potential for enzymeless electrochemical sensor applications.     

Sintering LiTaO3 and KTaO3 with the aid of manganese oxide

The sintering of LiTaO₃ and KTaO₃ with the aid of manganese oxide was studied at 1080 to 1300° C by X-ray analysis, scanning electron microscopy (SEM) and X-ray microanalysis (XMA). The sintering of pure LiTaO₃ and KTaO₃ proceeds concurrently with grain growth, but only achieves a density of 83% at 1300° C and of 72% at 1280° C, respectively. The addition of 3 wt% of MnO₂ or Mn₃O₄ results in rapid densification of LiTaO₃ to 90 to 92% within 30 min at 1190° C. In the presence of manganese oxide, KTaO₃ densifies to 95% at 1280° C. The action of manganese oxide is attributed to the substitution of Mn³⁺ for Ta⁵⁺ in the LiTaO₃ or KTaO₃ lattice which enhances the diffusion of the rate-determining species, oxygen, in the oxide. In addition, a liquid phase formed at 1250° C in KTaO₃ may significantly contribute to the achievement of 95% densification.     

Structure and surface morphology of Mn-implanted TiO2

A study of structure and surface morphology together with magnetic properties of Mn-implanted rutile-type TiO₂ single crystals is performed. Homogenous thin films of about 100 nm with different Mn_xTi_1 − xO₂ (x = 0.03; 0.05 and 0.07) chemical formula were obtained. The Mn ion implanted surface exhibited a dense microstructure with a nano grain size. The dependence of c/a axial ratio on manganese content suggests that Mn³⁺ species substituted tetragonal Ti⁴⁺. The annealing at 873 K caused changes in surface structure, morphology and roughness. A migration of manganese ions into the rutile single crystal takes place and in certain conditions Ti₂O phase occurs. Mn-implanted samples exhibit room temperature ferromagnetism and a Curie temperature of 680 K. Electron spin resonance analysis evidenced that manganese is incorporated by substitution as magnetically isolated Mn⁴⁺, Mn³⁺ and Mn²⁺ species. At 0.07% contents the Mn³⁺ species may enter in interstitial sites contributing to extinction of substitutional magnetic moment.     

Preparation of reduced graphene oxide-NiFe2O4 nanocomposites for the electrocatalytic oxidation of hydrazine

A reduced graphene oxide (RGO)-NiFe₂O₄ nanocomposite was synthesized by a simple one step hydrothermal approach and its application in the electrocatalytic oxidation of hydrazine was demonstrated. The as-synthesized nanocomposite was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, UV–visible spectroscopy, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, Thermogravimetric analysis, Field emission-scanning electron microscopy (FE-SEM), and Transmission electron microscopy (TEM). The FE-SEM and TEM image analyses revealed that the NiFe₂O₄ nanoparticles were uniformly distributed on the RGO sheets with a diameter and length of ∼10 and ∼100 nm, respectively. The XPS analysis confirmed the ionic states of Ni and Fe to be Ni³⁺ and Ni²⁺, and Fe²⁺ and Fe³⁺, respectively. Further, the electrochemical activity of the RGO-NiFe₂O₄ nanocomposite was investigated by studying the oxidation of hydrazine. The RGO-NiFe₂O₄ modified glassy carbon electrode (GCE) showed an outstanding electrocatalytic activity towards the oxidation of hydrazine as compared to the NiFe₂O₄ and RGO modified electrodes. The enhanced electrocatalytic activity is due to the synergistic effect between RGO and NiFe₂O₄. Using amperometry, the lowest detection limit of 200 nM was achieved with the RGO-NiFe₂O₄ modified GCE. Therefore, the RGO-NiFe₂O₄ modified GCE can be used for the electrochemical oxidation of hydrazine.     

Fluorine-doped LiNi0.5Mn1.5O4 for 5 V cathode materials of lithium-ion battery

Fluorine-doped 5 V cathode materials LiNi_0.5Mn_1.5O_4−xF_x (0.05 ≤ x ≤ 0.2) have been prepared by sol-gel and post-annealing treatment method. The results from X-ray diffraction and scanning electron microscopy (SEM) indicate that the spinel structure changes little after fluorine doping, but the particle size varies with fluorine doping and the preparation conditions. The electrochemical measurements show that stable cycling performance can be obtained when the fluorine amount x is higher than 0.1, but the specific capacity is decreased and 4 V plateau capacity resulting from a conversion of Mn⁴⁺/Mn³⁺ remains. Moreover, influence of the particle size on the reversible capacity of the electrode, especially on the kinetic property, has been examined.     

Characterization of copper manganite oxide-polypyrrole composite electrodes cathodically polarized in acidic medium

We have studied the electrochemical behaviour induced by polarization in sandwich-type composite electrodes with the structure GC/PPy/PPy(Ox)/PPy where GC stands for glassy carbon, PPy for polypyrrole and Ox for Cu_1.4Mn_1.6O₄ nanoparticles. The electrodes were polarized at ?0.45 V/SCE in 0.15 M KCl aqueous solution at pH 2.2 either saturated in Ar or O₂ at 25 °C. The changes occurring on these electrodes were studied using X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (EXAFS and XANES) techniques. In previous work we have shown that when the oxide particles are incorporated into the PPy matrix the Cu⁺ present in the initial oxide suffers dismutation to give Cu²⁺ and metallic Cu. In this work we show that the polarized electrodes also reveal the presence of metallic Cu and Cu²⁺. The data also show that the oxide particles embedded in the polarized electrodes contain Mn³⁺ and Mn⁴⁺, although the Mn³⁺/Mn⁴⁺ ratio is different from that found in the fresh electrodes. The Cl 2p XPS data show that in the electrode polarized in O₂ there is an enhancement of the Cl covalent contribution that appears at 200.8 eV (which is already present in the fresh electrode although with a very small intensity). This result suggests that the oxygen reduction reaction leads to an increase of the OH^? concentration inside the composite electrode that explains the charge transport in PPy at negative potentials.     

Role of additives; sodium dodecyl sulphate and manganese chloride on morphology of Zn1−xMnxO nanoparticles and their photoluminescence properties

In the present study Zn_1−xMn_xO (x = 0, 0.05 and 0.1) nanoparticles (NPs) have been synthesised in aqueous solution phase at mild reaction temperature 100 °C in moderate alkaline medium (pH = 9.5), and the role of external additives; like sodium dodecyl sulphate and manganese chloride on the morphology and size of the products has been explored on the basis of transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectral analyses data. ZnO hexagonal nano-plates, core–shell like spherical/ellipsoidal Zn_0.95Mn_0.05O structures and thin sheets, thorn/needle mixed shaped Zn_0.9Mn_0.1O structures have been observed in TEM and SEM images. Zn(OH)₂ formed in moderate alkaline medium, converted to Zn(II) hydroxo complex ions on dissolution, which further recrystallizes to produce wurtzite ZnO at 100 °C. From XRD and EDX analysis, successful doping of Mn²⁺ ions at the Zn²⁺ sites in ZnO host has been proved. In the photoluminescence spectra, the observed blue shifts in NBE peaks and decrease of emissions intensity on Mn doping have thoroughly been discussed in the present investigation.     

Preparation of monodispersed cobalt-boron spherical nanoparticles and their behavior during the catalytic decomposition of hydrous hydrazine

Monodispersed cobalt-boron spherical nanoparticles have been prepared through solution plasma processing in the presence of hexadecyltrimethyl ammonium bromide for the first time. The particle size of cobalt-boron can be adjusted by changing either the plasma time or the concentration of hexadecyltrimethyl ammonium bromide. The samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. During the decomposition of hydrous hydrazine, the obtained monodispersed cobalt-boron spherical nanoparticles exhibit higher catalytic activity and hydrogen selectivity than regular cobalt-boron prepared by direct reduction of Co²⁺ with BH₄⁻. The experimental investigations indicate that hydrous hydrazine along with the monodispersed cobalt-boron spherical nanoparticles may find application in small-scale on-board hydrogen storage and supply.     

Properties and performance of La1.6Sr0.4NiO4+δ-Ce0.8Sm0.2O1.9 composite cathodes for intermediate temperature solid oxide fuel cells

La_1.6Sr_0.4NiO_4+δ-Ce_0.8Sm_0.2O_1.9 composite cathodes were prepared successfully using combustion synthesis method for intermediate temperature solid oxide fuel cells. The chemical compatibility, thermal expansion behavior, electrical conductivity and electrode performance were studied. The X-ray diffraction of La_1.6Sr_0.4NiO_4+δ-Ce_0.8Sm_0.2O_1.9 composite result proved a slight reaction between La_1.6Sr_0.4NiO_4+δ and Ce_0.8Sm_0.2O_1.9. Both the thermal expansion coefficient and the electrical conductivity of La_1.6Sr_0.4NiO_4+δ-Ce_0.8Sm_0.2O_1.9 decreased with increasing Ce_0.8Sm_0.2O_1.9 content. AC impedance spectroscopy measurements indicated that the addition of 30 wt% Ce_0.8Sm_0.2O_1.9 to La_1.6Sr_0.4NiO_4+δ exhibited the lowest polarization resistance (0.238 Ωcm²) at 800 °C in air, which was only one fourth of the La_1.6Sr_0.4NiO_4+δ electrode measured at the same temperature.     

Structural, morphological, and electrical characteristics of the electrodeposited cobalt oxide electrode for supercapacitor applications

Cobalt oxide (Co₃O₄) thin films were prepared through electrodeposition on copper substrates using an ammonia-complexed cobalt chloride solution. The structural and morphological properties of the film were studied using an X-ray diffractometer and scanning electron microscopy, and the results showed that the electrodeposited cobalt oxide film had a nanocrystalline and porous structure. The electrochemical behavior of the electrodeposited cobalt oxide electrode was evaluated in a KOH solution using cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge-discharge tests. The electrodeposited cobalt oxide electrode exhibited a specific capacitance of 235 F/g at a scan rate of 20 mV/s. The specific energy and the specific power of the electrode were 4.0 Wh/kg and 1.33 kW/kg, respectively.     

Effects of Nd substitution on the polarization properties and electronic structures of bismuth titanate single crystals

Single crystals of Nd-substituted Bi₄Ti₃O₁₂ ferroelectrics were grown by a self-flux method, and the effects of Nd substitution on the polarization properties and optical transmission spectra of the crystals have been investigated. Bi_3.52Nd_0.48Ti₃O₁₂ crystals showed a smaller remanent polarization along the a axis of 29 μC/cm² than Bi₄Ti₃O₁₂ crystals (46 μC/cm²), and this result is in good qualitative agreement with the calculation of the spontaneous polarization based on Rietveld analysis of neutron diffraction. Electronic band structure calculations using the structural data suggest that the orbital hybridization between the Nd 5d and O 2p states stabilizes oxide ions in the perovskite layers, which is consistent with the much smaller leakage current observed for Nd-substituted crystals.     

Crystal structure and EPR study of Mn-doped β-tricalcium phosphate

Mn-doped β-tricalcium phosphate was prepared by solid state reaction at 1100 °C. The crystal structure of Ca_2.85Mn_0.15(PO₄)₂, was determined by single crystal X-ray diffraction and found to be rhombohedral, R3c. Unit cell parameters are: a = 10.3419(3); c = 37.025(3) Å (hexagonal setting), Z = 21. Structure refinement data show that from the five Ca positions the Ca(4) site is only half filled and that the Mn²⁺ ions occupy the hexacoordinated Ca(5) site solely. EPR spectroscopy reveals that manganese in solid solutions Ca_3−xMn_x(PO₄)₂ (x = 0.1; 0.28; 0.6) is divalent and supports the structure refinement results that Mn occupies the Ca(5) site with a geometry very near to a regular octahedron.