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.     

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.     

Structure and lithium ion conductivity of garnet-like Li5La3Sb2O12 and Li6SrLa2Sb2O12

Oxides with the nominal chemical compositions Li₅La₃Sb₂O₁₂ and Li₆SrLa₂Sb₂O₁₂ were prepared by solid-state reaction. The structures were refined by the Rietveld method using powder X-ray diffraction data. The synthesis of Li₅La₃Sb₂O₁₂ resulted in the well known garnet-related structure plus 5 wt.% of La₂LiSbO₆ in the bulk. In contrast to that, Li₆SrLa₂Sb₂O₁₂ could be synthesised in single garnet-related type phase. Lithium ion conductivities of Li₅La₃Sb₂O₁₂ and Li₆SrLa₂Sb₂O₁₂ were studied by the ac impedance method. The grain-boundary contribution to the total (bulk + grain-boundary) resistance is very small and about 5 and 3% for Li₅La₃Sb₂O₁₂ and Li₆SrLa₂Sb₂O₁₂, respectively, at 24 °C and decreases further with increase in temperature. Among the investigated compounds, Li₅La₃Sb₂O₁₂ exhibits the highest total (bulk + grain-boundary) and bulk ionic conductivity of 7.8 × 10⁻⁶ and 8.2 × 10⁻⁶ S cm⁻¹, respectively, at 24 °C. The structural data indicate that the coupled substitution Li + Sr ⇒ La leads to a closure of the bottle neck like O-O distances of the shared edges of neighbouring Li octahedra and therefore reduces the mobility of Li ions in Li₆SrLa₂Sb₂O₁₂. Scanning electron microscope (SEM) images of the Li₆SrLa₂Sb₂O₁₂ compound revealed well crystallised large homogeneous grains (∼4.8 μm) and the grains were in good contact with the neighbouring grain, which leads to a smaller grain-boundary contribution to the total resistance.     

One-pot syntheses of Li3V2(PO4)3/C cathode material for lithium ion batteries via ascorbic acid reduction approach

Monoclinic Li₃V₂(PO₄)₃/C composite synthesized by ascorbic acid reduction method is examined as a cathode material for Li-ion batteries. Transmission electron microscopy (TEM) images show that the nano-size particles are obtained. The reversible capacity of Li₃V₂(PO₄)₃/C prepared with LiOH and H₃PO₄ is 141.2 mAh g⁻¹ after 100 cycles at 1C discharge rate between 3 V and 4.8 V, and the retention rates of discharge capacity is 93.4%. Ascorbic acid plays not only as reduction reagent, but also as carbon sources. This strategy shortens the time of solid state reaction and facilitates the procedure of synthesis. Effects of different precursors materials on the performance of the Li₃V₂(PO₄)₃/C are investigated.     

Transport properties of LixV2O5 (x = 0.6-1.6) electrode material

The lithium vanadate Li_xV₂O₅ (x=0.6-1.6) has been prepared by the solid state reaction method. The electrical studies are carried out on the gold coated pellets. The diffusion constant (D) and the mean free path (a) have been calculated using Rice and Roth formalism. The conductivity parameters such as ion hopping frequency (ω_p) and the charge carrier concentration (K′) have been calculated using Almond and West formalisms. The variations of the above parameters with temperature and lithium content in Li_xV₂O₅ have been studied.     

Inorganic phosphate crystal Na15−n[Al(PO4)2F2]3−n[Ti(PO4)2F2]n (0 ≤ n < 1): A novel cation exchanger with high exchange selectivity for Li and Pb ions

A series of inorganic phosphate crystals have been hydrothermally synthesized, which have high chemical stability and can keep their crystal structure after acid/base treatments. Its cation-exchange properties have been investigated and the results show that it is an excellent ion exchanger with high exchange capacities for H⁺, Li⁺ and Pb²⁺ ions (12.74, 6.98 and 3.92 mequiv./g, respectively). Selective extractions of Li⁺ and Pb²⁺ from the synthetic mixtures containing (Li⁺, Sr⁺, K⁺, Mg²⁺, Ca²⁺ and Ba²⁺) and (Pb²⁺, Ca²⁺, Ba²⁺, Co²⁺, Ni²⁺, Zn²⁺ and Mg²⁺) have been observed. The reasons of the high exchange selection of NATP for Li⁺ and Pb²⁺ ions have been discussed.     

Synthesis of xLi2MnO3·(1 − x)LiMO2 (M = Cr, Mn, Co, Ni) nanocomposites and their electrochemical properties

A series of 0.4Li₂MnO₃·0.6LiMO₂ (M = Ni_1/3Co_1/3Mn_1/3 and Ni_1/3Cr_1/3Mn_1/3) cathode materials are prepared by a co-precipitation method with subsequent quenching. Crystal structures of samples are investigated by X-ray diffraction and electron diffraction, which show a co-existence of rhombohedral and monoclinic structures indicating nanocomposite characteristics of the sample of 0.4Li₂MnO₃·0.6Li Ni_1/3Cr_1/3Mn_1/3O₂. The average particle size distributions of the powders are analyzed to be an order 400 and 100 nm. The 0.4Li₂MnO₃·0.6LiMO₂ (M = Ni_1/3Co_1/3Mn_1/3 and Ni_1/3Cr_1/3Mn_1/3) electrodes, which consist of a well balanced partial phases of rhombohedral and monoclinic can deliver a high reversible capacity of 220-230 mAh/g during an extended cycling.     

Synthesis, crystal structure and magnetic properties of a new lithium cobalt metaphosphate, LiCo(PO3)3

A new lithium cobalt metaphosphate, LiCo(PO₃)₃, is reported for the first time, which was discovered during the exploratory synthesis in Li-Co-P-O system by solid state reaction. The structure has been refined by powder X-ray Rietveld refinement method (P2₁2₁2₁, a = 8.5398(2) Å, b = 8.6326(2) Å and c = 8.3520(2) Å, Z = 4, R_p = 13.6%, R_wp = 19.4%, R_exp = 17.7%, S = 1.11, χ² = 1.23). It is isostructural with LiM(PO₃)₃ (M = Fe, Cu). It contains (PO₃)¹⁻ chains with the Co atoms localized in the octahedral sites, bridging four neighboring chains. The magnetic susceptibility measurement showed a typical paramagnetic behavior of high spin of Co²⁺, following the Curie-Weiss law in the temperature range of 5-300 K. Unlike the olivine type lithium cobalt phosphate, LiCoPO₄, cyclic voltammetry of LiCo(PO₃)₃ assembled in the coin-type cell showed no electrochemical activity in the voltage region of 1-5 V versus Li/Li⁺.     

Synthesis and characterisation of the garnet-related Li ion conductor, Li5Nd3Sb2O12

In this paper the synthesis, conductivity, and structure of the garnet-related Li ion conductor, Li₅Nd₃Sb₂O₁₂, are reported. As for the related Li₅La₃M₂O₁₂ (M = Nb, Ta) materials, this phase shows high Li ion conductivity, with a conductivity at 300 °C of 9.2 × 10⁻³ S cm⁻¹. Structural studies using neutron diffraction indicate a cubic unit cell, space group Ia-3d, with Li located in two partially occupied sites. One of the sites is the traditional garnet structure tetrahedral site, while the other Li site is considerably more distorted. Although the latter is nominally a six coordinate site, a close inspection suggests that the coordination could be described as distorted tetrahedral, with the remaining two bonds being significantly longer (≈2.6 Å).     

Crystal structure, magnetic and thermal properties of LaFeTeO6

LaFeTeO₆ was prepared by solid state reaction of La₂O₃, Fe₂O₃ and TeO₂ in 1:1:2 molar ratios and characterized by powder X-ray diffraction, thermogravimetry and magnetometry. The detailed crystal structure analysis was carried out by Rietveld refinement. LaFeTeO₆ crystallizes in a trigonal lattice with unit cell parameters: a = 5.2049(1) Å and c = 10.3457(2) Å, V = 242.73(2) Å³. The crystal structure is built from sheets of the edge shared FeO₆ and TeO₆ octahedra stacked along the c-axis. These sheets are connected together by La³⁺ ions. Thermogravimetric analysis of the compound showed it to be thermally stable up to 1323 K and continuous loss of TeO₂ was observed above 1323 K leading to the formation of LaFeO₃. High temperature XRD studies revealed a normal expansion behavior of the compound. Temperature and field dependent magnetization of LaFeTeO₆ showed paramagnetic behavior in the temperature range of 3-300 K. The effective magnetic moment per Fe³⁺ ion (5.14 μB) indicates the high spin d⁵ state of Fe³⁺ ion.     

Metallization of La1/3NbO3 by lithium incorporation

Lithium ion was successfully introduced into La_1/3NbO₃ with an A-site-deficient perovskite-type structure. The crystal structure and transport properties of La_1/3Li_xNbO₃ were investigated as a function of Li content (x = 0-0.59). The lattice parameters of La_1/3Li_xNbO₃ with an orthorhombic cell were enlarged with increasing Li content for x ≤ 0.3, and the structure was transformed to a pseudo-tetragonal cell for x = 0.44. The temperature dependence of electrical resistivity gradually changed from insulating to metallic with increasing x, and thermoelectric power measurement indicated that the carriers were electrons. In X-ray photoelectron spectra of the incorporated samples, Nb_3d⁴⁺ peaks appeared in addition to Nb_3d⁵⁺ peaks, which was consistent with the change of the transport properties. In spite of the success of metallization, no diamagnetic signal indicative of supercondcutivity was observed in La_1/3Li_0.59NbO₃ down to 1.8 K.     

Influence of the B-site ordering on the magnetic properties of the new La3Co2MO9 double perovskites with M = Nb or Ta

Double perovskites La₃Co₂NbO₉ and La₃Co₂TaO₉ have been prepared by both solid state and sol-gel synthesis. The crystal structures have been studied from X-ray and neutron powder diffraction data. Rietveld refinements show that the crystal structure is monoclinic (P2₁/n), with different degrees of ordering of B′ and B″ cations, with octahedra tilted according to the Glazer notation a⁻b⁻c⁺. Occupancy refinements show that the solid state materials are more B-site ordered than the sol-gel ones. Magnetization measurements show that these perovskites show two magnetic contributions, one with spontaneous magnetization and other with linear behaviour with the magnetic field associated to antiferromagnetic correlations. In the samples synthesized by solid state the spontaneous magnetization is more important than those synthesized by the sol-gel and present T_C of 62 K for Nb and 72 K for Ta. On the other hand, materials prepared by sol-gel have T_C 20 K for Nb and 40 K for Ta, respectively and major presence of the antiferromagnetic contribution. The competition between these magnetic behaviours is interpreted, by a microscopic point of view, as to be due to the different degrees of Co²⁺ ions disorder on the B site of the double perovskite structure. This disorder affects the ratio between the antiferromagnetic Co²⁺-O-Co²⁺ and the ferromagnetic Co²⁺-O-M⁵⁺-O-Co²⁺ couplings proposed for the system.     

Elastic properties and spectroscopic studies of fast ion conducting Li2OZnOB2O3 glass system

Glass systems of the composition xLi₂O-20ZnO-(80 − x)B₂O₃ where (x = 5, 10, 15, 20, 25 and 30 mol%) have been prepared by melt quenching technique. Elastic properties, ¹¹B MAS-NMR and IR spectroscopic studies have been employed to study the structure of Li₂O-ZnO-B₂O₃ glasses. Elastic properties have been investigated using sound velocity measurements at 10 MHz. Elastic moduli reveal trends in their compositional dependence. The bulk modulus and shear modulus increases monotonically with increase of BO₄ units, which increase the dimensionality of the network. ¹¹B MAS-NMR and IR spectra show characteristic features of borate network and compositional dependent trends as a function of Li₂O/ZnO concentration. The results are discussed in view of borate network and the dual structural role of Zn²⁺ ions. The results indicate that the Zn²⁺ are likely to occupy network-forming positions in this glass system.     

Enhanced luminescence properties of YBO3:Eu phosphors by Li-doping

Different concentrations of Li-doped YBO₃:Eu³⁺ phosphors have been prepared by the conventional solid state reaction method and were characterized by X-ray diffraction, field emission scanning electron microscopy, photoluminescence excitation and emission measurements. An intense reddish orange emission is observed under UV excitation and the emitted radiation was dominated by an orange peak at 594 nm resulted from the ⁵D₀ → ⁷F₁ transitions of Eu³⁺ ions. The brightness of the YBO₃:Eu³⁺ phosphor was found greatly improved with Li-doping accompanied by slight improvement in the purity of the color which might be attributed to improvement in crystallinity, grain sizes and creation of oxygen vacancies with Li-doping. The observed results have been discussed in comparison with similar reported works.     

Preparation of KNbO3 by hydrothermal reaction

Perovskite-type KNbO₃ powder was prepared by hydrothermal reaction using Nb₂O₅ in KOH solution. A single phase of KNbO₃ was obtained when the molar ratio of KOH/Nb₂O₅ was above 20 and the reaction temperature was above 160 °C. Three types of KNbO₃ powder with the orthorhombic, tetragonal and cubic symmetries were obtained, depending on the reaction temperature and the ratio of KOH/Nb₂O₅. The molar ratios of K/Nb in the cubic and tetragonal phases were 0.91 and 0.94, respectively and that of the orthorhombic one was 0.98, and the mass loss was observed in the TG curves of tetragonal and cubic phases. The tetragonal and cubic phases were stabilized by OH⁻ and adsorbed water.     

Dielectric properties and substitution mechanism of samarium-doped Ba0.68Sr0.32TiO3 ceramics

Ba_0.68Sr_0.32TiO₃ ceramics of perovskite structure are prepared by solid state reaction method with addition of x mol% Sm₂O₃, and their dielectric properties are investigated. It is found that, integrating with the lattice parameters and tolerance factor t, there is an alternation of substitution preference of Sm³⁺ for the host cations in perovskite lattice. Owing to the replacement of Sm³⁺ ions for Ba²⁺ ions in the A site, T_c rises with the increase of Sm₂O₃ doping when the doping content is below 0.1 mol%; meanwhile, when the content is more than 0.1 mol%, Sm³⁺ ions tend to occupy the B-site, causing a drop of T_c. Owing to the modifications of Sm³⁺ doping, dielectric constant, dissipation factor and temperature stability of dissipation factor are influenced remarkably, making it a superior candidate for environment-friendly applications. Moreover, the creation of oxygen vacancies controls the dielectric constant when the addition is above 0.1 mol%, so the dielectric constant decreases with increasing of samarium.     

Chemical bonding of ion-exchange type sites in spinel-type manganese oxides Li1.33Mn1.67O4

The electronic structure and chemical bonding nature of spinel-type Li_1.33Mn_1.67O₄ system was calculated by a discrete-variational (DV)-Xα clusters method. In order to elucidate the reason for the selective exchange of Li⁺ ions, the bonding natures between tetrahedral and octahedral Li sites of the Li_1.33Mn_1.67O₄ were compared. Li in the manganese oxides is highly ionized in both sites, but the net charge of Li was greater for tetrahedral sites than octahedral. These calculations suggest that the tetrahedral sites have higher Li⁺/H⁺ exchangeability than the octahedral sites, and are preferable for the selective adsorption for Li⁺ ions.     

Synthesis of layered Li1.2+x[Ni0.25Mn0.75]0.8−xO2 materials (0 ≤ x ≤ 4/55) via a new simple microwave heating method and their electrochemical properties

Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55) was prepared by a new simple microwave heating method and the effect of extra Li⁺ content on electrochemistry of Li_1.2Ni_0.2Mn_0.6O₂ (x = 0) was firstly revealed. X-ray diffraction identified that they had layered α-NaFeO₂ structure (space group R-3m). Linear variation of lattice constant as a function of x value supported the formation of solid solution, that is, extra Li⁺ is possibly incorporated in structure of layered Li_1.2Ni_0.2Mn_0.6O₂ (x = 0), accompanying oxidization of Ni²⁺ to Ni³⁺ to form Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55). This was confirmed by X-ray photoelectron spectroscopy that Ni³⁺ appeared and increased in content with increasing x value. Charge–discharge tests showed that Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55) truly displayed different electrochemical properties (different initial charge–discharge plots, capacities and cycleability). Li_1.2Ni_0.2Mn_0.6O₂ (x = 0) in this work delivered the highest discharge capacity of 219 mAh g⁻¹ between 4.8 and 2.0 V. Increasing Li content (x value in Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂) reduced charge–discharge capacities, but significantly enhancing cycleability.     

Phase relations of the Li2O-Ta2O5-B2O3 and Li2O-WO3-B2O3 systems and promising nonlinear optical compounds in K2O-Ta2O5-B2O3 system

The subsolidus phase equilibria of the Li₂O-Ta₂O₅-B₂O₃, K₂O-Ta₂O₅-B₂O₃ and Li₂O-WO₃-B₂O₃ systems have been investigated mainly by means of the powder X-ray diffraction method. Two ternary compounds, KTaB₂O₆ and K₃Ta₃B₂O₁₂ were confirmed in the system K₂O-Ta₂O₅-B₂O₃. Crystal structure of compound KTaB₂O₆ has been refined from X-ray powder diffraction data using the Rietveld method. The compound crystallizes in the orthorhombic, space group Pmn2₁ (No. 31), with lattice parameters a = 7.3253(4) Å, b = 3.8402(2) Å, c = 9.3040(5) Å, z = 2 and D_calc = 4.283 g/cm³. The powder second harmonic generation (SHG) coefficients of KTaB₂O₆ and K₃Ta₃B₂O₁₂ were five times and two times as large as that of KH₂PO₄ (KDP), respectively.