Li-storage and cycling properties of spinel,CdFe<Subscript>2</Subscript>O<Subscript>4</Subscript>, as an anode for lithium ion batteries

Cadmium ferrite, CdFe₂O₄, is synthesized by urea combustion method followed by calcination at 900°C and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED) techniques. The Li-storage and cycling behaviour are examined by galvanostatic cycling, cyclic voltammetry (CV) and impedance spectroscopy in the voltage range, 0·005–3·0 V vs Li at room temperature. CdFe₂O₄ shows a first cycle reversible capacity of 870 (± 10) mAhg⁻¹ at 0·07C-rate, but the capacity degrades at 4 mAhg⁻¹ per cycle and retains only 680 (± 10) mAhg⁻¹ after 50 cycles. Heat-treated electrode of CdFe₂O₄ (300°C; 12 h, Ar) shows a significantly improved cycling performance under the above cycling conditions and a stable capacity of 810 (± 10) mAhg⁻¹ corresponding to 8·7 moles of Li per mole of CdFe₂O₄ (vs theoretical, 9·0 moles of Li) is maintained up to 60 cycles, with a coulombic efficiency, 96–98%. Rate capability of heat-treated CdFe₂O₄ is also good: reversible capacities of 650 (± 10) and 450 (± 10) mAhg⁻¹ at 0·5 C and 1·4 C (1 C = 840 mAg⁻¹) are observed, respectively. The reasons for the improved cycling performance are discussed. From the CV data in 2–15 cycles, the average discharge potential is measured to be ∼0·9 V, whereas the charge potential is ∼2·1 V. Based on the galvanostatic and CV data, ex situ-XRD, -TEM and -SAED studies, a reaction mechanism is proposed. The impedance parameters as a function of voltage during the 1st cycle have been evaluated and interpreted. Dedicated to Prof. C N R Rao on his 75th birthday, and his contributions to science for the past 56 years     

Synthesis,characterization and application of semiconducting oxide (Cu<Subscript>2</Subscript>O and ZnO) nanostructures

In the present study, we report the synthesis, characterization and application of nanostructured oxide materials. The oxide materials (Cu₂O and ZnO) have been synthesized by electrolysis based oxidation and thermal oxidation methods. Cuprous oxide (Cu₂O) nanostructures have been synthesized by anodic oxidation of copper through a simple electrolysis process employing plain water (with ionic conductivity, ～6 μS/m) as electrolyte. In this method no special electrolytes, chemicals and surfactants are needed. The method is based on anodization pursuant to the simple electrolysis of water at different voltages. Two different types of Cu₂O nanostructures have been found. One type got delaminated from copper anode and was collected from the bottom of the electrochemical cell and the other was located on the copper anode itself. The nanostructures collected from the bottom of the cell are either nanothreads embodying beads of different diameters, ～ 10–40 nm or nanowires (length, ～ 600–1000 nm and diameter, ～ 10–25 nm). Those present on the copper anode were nanoblocks with preponderance of nanocubes (nanocube edge, ～ 400 nm). The copper electrode served as a sacrificial anode for the synthesis of different nanostructures. Aligned ZnO nanorod array has been successfully synthesized by simple thermal evaporation catalyst free method. Detailed structural characterizations revealed that the as synthesized aligned ZnO nanorods are single crystalline, with a hexagonal phase, and with growth along the [0001] direction. The room-temperature photoluminescence spectra showed a weak ultraviolet emission at 380 nm, a broad blue band at 435 nm and a strong orange-red emission at 630 nm. Structural/microstructural characterization of these nanomaterials have been carried out employing scanning (XL-20) and transmission electron microscopic (Philips EM, CM-12 and Technai 20G²) techniques and X-ray diffraction techniques having graphite monochromater with CuKα radiation (λ =1.54439 Å) (X’Pert PRO PAN analytical). The UV-visible absorption spectra were recorded on Model-VARIAN, Cary 100, and Bio UV-visible spectrophotometer. The photoluminescence (PL) measurement was carried out at room temperature with a He-Cd, a laser excited at 325 nm.     

Phonons in mixed superionic fluorites (BaF<Subscript>2</Subscript>)<Subscript>1-x</Subscript>(LaF<Subscript>3</Subscript>)<Subscript>x</Subscript>

In recent years, the fluorite-structured solid solutions with the general formula, (MF₂)_1-x(RF₃)_x (M = Ca, Sr, Ba, Pb and R is a rare-earth element or Y), have been the subject of numerous experimental studies focussed on their superionic properties. The overall cubic crystal symmetry (space group Fm3m) is conserved up to x ≶ x_max, where x_max ⊁ 0.4-0.5 depending on M and R. The zone centre phonons and phonon dispersion along three symmetry directions of the mixed superionic compound (BaF₂)_1-x(LaF₃)_x have been investigated by applying de Launey angular force model for x ≶ x_max. The calculated results are compared and explained with available experimental results.     

Effects of talc and clay addition on pressureless sintering of porous Si<Subscript>3</Subscript>N<Subscript>4</Subscript> ceramics

Porous Si₃N₄ ceramics were successfully synthesized using cheaper talc and clay as sintering additives by pressureless sintering technology and the microstructure and mechanical properties of the ceramics were also investigated. The results indicated that the ceramics consisted of elongated β-Si₃N₄ and small Si₂N₂O grains. Fibrous β-Si₃N₄ grains developed in the porous microstructure, and the grain morphology and size were affected by different sintering conditions. Adding 20% talc and clay sintered at 1700°C for 2 h, the porous Si₃N₄ ceramics were obtained with excellent properties. The final mechanical properties of the Si₃N₄ ceramics were as follows: porosity, P ₀ = 45·39%; density, ρ = 1·663·g·cm⁻³; flexural strength, σ _b (average) = 131·59 MPa; Weibull modulus, m = 16·20.     

Nano Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Induced Fluxoid Jumps and Low Field Enhanced Critical Current Density in MgB<Subscript>2</Subscript> Superconductor

Nano particle of Fe₃O₄ (nFe₃O₄) up to 6 at% were doped in the superconducting MgB₂ samples. Despite the strong ferromagnetic nature of Fe₃O₄, both the ac susceptibility and the resistivity measurements show that up to 4 at% of Fe₃O₄, T _c =38 K is not changed, whereas for 6% T _c decreases by 6 K. This indicates that a low concentration of Fe does not substitute either the Mg or B sites and probably occupies the intergrain spaces. For 0.5% doped Fe₃O₄, an increase in J _c with respect to the pure MgB₂ samples is observed in the lower field and temperature regions (H<2 T and 20 K) indicating an enhanced flux pinning and the magnetic activation, i.e., the interaction between the magnetic dipole of Fe ion and the vortices is weak in comparison to the effective pinning potential. Whereas, at H>2 T, J _c of the doped samples is always less than that of MgB₂, and the activation is dominant in comparison with the effective pinning potential provided by the doping. Flux jumps are observed in lower T and H regions for the samples doped up to 1% nFe₃O₄ only. Magnetization plots of higher Fe content samples exhibited clear paramagnetic background. Mossbauer measurements for the higher (4, 6 at%) nFe₃O₄ doped MgB₂ samples show that at RT, the hyperfine field for both samples is ∼100 kOe and ∼120 kOe at 90 K. This means that the nFe₃O₄ particles decompose and form possibly an intermetallic Fe-B phase in the matrix.     

Preparation of microwave dielectric,Sn<Subscript>0.2</Subscript>Zr<Subscript>0.8</Subscript>TiO<Subscript>4</Subscript>

A simple coprecipitation technique is described for the preparation of tin substituted zirconium titanate ceramic powders.     

Room-Temperature Photomagnetic Effect of Fe<Subscript>3</Subscript>Ga<Subscript>4</Subscript> Grown on GaAs Substrates

Ga–As–Fe composite films prepared by molecular beam epitaxy at 600°C on GaAs(100) substrates with the stacking sequence of [100-nm GaAs/50-nm Fe₃Ga_{2− x} As _x /100-nm GaAs] exhibit the distinct photo-enhanced magnetization at room temperature. Transmission electron microscopy reveals the formation of metamagnetic Fe₃Ga₄ grains on the sample surface. Illumination power dependence of the enhanced magnetization has been carefully compared with the antiferromagnetic-type magnetization–temperature (M–T) curve (Neel temperature of T _N = 340–390 K), from which we have discussed the existence of photon-mode photo-enhanced magnetization of some sort in addition with the enhancement due to the light-induced heating.     

Study of gel grown mixed crystals of Ba<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>(IO<Subscript>3</Subscript>)<Subscript>4</Subscript>

The growth of mixed crystals of Ba _x Ca_1−x (IO₃)₄ were carried out with simple gel method. The effect of various parameters such as pH of gel solution, gel concentration, gel setting time, concentration of reactants on the growth was studied. Crystals having different morphologies and habits were obtained. The grown crystals were characterized by XRD, FT-IR, EDAX, TGA, DTA and DSC.     

Impedance analysis of Pb<Subscript>2</Subscript>Sb<Subscript>3</Subscript>LaTi<Subscript>5</Subscript>O<Subscript>18</Subscript> ceramic

Polycrystalline sample of Pb₂Sb₃LaTi₅O₁₈, a member of tungsten- bronze (TB family, was prepared using a high temperature solid- state reaction technique. XRD analysis indicated the formation of a single-phase orthorhombic structure. The dielectric studies revealed the diffuse phase transition and the transition temperature was found to be at 52° C. Impedance plots were used as tools to analyse the sample behaviour as a function of frequency. Cole-Cole plots showed Debye relaxation. The activation energy was estimated to be 0·634 eV from the temperature variation of d.c. conductivity. The nature of variation of d.c. conductivity with temperature suggested NTCR behaviour.     

Superconducting Properties of Iodine-Intercalated Bi<Subscript>2</Subscript>Sr<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>10+<Emphasis Type="Italic">x</Emphasis></Subscript>

The superconducting properties of iodine-intercalated high-temperature superconducting Bi₂Sr₂Ca₂Cu₃O_10+x phase (Bi-2223) were systematically studied. It was found that for samples containing a significant amount of Bi₂Sr₂CaCu₂O_8+x , iodine intercalation results in the dramatic decrease of the inter-granular critical current density, as well as a significant decrease of the critical temperature (T _c), the critical current density in the grains (J _cg), and of the amount of Bi-2223. For samples with a large amount of Bi-2223, T _c changes insignificantly, whereas J _cg can even increase. We argue that the different behavior of the superconducting parameters is the result of various oxygen concentrations, and we explain the effect of iodine intercalation based on the parabolic dependence between T _c and the number of holes per CuO₂ layer. The H(T) curves (determined from the peak position in the loss signal of ac susceptibility) for intercalated samples deviate significantly from the quasi 2D-like behavior, pointing toward an enhancement of the 3D fluctuations of vortices. For the change in the values and dimensionality of the flux pinning in the process of the intercalation, we attempted a qualitative explanation based on the models proposed in literature.     

Spectral parameters of Er<Superscript>3+</Superscript> ion in Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript>:KY(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal

The spectral parameters of Er³⁺ in Yb³⁺/Er³⁺:KY(WO₄)₂ crystal with space group C2/c have been investigated based on Judd-Ofelt theory. The spectral parameters were obtained: the intensity parameters are: ₂ = 6.33 × 10^–20 cm², ₄ = 1.35 × 10^–20 cm², ₆ = 1.90 × 10^–20 cm². The radiative lifetime and the fluorescence branch ratios were calculated. The emission cross section _e (at 1536 nm) is 2.0 × 10^–21 cm².     

Preparation of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> Buffer Layer on LaAlO<Subscript>3</Subscript> Substrate by TFA-MOD Method

Chemical solution deposition is a promising technique for fabrication of high-temperature superconducting films and oxide buffer layers due to its reproducibility and low cost. In this work, Y₂O₃ buffer layers were prepared on (100) LaAlO₃ substrates by mental organic deposition method using trifluoroacetate. The resulting Y₂O₃ films crystallized as a single phase at 900°C and showed a low degree ofc-axis orientation. The scanning electron micrography showed that the surface of the films was smooth with a uniform grain size of approximately 10 nm.     

Morphology and conductivity studies of a new solid polymer electrolyte: (PEG)<Subscript>x</Subscript>LiClO<Subscript>4</Subscript>

A new solid polymer electrolyte, (PEG)_xLiClO₄, consisting of poly(ethylene)glycol of molecular weight 2000 and LiClO₄ was prepared and characterized using XRD, IR, SEM, DSC, NMR and impedance spectroscopy techniques. XRD and IR results show the formation of the polymer-salt complex. The samples with higher salt concentration are softer, less opaque and less smooth compared to the low salt concentration samples. DSC studies show an increase in the glass transition temperature and a decrease in the degree of crystallinity with increase in the salt concentration. Melting temperature of SPEs is lower than the pure PEG 2000. Room temperature¹H and⁷Li NMR studies were also carried out for the (PEG)_xLiClO₄ system. The¹H linewidth decreases as salt concentration increases in a similar way to the decrease in the crystalline fraction and reaches a minimum at aroundx = 46 and then increases.⁷Li linewidth was found to decrease first and then to slightly increase after reaching a minimum atx = 46 signifying the highest mobility of Li ions for this composition. Room temperature conductivity first increases with salt concentration and reaches a maximum value (σ = 7.3 × 10⁻⁷ S/cm) atx = 46 and subsequently decreases. The temperature dependence of the conductivity can be fitted to the Arrhenius and the VTF equations in different temperature ranges. The ionic conductivity reaches a high value of ∼10 ⁻⁴S/cm close to the melting temperature.     

Spectral parameters of Nd<Superscript>3+</Superscript> ion in Sr<Subscript>6</Subscript>NdSc(BO<Subscript>3</Subscript>)<Subscript>6</Subscript> crystal

The spectroscopic study of Nd³⁺ in Sr₆NdSc(BO₃)₆ crystal had been performed. Based on the Judd-Ofelt theory to analyze the optical strengths measured in absorption spectra, the following spectral parameters were obtained: intensity parameters are ₂ = 1.108 × 10^–20 cm², ₄ = 2.884 × 10^–20 cm², ₆ = 3.085 × 10^–20 cm², the radiative lifetime is 385 s, the quantum efficiency is 12.5%. The fluorescence branch ratios were calculated: ₁ = 0.423, ₂ = 0.482, ₃ = 0.092, ₄ = 0.005.     

Enhanced Superconducting Properties of Air-Processed GdBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7-δ</Subscript> Single Domains with BaCO<Subscript>3</Subscript>/BaCuO<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript> Addition

Single domain GdBa₂Cu_7-δ (Gd123) bulk superconductors were fabricated in air by top-seeding melt-texture growth. Performance of the air-processed Gd123 was successfully enhanced by addition of both BaCO₃ and BaCuO_2−x , which suppress the formation of Gd_1+x Ba_2−x Cu₃O_7-δ solid solutions. The optimum doping amount ranges from 0.05 to 0.15, M BaCO₃ and 0.05 to 0.1, M BaCuO_2−x per molar Gd123. The distribution of the second phase particles was observed by scanning electron microscopy. A narrow band formed by Gd₂BaCuO₅ particle concentration appeared around the seeding zone in both a–b plane and c-growth sector in Gd123 single grain. Trapped magnetic field density reached 0.67, T for sample with 24 mm in diameter and 8, mm in thickness and a high critical current density J _c up to 91,200, A/cm² was achieved at 77, K under self-field.     

Synthesis and Optical Studies of Superconducting MgB<Subscript>2</Subscript> Thin Films

Synthesis and optical transmission of MgB₂ thin films on optically transparent glass are reported. In the 400–1000 nm regime as deposited films show high metallic reflectivity and very little transmission. After deposition, the films were annealedex situ and rendered superconducting withT _c of 38 K, approaching that of the bulk material. The reaction conditions where quite soft ∼ 10 min at 550°C. The optical absorption coefficient,α and photon energy,E followed a Tauc-type behavior, (αE)^1/2=β _T(E −E _g). The band gap (E _g) was observed to peak at 2.5 eV; but, the slope parameterβ _Tbehaved monotonically with reaction temperature. Our results indicate that an intermediate semiconducting phase is produced before the formation of the superconducting phase; also optical measurements provide valuable information in monitoring the synthesis of MgB₂ from its metallic constituents. In addition these films have interesting optical properties that may be integrated into optoelectronics.     

X-ray absorption spectroscopy of PbMoO<Subscript>4</Subscript> single crystals

X-ray absorption spectra of PbMoO₄ (LMO) crystals have been investigated for the first time in literature. The measurements have been carried out at Mo absorption edge at the dispersive EXAFS beamline (BL-8) of INDUS-2 Synchrotron facility at Indore, India. The optics of the beamline was set to obtain a band of 2000 eV at 20,000 eV and the channels of the CCD detector were calibrated by recording the absorption edges of standard Mo and Nb foils in the same setting. The absorption spectra have been measured for three LMO samples prepared under different conditions viz. (i) grown in air from stoichiometric starting charge, (ii) grown in argon from stoichiometric starting charge and (iii) grown in air from PbO-rich starting charge. The results have been explained on the basis of the defect structure analysed in LMO crystals prepared under different conditions. The Mo absorption edge is significantly influenced by the deviations in crystal stoichiometry.     

Ethanol gas sensing properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-doped ZnO thick film resistors

The characterization and ethanol gas sensing properties of pure and doped ZnO thick films were investigated. Thick films of pure zinc oxide were prepared by the screen printing technique. Pure zinc oxide was almost insensitive to ethanol. Thick films of Al₂O₃ (1 wt%) doped ZnO were observed to be highly sensitive to ethanol vapours at 300°C. Aluminium oxide grains dispersed around ZnO grains would result into the barrier height among the grains. Upon exposure of ethanol vapours, the barrier height would decrease greatly leading to drastic increase in conductance. It is reported that the surface misfits, calcination temperature and operating temperature can affect the microstructure and gas sensing performance of the sensor. The efforts are, therefore, made to create surface misfits by doping Al₂O₃ into zinc oxide and to study the sensing performance. The quick response and fast recovery are the main features of this sensor. The effects of microstructure and additive concentration on the gas response, selectivity, response time and recovery time of the sensor in the presence of ethanol vapours were studied and discussed.     

Structural,optical and non-linear investigation of Eu<Superscript>3+</Superscript>: Al(NO<Subscript>3</Subscript>)<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> sol-gel glass

Optical absorption and fluorescence spectra of Eu³⁺ ions in Al(NO₃)₃-SiO₂ sol-gel glass have been investigated using the Judd- Ofelt theory. JO intensity parameters (ω _λ ) and subsequent radiative properties for⁵ D ₀ ↔⁷ F _1,2,4,6 transitions are determined. The lifetime (τ_r) of⁵ D ₀ state is computed and along with JO parameters are compared with their corresponding values in other glasses prepared by conventional technique. A structural analysis, using IR and XRD spectra and non- linear parametrization of the silica gel glass is carried out. The study reveals the glass to be a very good third order non- linear amorphous optical material.     

Magnetic properties of ball-milled TbFe<Subscript>2</Subscript> and TbFe<Subscript>2</Subscript>B

The magnetic properties of ball-milled TbFe₂ and TbFe₂B were studied by magnetization measurements. X-ray diffraction studies on TbFe₂B showed that boron occupied interstitial position in the crystal structure, just as hydrogen did. The value of the saturation magnetization of TbFe₂B was found to be smaller than that of TbFe₂. This is explained on the basis of a charge transfer between the boron atoms and the 3d band of Fe. The anisotropy of TbFe₂B was found to be large compared to that of TbFe₂. X-ray diffractograms for the ball milled samples showed that after 80 h of milling, a predominantly amorphous phase was obtained. TbFe₂B was found to undergo easy amorphization compared to TbFe₂. Magnetization of TbFe₂ was found to decrease rapidly with initial milling hours and was found to be constant with further hours of milling. TbFe₂B exhibited an anomalous behaviour with an increase in moment with milling hours and this may be due to the segregation of α-Fe.