Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

Understanding δ-Bi2O3 fluorite degradation mechanism and related solutions for promising applications in distributed multigeneration

Oxygen selective membrane on the base of cermet δ-Bi₂O₃/Ag with an interpenetrating structure has the maximum potential efficiency of air separation. However, the degradation processes, including the phase degradation of fluorite δ-Bi₂O₃, do not make it possible to create a membrane with the required perfection and durability. In this work, the ordering of oxygen vacancies with the transformation of fluorite into the rhombohedral phase (S.G. R-3) was studied by powder HT XRD in situ at 600 °C on dense Bi_0.78Er_0.2Hf_0.02O_1.51 ceramics. Fast regeneration of disordered fluorite occurs at T = 640–700 °C. The phase degradation of fluorite due to the segregation of dopants at the second stage leads into stable phases - sillenite, tetragonal or rhombohedral phase (S.G. R-3m), depending on the composition of δ-Bi₂O₃. Fast regeneration of fluorite occurs when heated to 820 °C, which is unacceptable for membranes. Analysis of all available data allows us to propose approaches to optimize the composition of δ-Bi₂O₃ and technical solutions for creating durable oxygen selective membranes with promising use in distributed multigeneration. As a result of the analysis, a new solid electrolyte with better parameters was obtained.     

Microwave assisted-in situ synthesis of porous titanium/calcium phosphate composites and their in vitro apatite-forming capability

Microwave irradiation has been proven to be an effective heating source in synthetic chemistry, and can accelerate the reaction rate, provide more uniform heating and help in developing better synthetic routes for the fabrication of bone-grafting implant materials. In this study, a new technique, which comprises microwave heating and powder metallurgy for in situ synthesis of Ti/CaP composites by using Ti powders, calcium carbonate (CaCO₃) powders and dicalcium phosphate dihydrate (CaHPO₄·2H₂O) powders, has been developed. Three different compositions of Ti:CaCO₃:CaHPO₄·2H₂O powdered mixture were employed to investigate the effect of the starting atomic ratio of the CaCO₃ to CaHPO₄·2H₂O on the phase, microstructural formation and compressive properties of the microwave synthesized composites. When the starting atomic ratio reaches 1.67, composites containing mainly alpha-titanium (α-Ti), hydroxyapatite (HA), beta-tricalcium phosphate (β-TCP) and calcium titanate (CaTiO₃) with porosity of 26%, pore size up to 152 μm, compressive strength of 212 MPa and compressive modulus of 12 GPa were formed. The in vitro apatite-forming capability of the composite was evaluated by immersing the composite into a simulated body fluid (SBF) for up to 14 days. The results showed that biodissolution occurred, followed by apatite precipitation after immersion in the SBF, suggesting that the composites are suitable for bone implant applications as apatite is an essential intermediate layer for bone cells attachment. The quantity and size of the apatite globules increased over the immersion time. After 14 days of immersion, the composite surface was fully covered by an apatite layer with a Ca/P atomic ratio approximately of 1.68, which is similar to the bone-like apatite appearing in human hard tissue. The results suggested that the microwave assisted-in situ synthesis technique can be used as an alternative to traditional powder metallurgy for the fabrication of Ti/CaP biocomposites.     

Annealing temperature dependent structural and optical properties of electrodeposited CdSe thin films

Cadmium selenide films were synthesized using simple electrodeposition method on indium tin oxide coated glass substrates. The synthesized films were post annealed at 200 °C, 300 °C and 400 °C. X-ray diffraction of the films showed the hexagonal structure with crystallite size <3 nm for as deposited films and 3–25 nm for annealed films. The surface morphology of films using field emission scanning electron microscopy showed granular surface. The high resolution transmission electron microscopy of a crystallite of the film revealed lattice fringes which measured lattice spacing of 3.13 Å corresponding to (002) plane, indicating the lattice contraction effect, due to small size of CdSe nanocrystallite. The calculation of optical band gap using UV–visible absorption spectrum showed strong red-shift with increase in crystallite size, indicating to the charge confinement in CdSe nanocrystallite.     

Amination of biochar surface from watermelon peel for toxic chromium removal enhancement

Watermelon peel residues were used to produce a new biochar by dehydration method. The new biochar has undergone two methods of chemical modification and the effect of this chemical modification on its ability to adsorb Cr(VI) ions from aqueous solution has been investigated. Three biochars, Melon-B, Melon-BO-NH_2 and Melon-BO-TETA, were made from watermelon peel via dehydration with 50% sulfuric acid to give Melon-B followed by oxidation with ozone and amination using ammonium hydroxide to give Melon-BO-NH_2 or Triethylenetetramine(TETA) to give Melon-BO-TETA. The prepared biochars were characterized by BET, BJH,SEM, FT-IR, TGA, DSC and EDAX analyses. The highest removal percentage of Cr(VI) ions was 69% for Melon-B,98% for Melon-BO-NH_2 and 99% for Melon-BO-TETA biochars of 100 mg·L~(-1) Cr(VI) ions initial concentration and 1.0 g·L~(-1) adsorbents dose. The unmodified biochar(Melon-B) and modified biochars(Melon-BO-NH_2 and Melon-BO-TETA) had maximum adsorption capacities(Qm) of 72.46, 123.46, and 333.33 mg·g~(-1), respectively.The amination of biochar reduced the pore size of modified biochar, whereas the surface area was enhanced.The obtained data of isotherm models were tested using different error function equations. The Freundlich,Tempkin and Langmuir isotherm models were best fitted to the experimental data of Melon-B, Melon-BO-NH_2 and Melon-BO-TETA, respectively. The adsorption rate was primarily controlled by pseudo-second–order rate model. Conclusively, the functional groups interactions are important for adsorption mechanisms and expected to control the adsorption process. The adsorption for the Melon-B, Melon-BO-NH_2 and Melon-BO-TETA could be explained for acid–base interaction and hydrogen bonding interaction.     

In situ characterization of LiY(WO4)2 nanotubes for electrochemical energy storage

Here, LiY(WO₄)₂ nanotubes are prepared via a feasible electrospinning technique. This new anode material shows excellent electrochemical properties. The capacity loss of LiY(WO₄)₂ nanotubes is as low as 6.9% after 156 cycles, while bulk LiY(WO₄)₂ presents the capacity loss higher than 55.0%. Even after 600 long-life cycles, the capacity loss of the nanotubes is only 9%. It can be seen that the hollow structure with a rough surface and a porous morphology contributes to the improvement of electrochemical performance. Furthermore, online X-ray diffraction (XRD) method is firstly applied to understand the lithium ions insertion/extraction mechanism of LiY(WO₄)₂ nanotubes. It can be concluded that it is an asymmetrical two-phase reaction. A phase transformation from LiY(WO₄)₂ to Li₃Y(WO₄)₂ can be obviously seen from the in situ XRD during discharge process. While Li₂Y(WO₄)₂ appears as an intermediate phase with a reverse charge reaction. In addition, in situ XRD also demonstrates that LiY(WO₄)₂ nanotubes have surprised electrochemical reversibility. All the above results indicate that LiY(WO₄)₂ nanotubes can be expected to be anode candidate for rechargeable lithium ion batteries (LIBs).     

Synthesis and in vitro bioactivity assessment of injectable bioglass−organic pastes for bone tissue repair

The aim of this work was to study the bioactivity of systems based on a clinically tested bioactive glass (BG) particulates (mol%: 4.33 Na₂O−30.30 CaO−12.99 MgO−45.45 SiO₂−2.60 P₂O₅−4.33 CaF₂) and organic carriers. The cohesiveness of injectable bone graft products is of high relevance when filling complex volumetric bone defects. With this motivation behind, BG particulates with mean sizes within 11−14 μm were mixed in different proportions with glycerol (G) and polyethylene glycol (PEG) as organic carriers and the mixtures were fully injectable exhibiting Newtonian flow behaviors. The apatite forming ability was investigated using X-ray diffraction and field emission scanning electron microscopy under secondary electron mode after immersion of samples in simulated body fluid (SBF) for time durations varying between 12 h and 7 days. The results obtained revealed that in spite of the good adhesion of glycerol and PEG carriers to glass particles during preparation stage, they did not hinder the exposure of bioactive glass particulates to the direct contact with SBF solution. The results confirmed the excellent bioactivity in vitro for all compositions expressed by high biomineralization rates with the formation of crystalline hydroxyapatite being identified by XRD after 12 h of immersion in SBF solution.     

Synthesis and characterization of Manganese doped Tungsten oxide by Microwave irradiation method

The aim of this article is to synthesis tungsten oxide (WO₃) nanoparticle along with Manganese (3 wt% and 10 wt%) by Microwave irradiation method. The physical properties of the synthesized Manganese doped Tungsten oxide materials were characterized by X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Transmission Electron Microscope (TEM), UV-Diffuse Reflectance Spectroscopy, SEM-EDAX and Photoluminescence studies. The predominant peaks obtained in X-ray diffraction pattern reveal the crystalline nature of the nanoparticles and the structure belongs to Monoclinic for pure and Mn doped WO₃. FTIR analysis shows the presence of Tungsten and oxygen in the synthesis material and verified with EDAX. TEM analysis shows both pristine and Mn doped WO₃ nanopaticles. They are having spherical shaped morphology with average particle size from 35 to 40 nm. UV-DRS revealed that the bandgap energy for pure and Manganese doped WO₃ are discussed in this article. The Scanning Electron Microscope analysis shows the plate like morphology for pure WO₃ and the morphology were decreased by doping Manganese. The defects and oxygen deficiencies were analysed by photoluminescence spectroscopy.     

Experimental investigation of Co and Fe-Doped CuO nanostructured electrode material for remarkable electrochemical performance

The current research work presents a facile and cost–effective co-precipitation method to prepare doped (Co & Fe) CuO and undoped CuO nanostructures without usage of any type of surfactant or capping agents. The structural analysis reveals monoclinic crystal structure of synthesized pure CuO and doped-CuO nanostructures. The effect of different morphologies on the performance of supercapacitors has been found in CV (cyclic voltammetry) and GCD (galvanic charge discharge) investigations. The specific capacitances have been obtained 156 (±5) Fg^?1, 168(±5) Fg^?1 and 186 (±5) Fg^?1 for CuO, Co-doped CuO and Fe-doped CuO electrodes, respectively at scan rate of 5 mVs^?1, while it is found to be 114 (±5) Fg^?1, 136 (±5) Fg^?1 and 170 (±5) Fg^?1 for CuO, Co–CuO and Fe–CuO, respectively at 0.5 Ag^-1 as calculated from the GCD. The super capacitive performance of the Fe–CuO nanorods is mainly attributed to the synergism that evolves between CuO and Fe metal ion. The Fe-doped CuO with its nanorods like morphology provides superior specific capacitance value and excellent cyclic stability among all studied nanostructured electrodes. Consequently, it motivates to the use of Fe-doped CuO nanostructures as electrode material in the next generation energy storage devices.