Microstructural analysis of La2/3 − xLi3xTiO3 single crystals and quenched samples observed by high resolution transmission electron microscopy

The La ordering and domain structures of La_2/3 ? xLi_3xTiO₃ single crystals and quenched samples have been observed by high resolution electron microscopy. In single crystals, the grown single crystals are not real single crystals with mono-domain, but crystals with 90° oriented domains with 20–100 nm sizes. A remarkable difference of the domain size between polycrystals and single crystals has not been observed at the same composition. In quenched samples, the La disordering has been observed. Furthermore, domain structures of quenched samples are different from those of furnace-cooled ones. Domain structures change with the La disordering. The understanding of microstructures is necessary to clarify the Li-ion conduction mechanism.     

Structural investigations of migration pathways in lithium ion-conducting La2/3−xLi3xTiO3 perovskites

The average structure and microstructure of a lithium-ion conducting perovskite La_2/3−xLi_3xTiO₃ (x = 0.12) were investigated using neutron diffraction and transmission electron microscopy (TEM). The obtained results were compared with those of previous studies on La_2/3−xLi_3xTiO₃ series compounds, and the relationship between their structures and ionic conduction was discussed. The Rietveld refinement using neutron diffraction data reveals that the average structure (space group: Cmmm) of furnace-cooled Li-rich La_2/3−xLi_3xTiO₃ (x = 0.12) involves alternative ordered arrangement of La along the c-axis and anti-phase-tilt of TiO₆ octahedra along the b-axis as with Li-poor La_2/3−xLi_3xTiO₃(x = 0.05). It was found that the strong correlation between structure and percolative diffusion pathways in the perovskites is primarily referred to the ordered arrangement of La ions, and the “bottleneck” square—surrounded by four oxygen ions determined by the distortion and tilt of TiO₆ octahedra. In addition, the 90°-oriented micro-domain structure, which also influences the percolative diffusion pathways in La_2/3−xLi_3xTiO₃, was observed by TEM.     

Evolution of TiO2 coating layers on lamellar sericite in the presence of La and the pigmentary properties

TiO₂-coated sericite powders were prepared by the chemical deposition method starting from lamellar sericite and TiCl₄ in the presence or absence of La³⁺ cations. After calcination at 900 °C for 1 h, the resultant TiO₂ nanoparticles on the sericite surfaces existed in anatase phase. The light scattering indexes of the TiO₂-coated lamellar sericite powders were dozens of times higher than that of the naked lamellar sericite powders. The presence of La³⁺ in the deposition solution was beneficial to the formation of the small-sized anatase TiO₂ nanoparticles, resulting in the formation of the dense and uniform island-like TiO₂ coating layers in a large range of the weight ratios of TiO₂ to sericite from 5% to 20%. The TiO₂-coated lamellar sericite powders prepared in the presence of La³⁺ had higher light scattering index than that prepared in the absence of La³⁺. XPS analysis shows that when La³⁺ cations were absent in the reaction solution, TiO₂ coating layers anchored at the sericite surface via the Ti-O-Si and Ti-O-Al bonds. The presence of La³⁺ cations caused the formation of Si-O-La and Al-O-La bonds at the sericite surface and Ti-O-La bond at the surface of TiO₂ coating layers. After coating TiO₂ on the sericite surface, the yellowness of the TiO₂-coated sericite powders obviously increased and the brightness slightly decreased.     

Lithium-ionic diffusion and electrical conduction in the Li7La3Ta2O13 compounds

The electrical properties and the mechanism of lithium ionic diffusion in the Li₇La₃Ta₂O₁₃ compounds were investigated. The bulk and total conductivity at 300 K of the Li₇La₃Ta₂O₁₃ compound are about 3.3 × 10^? 6 S/cm and 2.6 × 10^? 6 S/cm, respectively. The activation energy of bulk and total conductivity is in the range of 0.38–0.4 eV. A prominent internal friction peak in Li₇La₃Ta₂O₁₃ compounds was observed around 280 K at 0.5 Hz, which is actually composed of two subpeaks (P₁ peak at lower temperature and P₂ peak at higher temperature). From the shift of peak position with frequency, the activation energy of 1.0 eV and the pre-exponential factor of relaxation time in the order of 10^? 18–10^? 21 s were obtained if one assumes Debye relaxation processes. These values of relaxation parameters strongly suggest the existence of interaction between the relaxation species (here lithium ions or vacancies). Based on the coupling model, the relaxation activation energies are deduced as 0.45 eV and the pre-exponential factor of relaxation time as 10^? 15 s. Judging from these relaxation parameters and the similarity of structure between Li₇La₃Ta₂O₁₃ and Li₅La₃Ta₂O₁₂ compounds, the P₁ and P₂ peaks are suggested to be related with the lithium ionic diffusion between 48g?48g and 24d?48g.     

Nanocrystalline Li<Subscript>2</Subscript>TiO<Subscript>3</Subscript> electrodes for supercapattery application

Nanocrystalline Li₂TiO₃ was successfully synthesized using solid-state reaction method. The microstructural and electrochemical properties of the prepared material are systematically characterized. The X-ray diffraction pattern of the prepared material exhibits predominant (002) orientation related to the monoclinic structure with C2/c space group. HRTEM images and SAED analysis reveal the well-developed nanostructured particles with average size of ～40 nm. The electrochemical properties of the prepared sample are carried out using cyclic voltammetry (CV) and chronopotentiometry (CP) using Pt//Li₂TiO₃ cell in 1 mol L^?1 Li₂SO₄ aqueous electrolyte. The Li₂TiO₃ electrode exhibits a specific discharge capacity of 122 mAh g^?1; it can be used as anode in Li battery within the potential window 0.0–1.0 V, while investigated as a supercapacitor electrode, it delivers a specific capacitance of 317 F g^?1 at a current density of 1 mA g^?1 within the potential range ?0.4 to +0.4 V. The demonstration of both anodic and supercapacitor behavior concludes that the nanocrystalline Li₂TiO₃ is a suitable electrode material for supercapattery application.     

Growth by laser ablation of Ti-based oxide films with different valency states

x La_2/3+yTiO_3-δ perovskite (with δ≤0.5) were deposited by the laser ablation technique from Li_0.33La_0.56TiO₃ targets. Their growth onto MgO substrateswas studied as a function of the oxygen pressure. For films grown in vacuum (10^-6 mbar), a La_0.63TiO_2.5 composition was obtained, meaning that Ti³⁺ alone is present in the films, while Li ions are not incorporated under these conditions. This material shows good electric conductivity (ρ=500 mΩ cm). By contrast, insulating films with a Li_0.1La_0.70TiO₃ composition corresponding to the Ti⁴⁺ species were obtained at high oxygen pressures (>0.05 mbar). For all conditions, textured films were grown with different orientations depending on the temperature and the oxygen pressure. Received: 10 September 1997/Accepted: 24 November 1997     

Capacitance of the La0.67Sr0.33MnO3/(Ba,Sr)TiO3 interface induced by electric field penetration into the manganite electrode

(001)La_0.67Sr_0.33MnO₃/(001)(Ba_xSr_{1 ? x} TiO₃/(001)La_0.67Sr_0.33MnO₃(x= 0–0.25) three-layer heterostructures are grown by laser evaporation on (001)La_0.3Sr_0.7Al_0.65Ta_0.35O₃ single-crystalline substrates. In a wide temperature range (≈150 K), effective permittivity ? of (1000 nm)Ba_0.25Sr_0.75TiO₃ and (1000 nm)SrTiO₃ films grown obeys the relationship ? ～ (T ? T _CW)^?1, where T _CW is the Curie-Weiss temperature for related bulk crystals. Using experimental dependences ?(T), the capacitance of the (001)La_0.67Sr_0.33MnO₃/(001)Ba_xSr_1?x TiO₃ and (001)La_0.67Sr_0.33MnO₃/(001)SrTiO₃ interfaces, which is due to electric field penetration into the manganite electrode, is estimated (C _int≈4μF/cm²). At bias voltages of ± 2.5 V, the change in the permittivity of the STO and BSTO films in the heterostructures studied reaches 25 and 45%, respectively.     

Crystallite size and magnetic properties of La0.7Mn1.3O3 ± Δ

The results of investigation into nanocrystalline lanthanum manganites La_0.7Mn_1.3O_{3 ± Δ} produced by repeated cold isostatic pressing of a charge material are reported. A powder compact with a crystallite size of 5–7 nm exhibits no magnetic properties, unlike a coarse-grained (20 nm) powder compact.     

Lithium ion conductivity of the B-site substitution in Li3xLa0.67−xRE y III Ti1−2yPyO3 system (REIII=Sc3+, Y3+, Nd3+, Sm3+, Eu3+, Yb3+)

The B-site substituted perovskite solid solution systems Li_3xLa_0.67−xRE_yTi_1−2yP_yO₃ (RE=Sc, Y, Nd, Sm, Eu, Yb) have been investigated. Perovskite solid solutions formed in the range of x=0.10, y<0.10 for RE=Sc³⁺, Y³⁺, Yb³⁺, x=0.10, y≤0.05 for RE=Nd³⁺, Sm³⁺, Eu³⁺. Li_0.3La_0.57Nd_0.05Ti_0.9P_0.05O₃ has the highest bulk conductivity of 4.31×10⁻⁴ S·cm⁻¹ and the highest total conductivity of 2.52×10⁻⁴ S·cm⁻¹ at room temperature in all prepared compositions. The compositions have low activation energies of about 24–30 kJ/mol in the temperature ranges of 298–523 K. SEM studies showed that the sample made by solid-state reaction has a sphere-like morphology and a rough particle with particle size of about 50 μm. The research results also indicated that the reaction temperature decreases and the electrochemical stabilities of the titanate-based perovskite-type solid solutions are improved by using RE³⁺ and P⁵⁺ replaced Ti⁴⁺ on B-site in the Li_3xLa_0.67−xTiO₃ parent.     

The effect of LaPO4 in the LixLa2/3Ti1−xPxO3+x system

Lithium ion conductors of the overall composition Li_xLa_2/3Ti_1−xP_xO_3+x (hereafter referred to as LTP) based on La_2/3TiO₃ were prepared by solid state reaction at high temperature (1300 °C). AC impedance measurements indicate that the total conductivities are of the order of 10⁻⁴ S·cm⁻¹ when x=0.28 − 0.35 at room temperature and have an activation energy of 18 kJ·mol⁻¹ in the temperature range from room temperature to 400 °C. X-ray powder diffraction patterns showed that the LTP system has a complex composition, which contains the solid solution perovskite Li_3xLa_2/3−xTiO₃ and LaPO₄.     

Effect of V5+ in the complex Li3xLa2/3−xTiO3-LaPO4 system

Lithium fast ion conductors of the composition Li_0.3La_2/3Ti_0.7P_0.3−xV_xO_3.3 (LTV) based on mixtures of Li_3xLa_2/3−xTiO₃ and LaPO₄ were prepared by solid state reaction at high temperature (≈ 1300 °C). AC impedance measurements indicate total conductivities of about 1 × 10⁻⁴ Scm⁻¹ for compositions of x=0∼0.3 at room temperature with an activation energy of ≈18 kJ·mol⁻¹ in the temperature range from 30 to 400 °C. X-ray powder diffraction patterns showed that the LTV system is composed of Li_3xLa_2/3−xTiO₃ perovskite solid solution and LaP_1−xV_xO₄ solid solution.     

Electrochemical behavior of Li intercalation processes into a Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 cathode

Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ (X=0.17, 0.25, 0.33, 0.5) compounds are prepared by a simple combustion method. The Rietvelt analysis shows that these compounds could be classified as having the α-NaFeO₂ structure. The initial charge-discharge and irreversible capacity increases with the decrease of x in Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂. Indeed, Li[Ni_0.50Mn_0.50]O₂ compound shows relatively low initial discharge capacity of 200 mAh/g and large capacity loss during cycling, with Li[Ni_0.17Li_0.22Mn_0.61]O₂ and Li[Ni_0.25Li_0.17Mn₀.₅₈]O₂ compounds exhibit high initial discharge capacity over 245 mAh/g and stable cycle performance in the voltage range of 4.8 -2.0 V. On the other hand, XANES analysis shows that the oxidation state of Ni ion reversibly changes between Ni²⁺ and about Ni³⁺, while the oxidation state of Mn ion sustains Mn⁴⁺ during charge-discharge process. This result does not agree with the previously reported ‘electrochemistry model’ of Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂, in which Ni ion changes between Ni²⁺ and NI⁴⁺. Based on these results, we modified oxidation-state change of Mn and Ni ion during charge-discharge process.     

Microwave synthesis of lithium lanthanum titanate

A microwave method has been developed for the preparation and sintering of lithium lanthanum titanate (LLTO) of the formula Li_0.35La_0.55TiO₃. The method is fast, clean, economical and gives phase pure product of high conductivity.     

Structure and lithium ionic conduction of B-site Al-ion substitution in La4/3-yLi3yTi2O6

The Al-substitution effect was studied in solid solutions La_4/3-yLi_3y□_2/3-2yTi₂O₆ (LLTO). The ionic conductivity strongly depended on the Al concentration. The crystal structure, lattice parameters, ions occupation and bottleneck size were obtained by Rietveld analysis. Finally, the ionic conduction mechanism was discussed from the viewpoint of crystallographic factors.     

Electrode reaction and microstructure of La0.6Sr0.4CoO3−δ thin films

Dense La_0.6Sr_0.4CoO_3−δ film electrodes were deposited by pulsed laser deposition (PLD) on Ce_0.9Gd_0.1O_1.95 electrolytes. The grain size of one film was 300–500 nm, and the other was 30–50 nm. DC polarization and AC impedance measurements were performed at 873 K–1073 K in O₂–Ar gas mixtures. From investigations of the electrochemical capacitances, the rate determining process for both electrodes were confirmed to be the surface reaction. The analyses in the electrochemical resistance revealed that the oxygen adsorption/desorption rate was faster on the electrode with smaller grain size. DC responses agreed with AC results, so the current density on the nano-grain electrode was larger by half an order than those of the sub-micron-grain electrode. Under a dilute oxygen atmosphere, the rate determining step transferred from a surface reaction to a gas phase diffusion.     

Nanocrystal formation in gas-atomized amorphous Al85Ni10La5 alloy

An Al₈₅Ni₁₀La₅ amorphous alloy, produced via gas atomization, was selected to study the mechanisms of nanocrystallization induced by thermal exposure. High resolution transmission electron microscopy results indicated the presence of quenched-in Al nuclei in the amorphous matrix of the atomized powder. However, a eutectic-like reaction, which involved the formation of the Al, Al₁₁La₃, and Al₃Ni phases, was recorded in the first crystallization event (263°C) during differential scanning calorimetry continuous heating. Isothermal annealing experiments conducted below 263°C revealed that the formation of single fcc-Al phase occurred at 235°C. At higher temperatures, growth of the Al crystals occurred with formation of intermetallic phases, leading to a eutectic-like transformation behaviour at 263°C. During the first crystallization stage, nanocrystals were developed in the size range of 5 ～ 30 nm. During the second crystallization event (283°C), a bimodal size distribution of nanocrystals was formed with the smaller size in the range of around 10 ～ 30 nm and the larger size around 100 nm. The influence of pre-existing quenched-in Al nuclei on the microstructural evolution in the amorphous Al₈₅Ni₁₀La₅ alloy is discussed and the effect of the microstructural evolution on the hardening behaviour is described in detail.     

Transport parameters of granular La0.67Ca0.33MnO3 films grown on an R-plane sapphire

Precisely (100)-oriented, 200-nm thick La_0.67Ca_0.33MnO₃ films have been grown by laser ablation on a sapphire (R-plane) substrate covered by a (100)SrTiO₃/(001)Bi₂SrNb₂O₉/(001)CeO₂ trilayer buffer. The azimuthal misorientation of crystal grains (50–300 nm) in the La_0.67Ca_0.33MnO₃ films decreased by about 40% as the condensation temperature was increased ered from 760 to 810° C. The lattice parameter of the grown manganate films was reduced to 3.81–3.82 Å by enriching them with oxygen. The maximum in the temperature dependence of the electrical resistivity of the La_0.67Ca_0.33MnO₃ films grown was shifted toward lower temperatures by 20–50 K relative to its position for bulk ceramic samples of a stoichiometric composition. The largest magnetoresistance (MR=42% at H=0.4 T) was found in La_0.67Ca_0.33MnO₃ films with a Mn⁴⁺ concentration on the order of 50% (T=166 K).     

Effect of phase stratification into electro- and magnetotransport in heteroepitaxial La2/3Ca1/3MnO3 films

The La_2/3Ca_1/3MnO₃ films 25-nm thick biaxially compressed in the substrate plane, grown quasi-coherently on the (001) surface of the LaAlO₃ single crystal, were studied using laser vaporization. It was found that mechanical stresses acting during nucleation and growth promoted calcium enrichment of the cation sublattice of the manganite layer, which caused a decrease in its unit cell volume. Crystalline grains in manganite films were distinctly oriented along the normal to the substrate plane; the grain size in the substrate plane was within 20–40 nm, and the relative grain misorientation in the substrate plane did not exceed 0.2°. In zero magnetic field, the maximum in the temperature dependence of the resistivity ρ of La_2/3Ca_1/3MnO₃ films was observed at temperatures close to 210 K. At T < 100 K and μ₀ H = 2 T, the magnetoresistance of manganite films was negative, weakly depended on temperature, its value was about–0.45. The magnetic field caused transformation of nonferromagnetic phase inclusions to ferromagnetic ones, which resulted in a decrease in the La_2/3Ca_1/3MnO₃ film resistivity with increasing magnetic field. At low temperatures (T < 100 K), a hysteresis was observed in the dependences of the film resistivity on the magnetic field.     

Microstructure and dielectric properties of Li2CO3 doped 0.7(Ba,Sr)TiO3–0.3MgO ceramics

Microstructure and dielectric properties of Li₂CO₃ doped 0.7(Ba,Sr)TiO₃–0.3MgO ceramics for the low temperature sintering and microwave applications will be presented. In these days, low temperature sintering process has been widely spread out for the integrated electronic modules for the communication systems such as front-end modules, antenna modules, and switching modules. We have added Li₂CO₃ and MgO to (Ba,Sr)TiO₃ material to reduce the sintering temperature and improve dielectric properties such as loss tangent, and frequency dispersion.In this paper, we have discussed the crystalline properties, dielectric properties, and the microstructures of Li₂CO₃ doped 0.7(Ba,Sr)TiO₃–0.3MgO ceramics. No pyro phase was observed in the X-ray diffraction method. Very weak frequency dispersion (<0.7%) of dielectric permittivity was observed from the 1 kHz to 1 MHz range. We found that the grain size of BST is around 2 μm, while the grain size of Li₂CO₃ dope 0.7BST–0.3MgO is around 4 μm from the SEM analysis.     

Lithium ion conduction in A-site deficient perovskites R1/4Li1/4TaO3 (R=La,Nd, Sm and Y)

New lithium ion conductors of perovskite-type compounds R_1/4Li_1/4TaO₃ (R=La, Nd, Sm and Y) were synthesized, and their crystal structure and lithium ion conductivity were characterized. Symmetry of the perovskite lattice changed from cubic for La_1/4Li_1/4TaO₃ to tetragonal for Nd_1/4Li_1/4TaO₃ and Sm_1/4Li_1/4TaO₃, and to orthorhombic for Y_1/4Li_1/4TaO₃. The alternate ordering of R and Li ions and vacancies at the A-sites was observed for Nd_1/4Li_1/4TaO₃, Sm_1/4Li_1/4TaO₃ and Y_1/4Li_1/4TaO₃. The cube root (V^1/3) of the subcell volume decreased with decreasing the ionic radius of R cations which act as spacers for the perovskite lattice. With decrease in V^1/3 from La_1/4Li_1/4TaO₃ to Y_1/4Li_1/4TaO₃, the bulk conductivity at 400 K decreased from 1.4×10⁻¹ S m⁻¹ to 5.0×10⁻⁷ S m⁻¹ and its activation energy increased from 0.35 eV to 0.85 eV. The subcell volume and the ordering at the A-sites are major factors in influencing lithium ion conduction in these perovskite-type conductors.