Microporous carbon derived from polyaniline base as anode material for lithium ion secondary battery

Microporous carbon with large surface area was prepared from polyaniline base using K₂CO₃ as an activating agent. The physicochemical properties of the carbon were characterized by scanning electron microscope, X-ray diffraction, Brunauer-Emmett-Teller, elemental analyses and X-ray photoelectron spectroscopy measurement. The electrochemical properties of the microporous carbon as anode material in lithium ion secondary battery were evaluated. The first discharge capacity of the microporous carbon was 1108 mAh g⁻¹, whose first charge capacity was 624 mAh g⁻¹, with a coulombic efficiency of 56.3%. After 20 cycling tests, the microporous carbon retains a reversible capacity of 603 mAh g⁻¹ at a current density of 100 mA g⁻¹. These results clearly demonstrated the potential role of microporous carbon as anode for high capacity lithium ion secondary battery.     

CTAB-assisted sol-gel synthesis of Li4Ti5O12 and its performance as anode material for Li-ion batteries

A simple CTAB-assisted sol-gel technique for synthesizing nano-sized Li₄Ti₅O₁₂ with promising electrochemical performance as anode material for lithium ion battery is reported. The structural and morphological properties are investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The electrochemical performance of both samples (with and without CTAB) calcined at 800 °C is evaluated using Swagelok™ cells by galvanostatic charge/discharge cycling at room temperature. The XRD pattern for sample prepared in presence of CTAB and calcined at 800 °C shows high-purity cubic-spinel Li₄Ti₅O₁₂ phase (JCPDS # 26-1198). Nanosized-Li₄Ti₅O₁₂ calcined at 800 °C in presence of CTAB exhibits promising cycling performance with initial discharge capacity of 174 mAh g⁻¹ (∼100% of theoretical capacity) and sustains a capacity value of 164 mAh g⁻¹ beyond 30 cycles. By contrast, the sample prepared in absence of CTAB under identical reaction conditions exhibits initial discharge capacity of 140 mAh g⁻¹ (80% of theoretical capacity) that fades to 110 mAh g⁻¹ after 30 cycles.     

The effect of Eu-activated InVO4 phosphors prepared by sol-gel method

Indium orthovanadate (InVO₄) doped with Eu³⁺ ions had been synthesized by sol-gel method. The precursor of InVO₄:Eu³⁺ powders were heated at 950 °C for 6 h in air, and the crystal structure, surface morphologies and photoluminescence properties were also investigated. XRD patterns indicated that the crystallinity of InVO₄:Eu³⁺ powders decreases with increasing Eu³⁺ ion concentrations. From the SEM micrographs, the shapes of the InVO₄ particles are uniform and like pebbles. With increasing Eu³⁺ ion concentrations, the shapes of the InVO₄:Eu³⁺ particles become smaller and irregular. In the PL studies, the sharp excitation peaks between 300 and 600 nm correspond to the Eu³⁺ intra-4f transitions. Excitation at 326 nm in terms of Eu³⁺ concentrations in (In_1−xEu_x)VO₄ powders shows that the (In_1−xEu_x)VO₄ phosphors display bright red luminescence at about 615 nm belonging to the ⁵D₀ → ⁷F₂ electric dipole transition, and the time-resolved ⁵D₀ → ⁷F₂ transition presents a single exponential decay behavior. The concentration quenching is active when the Eu³⁺ concentration is larger than 30 mol%, and the critical distance is about 8.024 Å.     

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.     

Lithium conducting glass ceramic with Nasicon structure

Lithium ion conducting glass and glass ceramic of the composition Li_1.4[Al_0.4Ge_1.6(PO₄)₃], have been synthesized. The monolithic glass pieces on thermal treatment resulted in single-phase glass ceramic with the Nasicon structure. Experiments with different electrodes proved that the lithium electrodes provide accurate values for the ionic conductivity using impedance spectroscopy. σ_ionic of the glass ceramic was found to be 3.8×10⁻⁵ S cm⁻¹ at 40°C with an activation energy (E_a) of 0.52 eV. The corresponding values for the glass are 2.7×10⁻⁹ S cm⁻¹ and 0.95 eV, respectively. The Arrhenius dependence of σ_ionic with temperature in glass and glass ceramic is interpreted with a hopping mechanism from which the microscopic characteristics of the lithium cation motion are deduced.     

Synthesis of spherical LiMnPO4/C composite microparticles

Spherical LiMnPO₄/C composite microparticles were prepared by a combination of spray pyrolysis and spray drying followed by heat treatment and examined as a cathode material for lithium batteries. The structure, morphology and electrochemical performance of the resulting spherical LiMnPO₄/C microparticles were characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electronic microscopy and standard electrochemical techniques. The final sample was identified as a single phase orthorhombic structure of LiMnPO₄ and spherical powders with a geometric mean diameter of 3.65 μm and a geometric standard deviation of 1.34. The electrochemical cells contained the spherical LiMnPO₄/C microparticles exhibited first discharge capacities of 112 and 130 mAh g⁻¹ at 0.05 C at room temperature and 55 °C, respectively. These also showed a good rate capability up to 5 C at room temperature and 55 °C.     

Magnetic properties of nano-clusters lanthanum chromite powders doped with samarium and strontium ions synthesized via a novel combustion method

A novel approach to synthesize a single-phase orthorhombic perovskite lanthanum chromite LaCrO₃ clusters doped with Sm³⁺ and Sr²⁺ ions via gel combustion route was reported. The producing materials were synthesized using metal nitrates as oxidizers and triethanol amine (TEA), N-butyl amine (NBA) or ethylene diamine (EDA) as a fuel. The effect of the annealing temperature, type of organic fuel and the variation of the samarium and/or strontium substitution and its impact on crystal structure, crystallite size, microstructure and magnetic properties of the LaCrO₃ powders formed was systematically studied. The results revealed that a well crystalline single phase of pure LaCrO₃ can be achieved at annealing temperature from 800 to 1000 °C for 2 h. Moreover, each organic carrier materials exhibited a different degree of effectiveness in the synthesis of the mixed oxide powders. The crystal structure was influenced by doped Sm³⁺ and/or Sr²⁺ ions. The crystallite size of the produced powders was increased with the increase the annealing temperature, increasing the Sm³⁺ ion and the decrease of Sr²⁺ ion substitution. The microstructures of the produced powders were found to be nanoclusters octahedra-like shaped. The saturation magnetization of the LaCrO₃ powders increased continuously with an increase in the Sm³⁺ ion concentration and it decreased with an increase in the Sr²⁺ ion up to 0.3 at annealing temperature of 1000 °C for 2 h. The maximum saturation magnetization (0.279 emu/g) was achieved at the Sm³⁺ ion molar ratio 0.3 and annealing temperature 1000 °C. Moreover, wide coercivities can be obtained at different synthesis conditions (49.25 to 522  Oe).     

Electrochemical lithium insertion in the solid solution Bi2WO6-Sb2WO6 with Aurivillius framework

Following the structural evolution of the Aurivillius crystalline framework in the solid solution Bi₂WO₆-Sb₂WO₆ we have carried out an electrochemical lithium insertion study in this system. A slight loss of the specific capacity of the electrochemical cell was observed as amount of Sb was increased. In general, the different compositions within solid solution Bi_2−xSb_xWO₆ (0.25 ≤ x ≤ 0.75) exhibited a similar behaviour featured mainly by two semiconstant potential regions located at 1.7 and 0.8 V versus Li⁺/Li^o. The oxide Sb₂WO₆ with Autivillius structure but without Bi was tested as cathode too. The maximum amount of lithium inserted, 13.5 lithium atoms per formula, is the same amount inserted in its homologous bismuth oxide Bi₂WO₆.     

Synthesis, characterization and evaluation of nano-zirconium vanadate ion exchanger by using three different preparation techniques

Sol-gel, homogeneous precipitation and hydrothermal synthesis are three different preparation techniques have been used as an attempt to synthesize nano-zirconium vanadate with properties suitable to be used as ion exchangers. The impact of the synthetic preparation variables such as the reactant concentrations, reaction temperature and reaction time on the ion exchange capacity of the produced ion exchanger has been considered for each preparation technique. One sample from each preparation technique having the largest ion exchange capacity has been selected to be physically and chemically characterized using various analytical techniques such as XRD, TGA, DSC, pH titration, FTIR and SEM in order to determine the properties of the ion exchanger produced from each technique. For all the studied ZrV samples it can be presumed that they have the ion exchange affinity sequences for alkali metal ions K > Na > Li, the order for the alkaline earth metals is Ba > Ca > Mg and their affinity for radioactive metals follow Cs > Sr. Moreover, the prepared materials are of high thermal and radiation stabilities. Also they have high chemical stabilities toward wide concentration ranges of acid, basic as well as polar solvents. It has been deduced from the X-ray analysis that ZrV produced from the sol-gel technique has an amorphous structural. While those produced from the homogeneous precipitation and hydrothermal synthesis techniques, in the nano-scale have semi-crystalline structural. Furthermore, SEM confirms that particle size of the all studied prepared ZrV samples have nano-diameters of range 50-60 nm. Specific surface area of the three different prepared ion exchangers are found to be equal to 187, 192 and 320 m²/g for sol-gel, homogeneous precipitation and hydrothermal, respectively. A tentative structural formula of Zr(OH)₂(HVO₄)₂·2H₂O has been proposed for all studied samples on the basis of on FTIR, DSC and TGA results.     

A novel compound with the formula Cd2InVO6

As a result of a solid-state reaction, a compound with the formula Cd₂InVO₆ has been obtained for the first time. This compound melts congruently at 1050 ± 10 °C. It crystallises in the monoclinic system and the unit cell parameters are: a = 0.7964(2) nm, b = 1.1311(3) nm, c = 0.6001(1) nm, γ = 104.1°, Z = 4.     

Third-order nonlinear optical properties of Bi2S3 nanocrystals doped in sodium borosilicate glass studied with Z-scan technique

The third-order nonlinear optical properties of Bi₂S₃ nanocrystals doped in sodium borosilicate glass are measured by Z-scan technique. The microstructures of the glass are characterized by means of X-ray diffraction, transmission electron microscopy, scanning transmission electron microscopy, energy dispersion X-ray spectra, and high-resolution transmission electron microscopy. The results show that the Bi₂S₃ nanocrystals ranging from 10 to 30 nm are determined to be of the orthorhombic crystalline phase, and the third-order optical nonlinear refractive index γ, absorption coefficient β, and susceptibility χ⁽³⁾ of the glass are determined to be 2.56 × 10⁻¹⁶ m² W⁻¹, 4.13 × 10⁻¹⁰ mW⁻¹, and 1.43 × 10⁻¹⁰ esu, respectively.     

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.     

Preparation, characterization and luminescence of La2TeO6 phosphor doped with Eu

Phosphors of La₂TeO₆ doped with Eu³⁺ ions have been synthesized by the oxidation of the corresponding rare-earths oxytellurides of formula La_2−xEu_xO₂Te (x = 0.02, 0.06, and 0.1) at 1050 K. Powder X-ray diffraction confirms that the as prepared materials consist of the orthorhombic La₂TeO₆ as main phase. The photoluminescence (PL) of red-emitting La_2−xEu_xTeO₆ powder phosphors is reported. The emission spectrum, exhibits an intense emission peak due to ⁵D₀ → ⁷F₂ transition at 616 nm, which indicates that the Eu³⁺ ion occupies a non-centrosymmetric site in the host lattice. These materials could find application for use as lamp phosphors in the red region.     

Ion exchange and electrochemical evaluation of the microporous phosphate Li9Fe7(PO4)10

A new lithium iron(III) phosphate, Li₉Fe₇(PO₄)₁₀, has been synthesized and is currently under electrochemical evaluation as an anode material for rechargeable lithium-ion battery applications. The sample was prepared via the ion exchange reaction of Cs₅K₄Fe₇(PO₄)₁₀1 in the 1 M LiNO₃ solution under hydrothermal conditions at 200 °C. The fully Li⁺-exchanged sample Li₉Fe₇(PO₄)₁₀2 cannot yet be synthesized by conventional high-temperature, solid-state methods. The parent compound 1 is a member of the Cs_9−xK_xFe₇(PO₄)₁₀ series that was previously isolated from a high-temperature (750 °C) reaction employing the eutectic CsCl/KCl molten salt. The polycrystalline solid 1 was first prepared in a stoichiometric reaction via conventional solid-state method then followed by ion exchange giving rise to 2. Both compounds adopt three-dimensional structures that consist of orthogonally interconnected channels where electropositive ions reside. It has been demonstrated that the Cs_9−xK_xFe₇(PO₄)₁₀ series possesses versatile ion exchange capabilities with all the monovalent alkali metal and silver cations due to its facile pathways for ion transport. 1 and 2 were subject to electrochemical analysis and preliminary results suggest that the latter can be considered as an anode material. Electrochemical results indicate that Li₉Fe₇(PO₄)₁₀ is reduced below 1 V (vs. Li) to most likely form a Fe(0)/Li₃PO₄ composite material, which can subsequently be cycled reversibly at relatively low potential. An initial capacity of 250 mAh/g was measured, which is equivalent to the insertion of thirteen Li atoms per Li_9+xFe₇(PO₄)₁₀ (x = 13) during the charge/discharge process (Fe²⁺ + 2e → Fe⁰). Furthermore, 2 shows a lower reduction potential (0.9 V), by approximately 200 mV, and much better electrochemical reversibility than iron(III) phosphate, FePO₄, highlighting the value of improving the ionic conductivity of the sample.     

Y2O3:Eu microstructures: Hydrothermal synthesis and photoluminescence properties

Hexagonal microprisms of yttrium hydroxide (Y(OH)₃) with tuned diameter and height have been successfully prepared for the first time via a facile hydrothermal process using sodium citrate as the shape modifying agent. Y(OH)₃ microspheres with diameter of ca. 2.5 μm and microtubes with an average length about 13 μm, outer diameter about 3 μm and tube thickness about 800 nm were also obtained in current reaction systems. The possible formation mechanism for the Y(OH)₃ microstructures was briefly proposed. Y₂O₃:Eu³⁺ (5%) microstructures with similar morphologies was obtained after thermal treatment of the as-prepared Y(OH)₃:Eu³⁺ microstructures at 700 °C for 4 h. Results show that the relative emission intensity of the Y₂O₃:Eu³⁺ microprisms is about 8 times as those of the Y₂O₃:Eu³⁺ microtubes and microspheres under excitation of 259 nm ultraviolet light. The products were characterized by XRD, SEM, and EDS.     

Preparation and electrochemical properties of Li-rich spinel-type lithium manganate coated LiMn2O4

Li-rich spinel-type lithium manganate (SC) coated LiMn₂O₄ composites were prepared and characterized by XRD, SEM, FT-IR, ICP, etc. Their charge/discharge behaviors were studied between 3.0 and 4.3 V at 40 mA g⁻¹ under room temperature, and the results showed that SC coated on surface of LiMn₂O₄ could improve cycling stability of composite electrodes. The composite (S1) containing 4.8 wt% of SC exhibited noticeably improved cycling stability, whereas the initial specific capacity was very close to that of LiMn₂O₄.     

Thermal stability against reduction of LaMn1−yCoyO3 perovskites

Thermal and reduction-oxidation stability of substituted LaMn_1−yCo_yO₃ perovskite-type oxides (0.0 ≤ y_Co ≤ 1.0) prepared by the citrate route have been studied by means of surface area, X-ray diffraction, FTIR spectroscopy and magnetic properties. The perovskite orthorhombic structure is found for y_Co ≤ 0.5, with the exception of y_Co = 0.1, which corresponds better to rhombohedral LaMnO_3.15. For y_Co > 0.5 the diffraction profiles are quite similar to the cobaltite’s rhombohedral structure. Magnetic iso-field studies (ZFC-FC) reveal that, for y_Co ≤ 0.50, the system presents an antiferromagnetic canted-like ordering of the Mn/Co sublattice, in which the presence of divalent Co ion creates Mn³⁺-Mn⁴⁺ pairs that interact ferromagnetically through the oxygen orbital. This interpretation is confirmed by the magnetization loops, in which the magnetic moment increases when substituting Mn for Co. Therefore, the general trend is: for y_Co ≤ 0.5, the Co ions are inserted in the manganite structure and for y_Co > 0.5, the Mn ions are inserted in cobaltite structure. The enhancement of the ferromagnetic properties and the thermal stability against reduction for y_Co = 0.5 is attributed to optimized Co²⁺-Mn⁴⁺ interactions.     

Synthesis and characterization of K2NiF4-type CaLnCoO4 (Ln = Sm and Gd)

K₂NiF₄-type CaLnCoO₄ (Ln = Sm and Gd) has been synthesized at 1173 or 1223 K in air using citric acid (CA) and ethylene glycol (EG). CaLnCoO₄ (Ln = Sm and Gd) has an orthorhombic structure with the space group Bmab. The average particle sizes are approximately 300 nm for CaSmCoO₄ and approximately 170 nm for CaGdCoO₄, respectively. The global instability index (GII) indicates that the crystal structure of CaGdCoO₄ is more stable than that of CaSmCoO₄. CaLnCoO₄ (Ln = Sm and Gd) is a p-type semiconductor and shows paramagnetic behavior above 5 K. The 1/χ-T curve of CaSmCoO₄ deviates from the Curie-Weiss law, whereas the 1/χ-T curve of CaGdCoO₄ follows the Curie-Weiss law in the temperature range of 5 ≤ T ≤ 300 K. From the values of the observed effective magnetic moment (μ_eff) of CaLnCoO₄ (Ln = Sm and Gd), it is considered that the spin state of the Co³⁺ ion is low.     

Synthesis and Li ion conductivity of Li2O-Nb2O5-P2O5 glasses and glass-ceramics

Glasses with the compositions of xLi₂O-(70 − x)Nb₂O₅-30P₂O₅, x = 30-60, and their glass-ceramics are synthesized using a conventional melt-quenching method and heat treatments in an electric furnace, and Li⁺ ion conductivities of glasses and glass-ceramics are examined to clarify whether the glasses and glass-ceramics prepared have a potential as Li⁺ conductive electrolytes or not. The electrical conductivity (σ) of the glasses increases monotonously with increasing Li₂O content, and the glass of 60Li₂O-10Nb₂O₅-30P₂O₅ shows the value of σ = 2.35 × 10⁻⁶ S/cm at room temperature and the activation energy (E_a) of 0.48 eV for Li⁺ ion mobility in the temperature range of 25-200 °C. It is found that two kinds of the crystalline phases of Li₃PO₄ and NbPO₅ are formed in the crystallization of the glasses and the crystallization results in the decrease in Li⁺ ion conductivity in all samples, indicating that any high Li⁺ ion conducting crystalline phases have not been formed in the present glasses. 60Li₂O-10Nb₂O₅-30P₂O₅ glass shows a bulk nanocrystallization (Li₃PO₄ nanocrystals with a diameter of ∼70 nm) and the glass-ceramic obtained by a heat treatment at 544 °C for 3 h in air exhibits the values of σ = 1.23 × 10⁻⁷ S/cm at room temperature and E_a = 0.49 eV.     

Chemical bath deposition of SnS2 nanowall arrays with improved electrochemical performance for lithium ion battery

A facile chemical bath deposition (CBD) approach has been developed to fabricating SnS₂ nanowall (NW) arrays directly on copper foils. As an anode material for lithium ion battery, the NW arrays exhibit enhanced lithium ion storage property. At a rate of 0.3 C, the NW arrays maintain a capacity of about 700 mA h g⁻¹ after 40 cycles. Even at a high rate of 1.2 C, the NW arrays can still deliver a stable capacity of 400 mA h g⁻¹. The high electrochemical performance is well related to the in situ growth of uniform SnS₂ nanostructures on a conductive copper current collector, which results in a robust adhesion for the SnS₂ NW on the copper, and leads to an enhanced electron conductivity, improved lithium ion transport, and sustained volume variations.