Study of electrochemical properties and the charge/discharge mechanism for Li<Subscript>4</Subscript>Mn<Subscript>5</Subscript>O<Subscript>12</Subscript>/MnO<Subscript>2</Subscript>-AC hybrid supercapacitor

Spinel Li₄Mn₅O₁₂ was prepared by a sol–gel method. The manganese oxide and activated carbon composite (MnO₂-AC) were prepared by a method in which KMnO₄ was reduced by activated carbon (AC). The products were characterized by XRD and FTIR. The hybrid supercapacitor was fabricated with Li₄Mn₅O₁₂ and MnO₂-AC, which were used as materials of the two electrodes. The pseudocapacitance performance of the Li₄Mn₅O₁₂/MnO₂-AC hybrid supercapacitor was studied in various aqueous electrolytes. Electrochemical properties of the Li₄Mn₅O₁₂/MnO₂-AC hybrid supercapacitor were studied by using cyclic voltammetry, electrochemical impedance measurement, and galvanostatic charge/discharge tests. The results show that the hybrid supercapacitor has electrochemical capacitance performance. The charge/discharge test showed that the specific capacitance of 51.3 F g⁻¹ was obtained within potential range of 0–1.3 V at a charge/discharge current density of 100 mA g⁻¹ in 1 mol L⁻¹ Li₂SO₄ solution. The charge/discharge mechanism of Li₄Mn₅O₁₂ and MnO₂-AC was discussed.     

Facile synthesis of nano-Li<Subscript>4</Subscript> Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> for high-rate Li-ion battery anodes

One of the most promising anode materials for Li-ion batteries, Li₄Ti₅O₁₂, has attracted attention because it is a zero-strain Li insertion host having a stable insertion potential. In this study, we suggest two different synthetic processes to prepare Li₄Ti₅O₁₂ using anatase TiO₂ nanoprecursors. TiO₂ powders, which have extraordinarily large surface areas of more than 250 m² g^-1, were initially prepared through the urea-forced hydrolysis/precipitation route below 100°C. For the synthesis of Li₄Ti₅O₁₂, LiOH and Li₂CO₃ were added to TiO₂ solutions prepared in water and ethanol media, respectively. The powders were subsequently dried and calcined at various temperatures. The phase and morphological transitions from TiO₂ to Li₄Ti₅O₁₂ were characterized using X-ray powder diffraction and transmission electron microscopy. The electrochemical performance of nanosized Li₄Ti₅O₁₂ was evaluated in detail by cyclic voltammetry and galvanostatic cycling. Furthermore, the high-rate performance and long-term cycle stability of Li₄Ti₅O₁₂ anodes for use in Li-ion batteries were discussed.     

A Resumable Fluorescent Probe BHN-Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript> Hybrid Nanostructure for Fe<Superscript>3+</Superscript> and its Application in Bioimaging

A multifunctional fluorescent probe BHN-Fe₃O₄@SiO₂ nanostructure for Fe³⁺ was designed and developed. It has a good selective response to Fe³⁺ with fluorescence quenching and can be recycled using an external magnetic field. With adding EDTA (2.5?×?10^?5 M) to the consequent product Fe³⁺-BHN-Fe₃O₄@SiO₂, Fe³⁺ can be removed from the complex, and its fluorescence probing ability recovers, which means that this constituted on-off type fluorescence probe could be reversed and reused. At the same time, the probe has been successfully applied for quantitatively detecting Fe³⁺ in a linear mode with a low limit of detection 1.25?×?10^?8 M. Furthermore, the BHN-Fe₃O₄@SiO₂ nanostructure probe is successfully used to detect Fe³⁺ in living HeLa cells, which shows its great potential in bioimaging detection.     

Optical characteristics of xSrO·yAl<Subscript>2</Subscript>O<Subscript>3</Subscript>: Eu phosphors excited by ultraviolet light emitting diodes

We investigated the optical characteristics of strontium aluminate phosphors excited by near ultraviolet light emitting diodes (UV LEDs). For UV LEDs applications, strontium aluminates doped with europium were prepared at high temperature in a weakly reductive atmosphere. The effect of boric acid as a flux was considered. The excitation and emission spectra of these phosphors indicated that all of them have a broad band and that the main emission peaks, situated at around 490 nm for 4SrO·7Al₂O₃ : Eu and 520 nm for SrOAl₂O₃ : Eu, are both due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺. The typical brightness of a phosphor-converted LED, which was made with synthesized phosphors and a blue LED, was 712 mcd. By using the synthesized phosphors, phosphor-converted white LEDs could be well fabricated with good optical characteristics. In this case, color coordinates could be controlled from x = 0.1373 and y = 0.4635 to x = 0.2386 and y = 0.6066 at 20 mA and 3.69 V.     

Comparative study of the preparation and electrochemical performance of LiNi<Subscript>1</Subscript><Subscript>/2</Subscript>Mn<Subscript>1/2</Subscript>O<Subscript>2</Subscript> electrode material for rechargeable lithium batteries

Positive electrode material LiNi_1/2Mn_1/2O₂ was synthesized via the carbonate co-precipitation method and the hydroxide precipitation route to study the effects of the precursor on its structural and electrochemical properties. The results of X-ray diffraction and Rietveld refinement show that the carbonate precursor of Ni²⁺ and Mn²⁺ exhibits one phase at a pH of 8.5, while the hydroxide deposit separates into Ni(OH)₂ and Mn(OH)₂ phases under the same experimental conditions. LiNi_1/2Mn_1/2O₂ material prepared from the hydroxide precursor shows 8.9% Li/Ni exchange and a large capacity loss of 11.3% in the first 10 cycles. By contrast, more uniform distribution of transition metal ions and stable Mn²⁺ in the carbonate precursor contribute to only 7.8% Li/Ni disorder in the obtained LiNi_1/2Mn_1/2O₂, which delivers a reversible capacity of about 182 mAh g⁻¹ at a current rate of 14 mA g⁻¹ between 2.5 and 4.8 V.     

Synthesis of Titanates with a Ramsdellite-Type Tunnel Structure Crystallizing in the Li<Subscript>2</Subscript>O-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> System in Different Gaseous Media

The ramsdellite-type phases crystallizing in the Li₂O-Fe₂O₃-TiO₂ system in the course of synthesis in gaseous media at different oxygen partial pressures are studied. Solid solutions based on the ramsdellite structure with the composition Li₂Ti_3?xFe _x O_{7 ? δ} (0 ≤ x ≤ 0.7) are prepared in an oxidizing medium (P_O2 = 1 atm) for the first time. Analysis of the results obtained by electron paramagnetic resonance and Mossbauer spectroscopy revealed that, in these solid solutions, all iron ions are in the oxidation state Fe⁺³.     

Effect of Al/Sr ratio on the luminescence properties of SrAl2O4:Eu2+, Dy3+ phosphors

Recent studies have brought out many phosphors like Eu²⁺, Dy³⁺-doped alkaline earth aluminates. The trivalent Dy³⁺ ions as co-dopants greatly enhance the duration and intensity of persistent luminescence. These phosphors show excellent properties, such as high quantum efficiency, long persistence of phosphorescence, good stability and suitable color emission.In this work the effect of Al/Sr ratio on the afterglow and phosphorescence decay properties of Eu²⁺ and Dy³⁺ co-activated strontium aluminates synthesized by a solid-state process has been investigated. The luminescence properties of samples were investigated by means of excitation spectra, emission spectra and X-ray diffraction analysis.A variety of strontium aluminates, such as SrAl₂O₄, Sr₄Al₂O₇, Sr₃Al₂O₆, Sr₃Al₂(Eu, Dy, Y)O_7.5, Al₅(Eu, Dy, Y)O₁₂, Sr₄Al₁₄O₂₅, SrAl₁₂O₁₉ and (Eu, Dy, Y)AlO₃ have been identified in the samples prepared from starting precursors with Al/Sr mole ratios ranging from 0.44 to 5. The afterglow decay rate was found to be the fastest for sample with Al/Sr ratio of 4.18, in which SrAl₄O₇ phase was dominant. The afterglow decay rate for phosphor with Al/Sr ratio of 2, in which SrAl₂O₄ phase was dominant, was detected to be slow. Moreover, the emission spectra of the samples shift to yellow-green long wavelength from bluish-green-ultraviolet short wave with the increase of Al/Sr ratios resulting from the change in the composition.     

Preparation and electrochemical performance of Li-rich layered cathode material,Li[Ni<Subscript>0.2</Subscript>Li<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>]O<Subscript>2</Subscript>, for lithium-ion batteries

The Li-rich layered cathode material, Li[Ni_0.2Li_0.2Mn_0.6]O₂, was synthesized via a “mixed oxalate” method, and its structural and electrochemical properties were compared with the same material synthesized by the sol–gel method. X-ray diffraction (XRD) shows that the synthesized powders have a layered O₃–LiCoO₂-type structure with the R-3m symmetry. X-ray photoelectron spectroscopy (XPS) indicates that in the above material, Ni and Mn exist in the oxidation states of +2 and +4, respectively. The layered material exhibits an excellent electrochemical performance. Its discharge capacity increases gradually from the initial value of 228 mA hg⁻¹ to a stable capacity of over 260 mA hg⁻¹ after the 10th cycle. It delivers a larger capacity of 258 mA hg⁻¹ at the 30th cycle. The dQ/dV curves suggest that the increasing capacity results from the redox-reaction of Mn⁴⁺/Mn³⁺.     

Europium(II) in glasses of the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript>-MnO-Eu<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Triply and doubly charged states of europium are revealed by ¹⁵¹Eu Mössbauer spectroscopy in the structure of glasses of the composition (mol %) 19.5Al₂O₃, 31.5SiO₂, 26.5MnO, and 22.5Eu₂O₃. The isomer shifts in the Mössbauer spectra of Eu³⁺ and Eu²⁺ ions in the structure of glasses differ from the isomer shifts in the spectra of the Eu₂O₃ and EuO compounds. This difference is explained by the fact that the electron density at ¹⁵¹Eu nuclei is affected by the manganese and aluminum atoms, which are not bound directly to the europium atoms. The broadening of the spectra of the Eu²⁺ ions in glasses is caused by the nonuniform isomer shift.     

Crystal structure of new compound (Rb,K)<Subscript>2</Subscript>Cu<Subscript>3</Subscript>(P<Subscript>2</Subscript>O<Subscript>7</Subscript>)<Subscript>2</Subscript>

A new compound of (Rb,K)₂Cu₃(P₂O₇)₂ is obtained by high-temperature reactions from a mixture of RbNO₃, KNO₃, Cu(NO₃)₂, and (NH₄)₄P₂O₇. The crystal structure was solved by direct methods and refined to R ₁ = 0.056 for 5022 independent reflections. The compound belongs to a rhombic crystal system, P2₁2₁2₁, Z = 8, a = 9.9410(7) Å, b = 13.4754(6) Å, c = 18.6353 (3) Å, and R = 0.056. The basis of the structure is a complex copper-phosphate skeleton of the composition of [Cu₃(P₂O₇)₂]^2–, which can be regarded as consisting of two types of heteropolyhedral layers parallel to the (001) plane. The layers are alternated with each other, forming a frame, in the cavities of which the positions of alkali cations are located, statistically populated with K⁺ and Rb⁺ ions. Based on the refined populations of the positions of alkali cations, an exact chemical formula of the compound can be written as Rb_1.28K_0.72Cu₃(P₂O₇)₂. The compound is the most complex among those known to this day of the composition of A₂ ^IB₃ ^II(P₂O₇)₂ (A = Li, Na, K, Rb, or Cs; B = Ni, Cu, or Zn).     

Roles of doping ions in persistent luminescence of SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript>: Eu<Superscript>2+</Superscript>,<Emphasis Type="Italic">RE</Emphasis><Superscript>3+</Superscript> phosphors

The polycrystalline Eu²⁺ and Dy³⁺ codoped strontium aluminates SrAl₂O₄: Eu²⁺,Dy³⁺ were prepared by a solid-state reaction. The UV-excited photoluminescence, persistent luminescence, and thermoluminescence of the SrAl₂O₄: Eu²⁺,Dy³⁺ phosphors with different compositions and ion doping was studied and compared. The results showed that the Eu²⁺ ion doped in SrAl₂O₄: Eu²⁺,Dy³⁺ phosphors is not only the UV-excited luminescent center but also the persistent luminescent center. The Dy³⁺ ion introduced into SrAl₂O₄: Eu²⁺ crystal matrix can hardly yield any luminescence under UV excitation but acts as an electron trap with a suitable depth for persistent luminescence. The Dy³⁺ codoping would effectively enhance the persistent luminescence and thermoluminescence. Different codoping RE ³⁺ ions have a different effect on persistent luminescence. Only the RE ³⁺ ions (for example, Dy³⁺ and Nd³⁺), which have suitable optical electronegativity, can form suitable electron traps and effectively improve the persistent luminescence of SrAl₂O₄: Eu²⁺. Based on the above observations, a persistent luminescence mechanism, electron transfer model, was proposed and illustrated. The text was submitted by the authors in English.     

Effects of adding B<Subscript>2</Subscript>O<Subscript>3</Subscript> as a flux on phosphorescent properties in synthesis of SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript>: (Eu<Superscript>2+</Superscript>, DY<Superscript>3+</Superscript> phosphor

SrAl₂O₄: (Eu²⁺, Dy³⁺) phosphor was prepared by solid state reaction. B₂O₅ as a flux was added in SrAl₂O₄:(Eu ²⁺, Dy³⁺) in order to accelerate a solid state reaction. In this paper, the effects of B₂O₃ on the crystal structure and the phosphorescent properties of the material have been evaluated. The synthesized phosphor exhibited a broad band emission spectrum peaking at 520 nm, and the spectrum peak showed little effect by the B₂O₃ contents. The maximum afterglow intensity of the SrAl₂O₄: (Eu²⁺, Dy³⁺) phosphor was obtained at the B₂O₃ content of 5%. Adding the B₂O₃ caused uniform distortion to the crystal structure of the phosphor and resulted in reducing the lengths of a and c axes and Β angle of the SrAl₂O₄ crystal. The uniform distortion was accompanied with crystal defects which can trap the holes generated by the excitation of Eu²⁺ ions. The afterglow characteristic of the SrAl₂O₄: (Eu²⁺, Dy³⁺) phosphor was thus enhanced.     

Effect of Li2O on the crystallization behavior of CaO-Al2O3-SiO2-Li2O-Ce2O3 mold slags

The effect of Li₂O on the crystallization properties of CaO-Al₂O₃-SiO₂-Li₂O-Ce₂O₃ slags was investigated. With increasing the Li₂O content, LiAlO₂ and CaCeAlO₄ were the main crystalline phases. LiAlO₂ formed for the charge compensating of Li⁺ ions to [AlO₄^5?]-tetrahedrons, and CaCeAlO₄ formed as a result of the charge balance of Ce³⁺ ions, Ca²⁺ ions, and [AlO₆^9?]-octahedrons. Increasing the content of Li₂O to 10%, the crystallization temperature was the highest, and the incubation time was the shortest. The crystallization ability was strong due to the three factors of strengthening the interaction between ions and ion groups, decreasing the polymerization degree, and increasing the melting temperature. Further increasing the content of Li₂O, the crystallization performance was obviously suppressed, because the melting temperature and the force between the cations and the anion groups decreased.     

Zero-thermal-quenching of LiAl5O8: Eu2+, Mn2+ phosphors by energy transfer and defects engineering

The photoluminescence behavior of inorganic phosphors is generally influenced by thermal stability, which determines the luminescence efficiency of the corresponding devices. Here, a series of Eu²⁺, Mn²⁺ co-doped LiAl₅O₈ blue-green-emitting phosphors with thermal robust are successfully fabricated. The concentration-dependent emission spectra and the decay curves of the as-obtained LiAl₅O₈: Eu²⁺, Mn²⁺ samples manifest the occurrence of the energy transfer from Eu²⁺ to Mn²⁺ ions via dipole-dipole interaction, and the corresponding emitted colors are gradually modulated from blue to green under the excitation of 310 nm. Moreover, the zero-thermal-quenching luminescence is observed when the operation temperature is up to 423 K, which is attributed to the energy release from the trapping centers to emitting centers (Eu²⁺ and Mn²⁺) at high temperature. Furthermore, a warm white light-emitting diodes (WLEDs) device with correlated color temperature of 5061 K, a color rendering index of 80.6 and long-term stability is fabricated by combining UV LED chip (λ_ex = 310 nm), as-obtained LiAl₅O₈: Eu²⁺, Mn²⁺ phosphor, commercially available red phosphor and green phosphor. These results prove the potential application of the as-obtained LiAl₅O₈: Eu²⁺, Mn²⁺ phosphor for UV-pumped WLEDs devices.     

Characterization of Fischer–Tropsch Cobalt-Based Catalytic Systems (Co/SiO<Subscript>2</Subscript> and Co/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) by X-ray Diffraction and Magnetic Measurements

Results of the characterization of six Co-based Fischer–Tropsch (FT) catalysts, with 15% Co loading and supported on SiO₂ and Al₂O₃, are presented. Room temperature X-ray diffraction (XRD), temperature and magnetic field (H) variation of the magnetization (M), and low-temperature (5 K) electron magnetic resonance (EMR) are used for determining the electronic states (Co⁰, CoO, Co₃O₄, Co²⁺) of cobalt. Performance of these catalysts for FT synthesis is tested at reaction temperature of 240 °C and pressure of 20 bars. Under these conditions, 15% Co/SiO₂ catalysts yield higher CO and syngas conversions with higher methane selectivity than 15% Co/Al₂O₃ catalysts. Conversely the Al₂O₃ supported catalysts gave much higher selectivity towards olefins than Co/SiO₂. These results yield the correlation that the presence of Co₃O₄ yield higher methane selectivity whereas the presence of Co²⁺ species yields lower methane selectivity but higher olefin selectivity. The activities and selectivities are found to be stable for 55 h on-stream.     

Quasi-crystalline Al<Subscript>70</Subscript>Cu<Subscript>20</Subscript>Fe<Subscript>10</Subscript> by thermal explosion: Effect of AlCu doping on magnetic properties

Polycrystalline quasi-crystals of icosahedral Al₇₀Cu₂₀Fe₁₀(i-Al₇₀Cu₂₀Fe₁₀) were prepared by thermal explosion (TE) of mechanically activated mixture of Al, Cu, Fe powders doped with AlCu. The effect of AlCu dopant was studied by XRD, field emission scanning electron (FESEM), optical microscopy (OM), atomic emission spectroscopy (AES), and energy-dispersive X-ray microanalysis (EDX). The synthesized i-Al₇₀Cu₂₀Fe₁₀ and intermetallics (Al₃Fe, Al₂Cu) show soft ferromagnetic and paramagnetic properties, respectively.      

EPR study of compounds in the LaAlO<Subscript>3</Subscript>-La<Subscript>0.67</Subscript>Sr<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> system

The EPR spectra of compounds in the LaAlO₃-La_0.67Sr_0.33Mn _y O₃ system at a frequency of 9.4 GHz have been investigated at the temperatures T = 77 and 300 K as a function of the manganese concentration y (y = 0.015, 0.030, 0.080). It has been revealed that, in the paramagnetic state at y = 0.015, there exist isolated Mn²⁺ and Mn⁴⁺ ions, which has been confirmed by simulating the EPR spectra. The parameters of the EPR spectra have been determined. The effective magnetic moments μ_eff of the Mn²⁺ and Mn⁴⁺ ions have been calculated from the EPR spectra. It has been demonstrated that an increase in the Mn concentration leads to a decrease in the number of isolated ions and to the formation of new spin clusters. This manifests itself in the predominance of a broad line with weak traces of the hyperfine structure due to the isolated manganese ions.     

Preparation of stable magnetic nanofluids containing Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@PPy nanoparticles by a novel one-pot route

Stable magnetic nanofluids containing Fe₃O₄@Polypyrrole (PPy) nanoparticles (NPs) were prepared by using a facile and novel method, in which one-pot route was used. FeCl₃·6H₂O was applied as the iron source, and the oxidizing agent to produce PPy. Trisodium citrate (Na₃cit) was used as the reducing reagent to form Fe₃O₄ NPs. The as-prepared nanofluid can keep long-term stability. The Fe₃O₄@PPy NPs can still keep dispersing well after the nanofluid has been standing for 1 month and no sedimentation is found. The polymerization reaction of the pyrrole monomers took place with Fe³⁺ ions as the initiator, in which these Fe³⁺ ions remained in the solution adsorbed on the surface of the Fe₃O₄ NPs. Thus, the core-shell NPs of Fe₃O₄@PPy were obtained. The particle size of the as-prepared Fe₃O₄@PPy can be easily controlled from 7 to 30 nm by the polymerization reaction of the pyrrole monomers. The steric stabilization and weight of the NPs affect the stability of the nanofluids. The as-prepared Fe₃O₄@PPy NPs exhibit superparamagnetic behavior.     

Li<Subscript>2</Subscript>Cu<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> + SiO<Subscript>2</Subscript>/Ti compositions for the catalytic afterburning of diesel soot

Two methods were used to obtain a catalytically active oxide coating on the surface of titanium for the catalytic afterburning of diesel soot: plasma electrochemical formation of an oxide film on the surface of titanium and extraction pyrolytic deposition of the Li₂Cu₂(MoO₄)₃ compound. The Li₂Cu₂(MoO₄)₃/TiO₂ + SiO₂/Ti compositions synthesized by the single-step extraction pyrolytic treatment of the oxidized surface of titanium ensured a high burning rate of soot of ∼300°C. The subsequent deposition of Li₂Cu₂(MoO₄)₃ lowers the activity of the catalyst, due probably to the growth of molybdate phase crystallites and the filling of open oxide film pores. Double lithium-copper molybdate is able to reduce appreciably the concentration of CO in the oxidation products of soot. The advantages of these methods are the possibility of forming high-cohesion durable coatings on surfaces of any complexity, the simplicity of their implementation, and high productivity and low cost. The obtained results can be recommended for use in developing methods for creating composite coatings on catalytic soot filters.     

Effect of CeO<Subscript>2</Subscript>-addition sequence on the performance of CeO<Subscript>2</Subscript>-modified Ni/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst in autothermal reforming of iso-octane

Two types of CeO₂-modified Ni/Al₂O₃ catalysts were prepared by a consecutive impregnation method with different sequences in the impregnation of Ni and CeO₂, and their performance in autothermal reforming (ATR) of isooctane was investigated. Catalysts prepared by adding CeO₂ prior to the addition of Ni, Ni/CeO₂-Al₂O₃, produced larger amounts of hydrogen than those obtained using catalysts prepared by adding the two components in an opposite sequence, Ni-CeO₂/Al₂O₃. The results of H₂ chemisorption and temperature-programmed reduction revealed that added CeO₂ increased the dispersion of the Ni species on Al₂O₃ and suppressed the formation of NiAl₂O₄ in the catalyst such that large amounts of Ni species were present as NiO, the active species for the ATR. The elemental and thermogravimetric analyses of deactivated catalysts indicated that Ni/CeO₂-Al₂O₃, which showed a longer lifetime than Ni-CeO₂/Al₂O₃, contained lesser amounts and different types of coke on the surface.