NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> polyhedra with controllable particle size as high-performance anode for lithium-ion battery

Different particle sizes of dodecahedron precursors are synthesized by controlling the polarity of the solution. Through the results of scanning electron microscope (SEM) images, it can be found that different particle sizes of precursors present obvious edge angles and their morphology can be well retained after annealing. X-ray diffraction (XRD) measurements suggest that the annealed polyhedral products are pure single-phase NiCo₂O₄. When tested as lithium-ion battery anode, 0.5 μm NiCo₂O₄ polyhedra exhibits a specific capacity of 1050 mAh g^?1 at 0.1 C at the 60th cycle, which was higher than theoretical capacity of single metal oxide (NiO 718 mAh g^?1 and Co₃O₄ 890 mAh g^?1). It also exhibits the highest rate capability with an average discharge capacity of 890, 700, 490, 330, and 300 mAh g^?1 at 0.5, 2, 4, 8, and 10 C, respectively. Those advantages are attributed to that small-sized particle with great surface areas decrease the actual current density at the surface and inner of the prepared electrode.     

Methane sensor based on SnO<Subscript>2</Subscript>/In<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanostructure

Two sets of samples of SnO₂/In₂O₃/TiO₂ system have been fabricated with different concentrations of component materials. In the first set TiO₂ with rutile structure was used, while in the second set it has the structure of anatase. Thin films (up to 50 nm) of obtained mixtures were deposited. Their sensitivity and selectivity with respect to methane (CH4) were studied. Nanostructure on the basis of 70%SnO₂ — 10%In₂O₃ — 20%TiO₂(anatase) exhibits sufficient sensitivity to methane.     

Influence of the preparation method on the morphology of templated NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel

The synthesis of NiCo₂O₄ spinel by several nanocasting strategies (i.e., multi-step nanocasting, one-step nanocasting and soft-templating), in which nickel and cobalt nitrates are used as precursors and Pluronic P123 as surfactant, is explored. First, in the multi-step nanocasting, the effect of the impregnation method (evaporation, solid–liquid and two-solvent) of the SBA-15 silica template on the morphology of NiCo₂O₄ replica is investigated. The evaporation method seems to be the best choice to obtain mesoporous NiCo₂O₄ powder which, after calcination at 375 °C and subsequent template removal, displays the highest surface area (93.1 m²/g). We have also checked the feasibility of the one-step nanoscating approach for the synthesis of ordered NiCo₂O₄ arrays, though this methodology entails severe difficulties, mainly related to the different decomposition temperature of the nitrate precursors and the P123 surfactant. Finally, randomly oriented, aggregated NiCo₂O₄ nanoparticles are obtained by means of P123 surfactant-assisted soft-templating approach.     

Electrosprayed NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles for long cycle life and high-power Li-ion battery anode

Electrospraying-based synthesis of NiCo₂O₄ (NCO-ES) nanoparticles that exhibit long cycle life and high rate capability is reported. The results are compared with a conventionally prepared NiCo₂O₄ sample by direct annealing (NCO-DA). The structure and morphology of NCO-ES and NCO-DA nanoparticles have been characterized by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy to confirm the size, morphology, structure, and surface chemistry of the as-prepared samples. Electrochemical testing established that the NCO-ES sample displayed enhanced Li-ion storage performance. The NCO-ES delivered a discharge capacity of almost 370 mAh/g at the end of 50 cycles at 1C rate (890 mA/g) while only 180 mAh/g was retained for the NCO-DA sample at the same condition. At a high rate of 5C (4450 mA/g), NCO-ES electrodes delivered a stabilized specific capacity of 225 mAh/g with almost 100% Coulombic efficiency over 1000 cycles. Its rate capability and cycle life were found to be superior to NCO-DA electrodes. The nanoscale grain boundaries in the NCO-ES sample enhanced the lithium-ion diffusion and enabled high rate capability. The impedance analysis at different stages of lithiation/delithiation indicates a lower impedance and better kinetics as one of the reasons for better performance of the NCO-ES sample.     

Formation of three-dimensional arrays of magnetic clusters NiO,Co<Subscript>3</Subscript>O<Subscript>4</Subscript>, and NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> by the matrix method

A method has been proposed for the formation of three-dimensional arrays of isolated magnetic clusters NiO, Co₃O₄, and NiCo₂O₄ in the sublattice of pores in the matrix of bulk synthetic opals through a single impregnation of the pores with melts of nickel and cobalt nitrate crystal hydrates and their thermal degradation. The method makes it possible to controllably vary the degree of filling of pores in the matrix with oxides within 10–70 vol %. The composition and structure of the synthesized materials, as well as the dependences of their static magnetic susceptibility on the magnetic field strength, have been investigated.     

Elevated electrochemical property of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> originated from nano-sized Mn<Subscript>3</Subscript>O<Subscript>4</Subscript>

By employment of nano-sized pre-prepared Mn₃O₄ as precursor, LiMn₂O₄ particles have been successfully prepared by facile solid state method and sol-gel route, respectively. And the reaction mechanism of the used precursors of Mn₃O₄ is studied. The structure, morphology, and element distribution of the as-synthesized LiMn₂O₄ samples are characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Compared with LiMn₂O₄ synthesized by facile solid state method (SS-LMO), LiMn₂O₄ synthesized by modified sol-gel route (SG-LMO) possesses higher crystallinity, smaller average particle size (~175 nm), higher lithium chemical diffusion coefficient (1.17 × 10^?11 cm² s^?1), as well as superior electrochemical performance. For example, the cell based on SG-LMO can deliver a capacity of 85.5 mAh g^?1 at a high rate of 5 °C, and manifests 88.3% capacity retention after 100 cycles at 0.5 °C when cycling at 45 °C. The good electrochemical performance of the cell based on SG-LMO is ascribed mainly to its small particle size, high degree of dispersion, and uniform element distribution in bulk material. In addition, the lower polarization potential accelerates Li⁺ ion migration, and the lower atom location confused degree maintains integrity of crystal structure, both of which can effectively improve the rate capability and cyclability of SG-LMO.     

Ionic liquid-based electrolyte with dual-functional LiDFOB additive toward high-performance LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> batteries

Manganese oxide-based cathodes are one of the most promising lithium-ion battery (LIB) cathode materials due to their cost-effectiveness, high discharge voltage plateau (above 4.0 V vs. Li/Li⁺), superior rate capability, and environmental benignity. However, these batteries using conventional LiPF₆-based electrolytes suffer from Mn dissolution and poor cyclic capability at elevated temperature. In this paper, the ionic liquid (IL)-based electrolytes, consisting of 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfon)imidate (PYR_1,4-TFSI), propylene carbonate (PC), lithium bis(trifluoromethanesulfon)imide (LiTFSI), and lithium oxalyldifluoroborate (LiDFOB) additive, were explored for improving the high temperature performance of the LiMn₂O₄ batteries. It was demonstrated that LiTFSI-ILs/PC electrolyte associated with LiDFOB addition possessed less Mn dissolution and Al corrosion at the elevated temperature in LiMn₂O₄/Li batteries. Cyclic voltammetry and electrochemical impedance spectroscopy implied that this kind of electrolyte also contributed to the formation of a highly stable solid electrolyte interface (SEI), which was in accordance with the polarization measurement and the Li deposition morphology of the symmetric lithium metal cell, thus beneficial for improving the cycling performance of the LiMn₂O₄ batteries at the elevated temperature. Cyclic voltammetry and electrochemical impedance spectroscopy implied that the cells using this kind of electrolyte exhibited better interfacial stability, which was further verified by the polarization measurement and the Li deposition morphology of the symmetric lithium metal cell, thus beneficial for improving the cycling performance of the LiMn₂O₄ batteries at the elevated temperature. These unique characteristics would endow this kind of electrolyte a very promising candidate for the manganese oxide-based batteries.     

Gas sensor based on nanosize In<Subscript>2</Subscript>O<Subscript>3</Subscript>:Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> film

Nanosize films of In₂O₃:Ga₂O₃ (96:4 weight %) have been deposited on a glassceramic substrate by the method of rf magnetron sputtering. The surfaces of fabricated films were studied with use of a scanning electron microscope; sizes of grains were determined and the thicknesses of films were measured. In order to prepare a gas-sensitive structure, a thin catalytic palladium layer and ohmic comb contacts were deposited on the In₂O₃:Ga₂O₃ film surface by the method of ion-plasma sputtering. The sensitivity of sensors based on the glassceramic/In₂O₃:Ga₂O₃ (96:4 weight %)/Pd structure to different concentrations of propane and butane gas mixture, as well as to methane was investigated at temperatures of working substance from 250 to 300°C.     

Structural Aspects of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> Magnetic Nanoparticles According to X-Ray and Neutron Scattering

Structural aspects of powders containing magnetic nanoparticles Fe₃O₄/CoFe₂O₄ with the anticipated “core-shell” structure are considered by means of comparative analysis with individual particles of Fe₃O₄, CoFe₂O₄ in accordance of data obtained from X-ray powder diffraction and small-angle scattering of X-ray (synchrotron) radiation and neutrons. It is shown that magnetic particles in the powders under study have a strong polydispersity and form complex aggregates. Characteristic sizes of the crystallites, as well as a ratio of magnetite to cobalt-ferrite in the composition of the Fe₃O₄/CoFe₂O₄ particles were evaluated from the analysis of the diffraction peaks. Аnalyzing the data on small-angle scattering, the dimensional characteristics of particles and aggregates, as well as the volume fraction of the last ones in the powders, have been obtained. Fractal dimensions of aggregates are determined. A significant difference is observed in the scattering on Fe₃O₄/CoFe₂O₄ particles and the total scattering consisting of partial contributions to scattering on individual magnetite (Fe₃O₄) and cobalt-ferrite (CoFe₂O₄) powders, which does not exclude the formation of the “core-shell” structure.     

Fabrication of urchin-like NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> microspheres assembled by using SDS as soft template for anode materials of Lithium-ion batteries

In this paper, the urchin-like NiCo₂O₄ microspheres assembled by using sodium dodecyl sulfate (SDS) as soft template are successfully fabricated by a facile procedure including microemulsion-solvothermal reaction and subsequent calcination at 400 °C for 4 h. The structure and morphology of synthesized NiCo₂O₄ particles are investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It has been clearly revealed that the prepared three-dimensional urchin-like NiCo₂O₄ microspheres are constituted by one-dimension nanowires. As it is applied to anode for lithium-ion batteries (LIBs), the initial coulombic efficiency is up to 75.7%, and the specific reversible capacity retains up to 1034.2 mAh/g even after 40 cycles at a current density of 100 mA/g. Furthermore, as the current density gradually increases to 800 mA/g, it still delivers the reversible capacity of 895.4 mAh/g. The high reversible specific capacity, perfect cyclability, and rate performance are attributed to the unique urchin-like NiCo₂O₄ microspheres, which can alleviate the volume expansion and shorten the diffusion path of ions and electrons during lithiation/delithiation process. The self-standing urchin-like NiCo₂O₄ microspheres may be a very promising candidate in place of the commercial graphite-based anode materials for high-performance LIBs.     

3D porous NiMoO<Subscript>4</Subscript> nanoflakes arrays for advanced supercapacitor electrodes

In recent years, supercapacitors have been considered as one of the auspicious energy storage devices. In this work, two different kinds of mixed metal oxide NiMoO₄ nanoflakes arrays were directly grown on 3D Ni foam. The electrode exhibited high specific capacitance of 2004 F/g at the current density of 2 A/g in 6 M KOH electrolyte. Additionally, it also exhibited low equivalent series resistance of 0.62 Ω and excellent cycling stability (80% capacitance retention after 1000 cycles). With these extraordinary electrochemical properties, the electrode material can be considered as potential candidate for supercapacitor applications.     

Spin dynamics in LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> and NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> low-dimensional helical magnets

Comprehensive NMR investigation of low-frequency spin dynamics of LiCu₂O₂ (LCO) and NaCu₂O₂ (NCO) low-dimensional helical magnets in the paramagnetic state has been carried out for the first time. Temperature dependences of the spin–lattice relaxation rate and anisotropy on various LCO/NCO nuclei have been determined at various orientations of single crystals in an external magnetic field. The spatial asymmetry of spin fluctuations in LCO multiferroic has been discovered. The quantitative analysis of the anisotropy of spin–lattice relaxation in LCO/NCO has allowed estimating the contributions of individual neighboring Cu²⁺ ions to the transferred hyperfine field on Li⁺(Na⁺) ions.     

Electronic excitations in BeAl<Subscript>2</Subscript>O<Subscript>4</Subscript>, Be<Subscript>2</Subscript>SiO<Subscript>4</Subscript>, and Be<Subscript>3</Subscript>Al<Subscript>2</Subscript>Si<Subscript>6</Subscript>O<Subscript>18</Subscript> crystals

Low-temperature (T = 7 K) time-resolved selectively photoexcited luminescence spectra (2–6 eV) and luminescence excitation spectra (8–35 eV) of wide-bandgap chrysoberyl BeAl₂O₄, phenacite Be₂SiO₄, and beryl Be₃Al₂Si₆O₁₈ crystals have been studied using time-resolved VUV spectroscopy. Both the intrinsic luminescence of the crystals and the luminescence associated with structural defects were assigned. Energy transfer to impurity luminescence centers in alexandrite and emerald was investigated. Luminescence characteristics of stable crystal lattice defects were probed by 3.6-MeV accelerated helium ion beams.     

Synthesis of ZnAl<Subscript>2</Subscript>O<Subscript>4</Subscript>/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> complex substrates and growth of GaN films

With the solid phase reaction between pulsed-laser-deposited (PLD) ZnO film and α-Al₂O₃ substrate, ZnAl₂O₄/α-Al₂O₃ complex substrates were synthesized. X-ray diffraction (XRD) spectra show that as the reaction proceeds, ZnAl₂O₄ changes from the initial (111)-oriented single crystal to poly-crystal, and then to inadequate (111) orientation. Corresponding scanning electron microscope (SEM) images indicate that the surface morphology of ZnAl₂O₄ transforms from uniform islands to stick structures, and then to bulgy-line structures. In addition, XRD spectra present that ZnAl₂O₄ prepared at low temperature is unstable at the environment of higher temperature. On the as-obtained ZnAl₂O₄/α-Al₂O₃ substrates, GaN films were grown without any nitride buffer using light-radiation heating low-pressure MOCVD (LRH-LP-MOCVD). XRD spectra indicate that GaN film on this kind of complex substrate changes fromc-axis single crystal to poly-crystal as ZnAl₂O₄ layer is thickened. For the single crystal GaN, its full width at half maximum (FWHM) of X-ray rocking curve is 0.4°. Results indicate that islands on thin ZnAl₂O₄ layer can promote nucleation at initial stage of GaN growth, which leads to the (0001)-oriented GaN film.     

Pulsed laser deposition of BaGa<Subscript>2</Subscript>O<Subscript>4</Subscript>

This paper reports the first results obtained on monobarium gallate thin films grown on silicon and platinum coated substrates by pulsed laser deposition. The influence of oxygen background pressure and substrate (or post-annealing) temperature on the film properties was studied. The films were characterized by XRD, RHEED, AFM, photoelectron and electrical impedance spectroscopy. The structure analysis showed that the films crystallized into a hexagonal phase, most probably into (metastable) α-BaGa₂O₄. Depending on deposition conditions, films with different (from nearly epitaxial to polycrystalline) textures were obtained.     

Co<Subscript>3</Subscript>O<Subscript>4</Subscript>@MnO<Subscript>2</Subscript> core shell arrays on nickel foam with excellent electrochemical performance for aqueous asymmetric supercapacitor

At present, a lot of attention has been paid to the reasonable design and synthesis of materials with core shell structure for high-performance supercapacitors. Herein, the Co₃O₄@MnO₂ core shell arrays on nickel foam are successfully synthesized via a facile and effective hydrothermal method followed with annealing process. The sample was characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Electrochemical performance of the Co₃O₄@MnO₂ material was studied using cyclic voltammetry, charge/discharge cycling, and electrochemical impedance measurements in 6 mol L^?1 KOH aqueous electrolyte. The results indicated that the Co₃O₄@MnO₂ material presented excellent electrochemical performance in terms of specific capacitance, cyclic stability, and charge/discharge stability.     

Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/functional exfoliation graphene on carbon paper nanocomposites for supercapacitor electrode

In this work, the commercial carbon paper was firstly peeled in K₂CO₃ solution and then was further treated in a KNO₃ solution to form functional exfoliation graphene (FEG) on the commercial carbon paper. The FEG/carbon paper was characterized by Raman spectra and scanning electron microscopy, confirming that some typical layered fold graphenes were successfully peeled off and stood on the carbon paper matrix. Then, Fe₃O₄ nanoparticles (NPs) were grown on the surface of FEG/carbon paper and the as-prepared Fe₃O₄ NPs/FEG/carbon paper was directly used as supercapacitor electrode. The specific capacitance of Fe₃O₄ NPs/FEG/carbon paper was about 316.07 F g^?1 at a current density of 1 A g^?1. Furthermore, the FEG/carbon papers were also functionalized by benzene carboxylic acid to form FFEG/carbon papers, and then the Fe₃O₄ NPs were grown on the surface of FFEG/carbon paper. The specific capacitance of Fe₃O₄ NPs/FFEG/carbon paper was 470 F g^?1 at a current density of 1 A g^?1, superior to some previous reported results. This work might provide a new strategy to prepare various nanostructures on FFEG/carbon papers for future applications.     

The magnetization reversal in CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/CoFe<Subscript>2</Subscript> granular systems

The temperature-dependent field cooling (FC) and zero-field cooling (ZFC) magnetizations, i.e., M _FC and M _ZFC, measured under different magnetic fields from 500 Oe to 20 kOe have been investigated on two exchange–spring CoFe₂O₄/CoFe₂ composites with different relative content of CoFe₂. Two samples exhibit different magnetization reversal behaviors. With decreasing temperature, a progressive freezing of the moments in two composites occurs at a field-dependent irreversible temperature T _irr. For the sample with less CoFe₂, the curves of ?d(M _FC ? M _ZFC)/dT versus temperature T exhibit a broad peak at an intermediate temperature T ₂ below T _irr , and the moments are suggested not to fully freeze till the lowest measuring temperature 10 K. However, for the ?d(M _FC ? M _ZFC)/dT curves of the sample with more CoFe₂, besides a broad peat at an intermediate temperature T ₂, a rapid rise around the low temperature T ₁~15 K is observed, below which the moments are suggested to fully freeze. Increase of magnetic field from 2 kOe leads to the shift of T ₂ and T _irr towards a lower temperature, and the shift of T ₂ is attributable to the moment reversal of CoFe₂O₄.

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Graphical abstract CoFe₂O₄/CoFe₂ composites with different relative content of CoFe₂ were prepared by reducing CoFe₂O₄ in H₂ for 4 h (S4H) and 8 h (S8H). The temperature-dependent FC and ZFC magnetizations, i.e., M _FC and M _ZFC, under different magnetic fields from 500 Oe to 20 kOe have been investigated. Two samples exhibit different magnetization reversal behaviors. With decreasing temperature, a progressive freezing of the moments in two composites occurs at field-dependent irreversible temperature T _irr. For the S4H sample, the curves of ?d(M _FC ? M _ZFC)/dT versus temperature T exhibit a broad and field-dependent relaxing peak at T ₂ below T _irr (figure a), and the moments were suggested not to fully freeze till the lowest measuring temperature 10 K. However, for the S8H sample, it exhibits the reentrant spin-glass state around 50 K, as evidenced by a peak in the M _FC curve (inset in figure b) and as a result of the cooperative effects of the random anisotropy of CoFe₂O₄, exchange–spring occurring at the interface of CoFe₂O₄ and CoFe₂ together with the inter-particle dipolar interaction (figure c); in ?d(M _FC ? M _ZFC)/dT curves, besides a broad relaxing peat at T ₂, a rapid rise around the low-temperature T ₁~15 K is observed, below which the moments are suggested to fully freeze. Increase of magnetic field from 2 kOe leads to the shift of T ₂ and T _irr towards a lower temperature, and the shift of T ₂ is attributable to the moment reversal of CoFe₂O₄.

     

Magnetic properties and local configurations of <Superscript>57</Superscript>Fe atoms in CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> powders and CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/PVA nanocomposites

The composition and magnetic properties of the powders extracted from CoFe₂O₄ aqueous suspensions and the CoFe₂O₄/PVA (PVA is polyvinyl alcohol) nanocomposites with a cobalt ferrite content of 10–30 wt % have been investigated using Mössbauer spectroscopy, transmission electron microscopy, and vibration magnetometry. The cationic formulas of the cobalt ferrites synthesized have been determined. The differences between samples synthesized at temperatures of 72.5 and 82.5°C have been revealed. The specific features of the observed changes in the agglomeration of CoFe₂O₄ particles after introducing into the PVA matrix have been studied. It has been shown that the iron ion distribution determined by Mössbauer spectroscopy in octahedral and tetrahedral lattice sites correlates with vibration magnetometry data.     

Evolution of MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> crystals in Al-Mg-SiO<Subscript>2</Subscript> composites

The present study analyzes the morphological transformations of reaction products i.e., MgO, MgAl₂O₄ occurring during the reaction between SiO₂ and Al-Mg alloy in Al-Mg-SiO₂ composite processed by the liquid metallurgy technique. Different phases of platelet and hexagonal morphologies are detected and their composition analysis by EDS has confirmed them as being transition phases existing between MgO, MgAl₂O₄ and Al₂O₃. This study has also revealed the gradual transformation of (i) MgO needles to octahedral MgAl₂O₄ through Mg-Al-Si-O and Mg-Al-O transition phases having platelet morphologies and (ii) MgAl₂O₄ to Al₂O₃ through hexagonal transition phases on holding of Al-5Mg-SiO₂ and Al-1Mg-SiO₂ composites respectively at 1023K. Fully developed α-Al₂O₃ crystals are not observed under the present experimental conditions, wherein the Mg content is well above the equilibrium Mg content required for the formation of stable Al₂O₃ (<0.05 wt. %). PACS 05.70.Np