Phase equilibria in the system Li2O-TiO2

The system Li₂O-TiO₂ contains four stable phases: Li₄TiO₄, Li₂TiO₃, Li₄Ti₅O₁₂ and Li₂Ti₃O₇, and one metastable phase, H. Li₂TiO₃ undergoes an order-disorder phase transition at 1215°C. High Li₂TiO₃ forms an extensive range of solid solution between ～44 and 66 mole % TiO₂ and low Li₂TiO₃ forms a more limited range of solid solution between ～47 and 51% TiO₂. The temperature of the order-disorder transition decreases to either side of the Li₂TiO₃ composition. The spinel phase Li₄Ti₅O₁₂, has an upper limit of stability at 1015 ± 5°C, above which it decomposes to high Li₂TiO₃ ss and Li₂Ti₃O₇. Li₂Ti₃O₇ has a lower limit of stability at 957 ± 20°C, below which it decomposes to Li₄Ti₅O₁₂ and rutile. During this decomposition of Li₂Ti₃O₇, phase H, a metastable phase of unknown composition, forms as an intermediate. Li₂Ti₃O₇ forms a short range of solid solutions between ～74 and 76% TiO₂. A phase diagram for the system Li₂O-TiO₂ has been constructed using a combination of results determined here and those reported by GICQUEL, MAYER and BOUAZIZ. X-ray powder diffraction data are given for Li₂Ti₃O₇, Li₄Ti₅O₁₂ and phase H.     

Ionic conductivities of Na2Ti3O7, K2Ti4O9 and their related materials

Ionic conductivities were measured on the polycrystalline samples of layered titanates, Na₂Ti₃O₇ and K₂Ti₄O₉, and their derivatives. The activation energies and the prefactors of the conductions were 0.70 eV and 7.9 × 10 (Ωcm)^?1K for Na₂Ti₃O₇ and 0.81 eB and 1.1 × 10³ (Ωcm)^?1K for K₂Ti₄O₉. A small amount of Nb₂O₅ was doped to these titanates substituting TiO₂. Remarkable enhancements of ionic conductivities were observed with the doping. A new metastable phase, Li₂Ti₃O₇, was prepared by ion-exchange of Na₂Ti₃O₇ and its ionic conductivity was measured.     

New rutile solid solutions,Ti1−4xLixM3xO2: M = Nb,Ta, Sb

Three extensive new rutile solid solution series have been prepared in which Ti⁴⁺ is replaced by a combination of Li⁺ and a pentavalent cation: Nb⁵⁺, Ta⁵⁺, Sb⁵⁺. The formulae are Ti_1?4xLi_xM_3xO₂: 0 < x ? 0.15, M = Ta; 0 < x ? 0.17, M = Nb; 0 < x ? 0.12, M = Sb. The solid solutions were characterised by X-ray powder diffraction and density measurements. In addition to the rutile solid solutions, LiNb₃O₈ forms a limited range of solid solutions, Li_1?yNb_3?3yTi_4yO₈: 0 < y ? 0.06.     

Luminescent properties of Gd2Ti2O7: Eu phosphor films prepared by sol-gel process

Gd₂Ti₂O₇: Eu³⁺ thin film phosphors were fabricated by a sol-gel process. X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 800 °C and the crystallinity increased with the elevation of annealing temperatures. Uniform and crack free phosphor films were obtained, which mainly consisted of grains with an average size of 70 nm. The doped Eu³⁺ showed orange-red emission in crystalline Gd₂Ti₂O₇ phosphor films due to an energy transfer from Gd₂Ti₂O₇ host to them. Both the lifetimes and PL intensity of the Eu³⁺ increased with increasing the annealing temperature from 800 to 1000 °C, and the optimum concentrations for Eu³⁺ were determined to be 9 at.%. of Gd³⁺ in Gd₂Ti₂O₇ film host.     

Novel Li4Ti5O12/Sn nano-composites as anode material for lithium ion batteries

Li₄Ti₅O₁₂/Sn nano-composites have been prepared as anode material for lithium ion batteries by high-energy mechanical milling method. Structure of the samples has been characterized by X-ray diffraction (XRD), which reveals the formation of phase-pure materials. Scanning electron microscope (SEM) and transmission electron microscope (TEM) suggests that the primary particles are around 100 nm size. The local environment of the metal cations is confirmed by Fourier transform infrared (FT-IR) and the X-ray photoelectron spectroscopy (XPS) confirms that titanium is present in Ti⁴⁺ state. The electrochemical properties have been evaluated by galvanostatic charge/discharge studies. Li₄Ti₅O₁₂/Sn-10% composite delivers stable and enhanced discharge capacity of 200 mAh g⁻¹ indicates that the electrochemical performance of Li₄Ti₅O₁₂/Sn nano-composites is associated with the size and distribution of the Sn particles in the Li₄Ti₅O₁₂ matrix. The smaller the size and more homogeneous dispersion of Sn particles in the Li₄Ti₅O₁₂ matrix exhibits better cycling performance of Li₄Ti₅O₁₂/Sn composites as compared to bare Li₄Ti₅O₁₂ and Sn particles. Further, Li₄Ti₅O₁₂ provides a facile microstructure to fairly accommodate the volume expansion during the alloying and dealloying of Sn with lithium.     

NMR study of the cation distribution in the systems Li1+5xTa1−xO3 and Li1+xTa1−xTixO3

A ⁷Li NMR study of members of the solid-solution systems Li_1+5xTa_1?xO₃ and Li_1+xTa_1?xTi_xO₃ has indicated that the excess Li⁺ ions occupy interstitial tetrahedral sites in the former. In the latter system, the Li⁺ ions appear to occupy interstitial tetrahedral sites for small values of x, but mostly octahedral sites for x > 0.1. Defect-cluster models are proposed that rationalize these findings as well as the evolution with x of the ferroelectric Curie temperature.     

Enhanced cycling stability of microsized LiCoO2 cathode by Li4Ti5O12 coating for lithium ion battery

The effect of Li₄Ti₅O₁₂ (LTO) coating amount on the electrochemical cycling behavior of the LiCoO₂ cathode was investigated at the high upper voltage limit of 4.5 V. Li₄Ti₅O₁₂ (≤5 wt.%) is not incorporated into the host structure and leads to formation of uniform coating. The cycling performance of LiCoO₂ cathode is related with the amount of Li₄Ti₅O₁₂ coating. The initial capacity of the LTO-coated LiCoO₂ decreased with increasing Li₄Ti₅O₁₂ coating amount but showed enhanced cycling properties, compared to those of pristine material. The 3 wt.% LTO-coated LiCoO₂ has the best electrochemical performance, showing capacity retention of 97.3% between 2.5 V and 4.3 V and 85.1% between 2.5 V and 4.5 V after 40 cycles. The coulomb efficiency shows that the surface coating of Li₄Ti₅O₁₂ is beneficial to the reversible intercalation/de-intercalation of Li⁺. LTO-coated LiCoO₂ provides good prospects for practical application of lithium secondary batteries free from safety issues.     

Sur quelques nouveaux oxydes mixtes de formule BaLn2Fe2O7 et SrLn2Fe2O7

Several new compounds have been prepared, with the general formula : BaLn₂Fe₂O₇ (Ln³⁺ = La to Gd) and SrLn₂Fe₂O₇ (Ln³⁺ = Nd to Tb). The experimental conditions are given, along with some crystal data. The diffraction patterns show a close similarity with that of Sr₃Ti₂O₇.     

Les phases SrLa2Al2O7 et SrGd2Al2O7

SrLa₂Al₂O₇ and SrGd₂Al₂O₇ belong to the structural type Sr₃Ti₂O₇. In SrGd₂Al₂O₇ strontium and gadolinium occupy respectively the 12 and 9 coordinated sites, whereas in SrLa₂Al₂O₇ the homologous cations are statistically distributed. The fluorescence spectra of both phases activated by Eu³⁺ ions show that the only possible position of Eu³⁺ is the 9 coordinated site.     

Lithium-Battery Anode Gains Additional Functionality for Neuromorphic Computing through Metal–Insulator Phase Separation

Specialized hardware for neural networks requires materials with tunable symmetry, retention, and speed at low power consumption. The study proposes lithium titanates, originally developed as Li-ion battery anode materials, as promising candidates for memristive-based neuromorphic computing hardware. By using ex- and in operando spectroscopy to monitor the lithium filling and emptying of structural positions during electrochemical measurements, the study also investigates the controlled formation of a metallic phase (Li₇Ti₅O₁₂) percolating through an insulating medium (Li₄Ti₅O₁₂) with no volume changes under voltage bias, thereby controlling the spatially averaged conductivity of the film device. A theoretical model to explain the observed hysteretic switching behavior based on electrochemical nonequilibrium thermodynamics is presented, in which the metal-insulator transition results from electrically driven phase separation of Li₄Ti₅O₁₂ and Li₇Ti₅O₁₂. Ability of highly lithiated phase of Li₇Ti₅O₁₂ for Deep Neural Network applications is reported, given the large retentions and symmetry, and opportunity for the low lithiated phase of Li₄Ti₅O₁₂ toward Spiking Neural Network applications, due to the shorter retention and large resistance changes. The findings pave the way for lithium oxides to enable thin-film memristive devices with adjustable symmetry and retention.     

Preparation and photocatalytic activity of alkali titanate nano materials A2TinO2n+1 (A = Li, Na and K)

Photocatalysts nano A₂Ti_nO_2n+1 (A = Li, Na, K) were prepared successfully by novel hydrothermal synthesis process. Powders were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible (UV-vis) absorption spectra and field-emission scanning electron microscope (FE-SEM) measurements. These results showed that the compositions of lithium, sodium and potassium titanates were Li₂TiO₃, Na₂Ti₃O₇ and K₂Ti₈O₁₇, respectively. The nano crystals of Li₂TiO₃ were self-assembled as snowflakes while that of Na₂Ti₃O₇ and K₂Ti₈O₁₇ were nanorods. Photocatalytic properties of alkali titanates were also investigated. The results indicated that alkali titanates as prepared have higher photocatalytic activities compared with P25 TiO₂ in the degradation of chloroform under UV light irradiation. A combination of K₂Ti₈O₁₇ and NiO produces a photocatalyst effective for the degradation of chloroform in aqueous solution. The framework of the tunnel structure was suitable for accommodating cocatalysts such as NiO to induce a strong interaction between the active species and cocatalysts. Na₂Ti₃O₇ has high photocatalytic activity under visible-light irradiation due to its strong absorption in the visible light region. The photocatalytic properties of Li₂TiO₃ are inferior to that of Na₂Ti₃O₇ and K₂Ti₈O₁₇ due to its mono-perovskite structure.     

Structural characterization of the lithiated iron oxides LixFe3O4 and LixFe2O3 (0<x<2)

Lithium has been inserted into Fe₃O₄ and α-Fe₂O₃ at room temperature both chemically and electrochemically; a compositional range 0<x<2 has been established for both Li_xFe₃O₄ and Li_xFe₂O₃. Powder X-ray-diffraction data of Li_1.5Fe₃O₄ indicate that the [Fe₂]O₄ subarray of the spinel structure remains intact; the A-site Fe³⁺ ions are displaced to empty octahedral positions and the Li⁺ ions in excess of x = 1 are located in tetrahedral sites. Lithiation of α-Fe₂O₃ causes the anion array to transform from hexagonal to cubic close packing; in this case the Li⁺ ions are distributed over both 16c and 16d octahedral sites of the cubic space group Fd3m.     

Structural and optical properties of Er-doped Y2Ti2O7 thin films by sol-gel method

Er³⁺-doped Y₂Ti₂O₇ and Er₂Ti₂O₇ thin films were fabricated by sol-gel spin-coating method. A well-defined pyrochlore phase Er_xY_2-xTi₂O₇ was observed while the annealing temperature exceeded 800 °C. The average transmittance of the Er_xY_2-xTi₂O₇ thin films annealed at 400 to 900 °C reduces from ∼ 87 to ∼ 77%. The refractive indices and optical band gaps of Er_xY_2-xTi₂O₇ (x = 0-2) annealed at 800 °C/1 h vary from 2.20 to 2.09 and 4.11 to 4.07 eV, respectively. The ∼ 1.53 μm photoluminescence spectrum of Er³⁺ (5 mol%)-doped Y₂Ti₂O₇ thin films annealed at 700 °C/1 h exhibits the maximum intensity and full-width at half maximum (∼ 60 nm).     

Multi-photon luminescence in Er/Yb:SrO⋅TiO2 glass ceramic

Er³⁺/Yb³⁺ doped strontium titanate borosilicate glass was prepared. Glass ceramic was prepared by controlled heat treatment (at 955 °C) of glass. Ti₁₀O₁₉ and Sr₃Ti₂O₇ were found as major crystalline phases. The emission spectra of glass and glass ceramic samples were investigated under 976 nm laser excitation. In glass ceramic, the intensity of the emitted radiation was much higher (≈50 times for green and ≈10 times for red emission) than in the glass. A new three photon process was found to be responsible for emission at low power which is not yet observed in Er³⁺/Yb³⁺:SrO⋅TiO₂ glass ceramic system to the best of our knowledge. The details of upconversion mechanisms e.g. Energy Transfer (ET) and Excited State Absorption (ESA) were studied by power-intensity log dependence. It is expected that Er³⁺/Yb³⁺ doped nanocrystalline (?10 nm) Sr₃Ti₂O₇ phase was responsible for the observed upconversion phenomenon in glass ceramic.     

Comparative analysis of crystal field effects and optical spectroscopy of six-coordinated Mn ion in the Y2Ti2O7 and Y2Sn2O7 pyrochlores

The electronic energy levels of the six-coordinated Mn⁴⁺ ion in the pyrochlores Y₂B₂O₇ (B = Sn⁴⁺, Ti⁴⁺) have been computed using the exchange charge model of crystal field theory. The calculated Mn⁴⁺ energy levels and their trigonal splitting are in good agreement with the experimental spectra. The calculated crystal field parameters show that the higher crystal field strength in Y₂Sn₂O₇ arises from an increased orbital overlap effect between the Mn⁴⁺ ion and the nearest oxygen ions, which are located at the 48f crystallographic position of the pyrochlore lattice. This increased overlap in Y₂Sn₂O₇ occurs despite the fact that the Mn⁴⁺-O²⁻ bond distance in Y₂Sn₂O₇ is longer than in Y₂Ti₂O₇ and is attributed to a lack of hybridization (covalent bonding) between the filled 2p orbital of oxygen ion occupying the 48f site of the pyrochlore lattice and the filled Sn⁴⁺ 4d¹⁰ orbital. The low temperature emission spectrum of Mn⁴⁺ activated Y₂Sn₂O₇ is analyzed in terms of a weak zero phonon line (R-line) with accompanying vibrational side bands.     

Morphology design of highly oriented nonlinear optical Ba2TiSi2O8 crystals at the glass surface by crystallization in reduced atmosphere

The crystallization behavior of 40BaO–20TiO₂–40SiO₂ glass (mol%) in a reduced atmosphere (7%H₂/93%Ar) is examined to develop a new approach for the design and control of the morphology of nonlinear optical fresnoite (Ba₂TiSi₂O₈) crystals. It is found that the glass exhibits surface crystallization when heated in a reduced atmosphere, resulting in c-axis orientations of Ba₂TiSi₂O₈ crystals at the glass surface and enhanced second harmonic intensities. The formation of Ti³⁺ ions at the surface, through the reduction of Ti⁴⁺ ions in the reduced atmosphere, is confirmed from electron spin resonance spectra. It is clarified that the presence of Ti³⁺ ions at the surface induces the prominent change in the crystallization behavior from bulk nanocrystallization to surface crystallization of stoichiometric fresnoite.     

Systeme Li0,5Ga2,5−xCrxO4 (0 ⩽ x ⩽ 2) : Correlations entre structure cristalline,proprietes optiques et spectre vibrationnel

The order-disorder transitions P4₃32 → Fd3m and F4?3m → Fd3m in the system Li_0,5Ga_2,5?xCr_xO₄ occur respectively for x = 1,25 and x = 1,75. The absorption spectra (d.r.s) disclose Cr³⁺ ions in Td symetry from x = 0,75 to x = 2 (ligand-field parameters of Cr³⁺ in A sites : Dq = 700 cm^?1, B = 500 cm^?1). Structure of Li_0,5Ga_0,875Cr_1,625 is established by means of X-ray and neutronic diffraction : Li⁺_0,24Ga³⁺_0,74Cr³⁺_0,02 [Li⁺_0,26Ga³⁺_0,135Cr³⁺_1,605] O^2?₄. Infrared and Raman spectra of ⁶Li_0,5Ga_2,5O₄ and ⁷Li_0,5Ga_2,5O₄ are reported. The IR spectra of ordered spinels (0 ? x ? 0,5 ; 1,75 < x ? 2) are discussed and partly assigned with the help of ⁶Li ? ⁷Li isotopic shifts.     

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.     

Low temperature biomimetic synthesis of the Li2ZrO3 nanoparticles containing Li6Zr2O7 and high temperature CO2 capture

Li₂ZrO₃ nanoparticles containing Li₆Zr₂O₇ were prepared by a biomimetic soft solution route and characterized with X-ray diffraction (XRD), transmission electron microscope (TEM) and nitrogen adsorption. The results show that the tetragonal Li₂ZrO₃ nanoparticles containing monoclinic Li₆Zr₂O₇ can be obtained using this simple method. The mean diameter of the nanoparticles is approximately 90 nm and the corresponding specific surface area is 23.7 m² g^− 1. Moreover, the Li₂ZrO₃ nanoparticles obtained were thermally analyzed under a CO₂ flux to evaluate their CO₂ capture capacity at high temperature. It was found that the as-prepared Li₂ZrO₃ nanoparticles would be an effective acceptor for high temperature CO₂ capture.     

A novel blue-emitting Sr3Al2O5Cl2:Ce,Li phosphor for near UV-excited white-light-emitting diodes

A novel blue-emitting Sr₃Al₂O₅Cl₂:Ce³⁺,Li⁺ phosphor has been synthesized by solid state reaction. The excitation spectrum shows a broad band extending from 300 to 400 nm, and the emission spectrum shows a broad blue band peaking at 450 nm with a half width of about 100 nm. The emission intensity at 250 °C remains at about 50% of that at room temperature. The decay curve at the emission peak consists of fast and slow components. The Sr₃Al₂O₅Cl₂:Ce³⁺,Li⁺ should be a promising blue phosphor for near ultraviolet-based white-light-emitting diodes.