Synthesis of single-crystalline perovskite nanorods composed of barium titanate and strontium titanate

We report the solution-based synthesis of single-crystalline nanorods composed of barium titanate (BaTiO3) and strontium titanate (SrTiO3), which yields well-isolated nanorods with diameters ranging from 5 to 60 nm and lengths reaching up to >10 mum. Electron microscopy and diffraction measurements show that these nanorods are composed of single-crystalline cubic perovskite BaTiO3 and SrTiO3 with a principal axis of the unit cell preferentially aligned along the wire length. These BaTiO3 and SrTiO3 nanorods should provide promising materials for fundamental investigations on nanoscale ferroelectricity, piezoelectricity, and paraelectricity.     

锆钛酸镧铅结构象和缺陷

锆钛酸镧铅(简称 PLZT)是一种十分重要的铁电材料.利用 PLZT 透明陶瓷的场致相变,还有可能在图象存贮和显示中得到应用.目前,在利用 La/Zr/Ti 比为7.9/70/30或8/65/35的 PLZT 透明陶瓷制作平面显示器、散射光开关和电光图象存贮器等方面开展了不少工作.PLZT 透明陶瓷的基本组成是锆钛酸铅掺 La 改性,形成(Pb,La)(Zr,Tj)O_3四元系固溶体.化学式倾向于:Pb_(1-x),La_x(Zr_(1-y),Ti_y)_(1-x/4)O_3.其中,La 的浓度 x 可在2～30％之间改变,而 Zr 与 Ti 的相互比例可连续变化.为了提高 PLZT 性能,人们往往通过改变这一比例加以实现.然而,我们的计算结果指出,这一比例的改变将使晶格能发生变化.我们用高分辨电子显微镜在晶格水平上对配比为8/65/35和7.9/70/30的 PLZT 进行了观察,发现配方7.9/70/30有更多的缺陷.计算表明,这可能是由于7.9/70/30的晶格能比8/65/35相对较低造成的.     

Porous SnO2/layered titanate nanohybrid with enhanced electrochemical performance for reversible lithium storage

A porous hybrid of titanate nanosheets with SnO(2) nanoparticles has been realized by an exfoliation and reassembling route. The present nanohybrid shows a large reversible capacity of 860 mA h g(-1) with a good capacity retention (about 60% retention of the initial capacity after 50 cycles).     

Lithium storage in hollow spherical ZnFe2O4 as anode materials for lithium ion batteries

Hollow microspheres composed of phase-pure ZnFe₂O₄ nanoparticles (hierarchically structured) have been prepared by hydrothermal reaction. The unique hollow spherical structure significantly increases the specific capacity and improves capacity retention of this material. The product of each phase transition during initial discharge (ZnFe₂O₄ ? Li_0.5ZnFe₂O₄ ? Li₂ZnFe₂O₄ → Li₂O + Li–Zn + Fe) and their structural reversibility are recognized by X-ray diffraction and electrochemical characterization. The products of the deeply discharged (Li–Zn alloy and Fe) and recharged materials (Fe₂O₃) were clarified based on high resolution transmission electron microscopic technique and first-principle calculations.     

Synthesis of silica-pillared layered lanthanum titanate with high thermal stability

It is now well established that layered solids other than smectite clays may bepillared to form three-dimensional crosslinked materials, the porosity of which isultimately tunable by the nature of the host substrate and the chemical species     

Electrochemical and structural characterization of lithium titanate electrodes

Lithium titanate (LTO) materials of different particle size, surface area, and morphology were characterized by constant current cycling and cyclic voltammetry. By examining the particles and electrodes with scanning electron microscopy, we show that particle morphology, in addition to particle size, has important implications for high-rate performance. Large agglomerates, even when porous and made of small crystallites, cannot effectively form homogenous electrodes with the polymer binder and carbon conducting diluents; hence, low power performance results. Another nanostructured LTO of very high surface area was found to have poor electrochemical performance most likely due to its high concentration of structural defects. We recommend further development in nanoparticles of LTO of optimal crystallinity as well as improved electrode homogeneity through the use of more compatible binders and conducting diluents and better electrode processing techniques. Simultaneous realization of these imperatives should facilitate the development of LTO-based high-power batteries for automotive applications.     

Lithium aluminate-doped lithium orthosilicate: Sol-gel ceramics and lithium dynamics

Dense ceramics (Li_4+xSi_1−xAl_xO₄ with 0 ≤ x ≤ 0.3) are obtained by sintering at 700–900°C, without prior calcination, of sol-gel powders prepared by an alkoxide-hydroxide route. In comparison with the pure lithium orthosilicate (3 × 10⁻⁴ S · cm⁻¹ at 350°C), only a slight enhancement of the ionic conductivity is noted for monophase ceramics with Li₄SiO₄-type structure (5 × 10⁻⁴ S · cm⁻¹ at 350°C for x = 0.3). Higher conductivity (2 × 10⁻² S · cm⁻¹ at 350°C) is observed for an heterogeneous material formed of a lithium silicoaluminate phase (x = 0.2) with the Li₄SiO₄-type structure coexisting with lithium hydroxide. In this two-phase material, ac conductivity and ⁷Li spin-lattice relaxation data are consistent with the formation of a new kinetic path, via a thin layer along the interface, which enhances the lithium mobility.     

Lithium storage in single-walled carbon nanotubes

Here, we investigated the lithium insertion/extraction mechanism in single-walled carbon nanotubes (SWNTs) based both on the empty SWNTs and filled SWNTs, including ferrocene-filled SWNTs (Fc@SWNTs) and C₆₀-filled SWNTs (C₆₀@SWNTs). SWNTs, C₆₀@SWNTs and Fc@SWNTs were systematically investigated as anode materials for Li-ion batteries. The electrochemical performance of the C₆₀@SWNT electrode was slightly better than that of the SWNTs, and the reversible capacity of Fc@SWNTs per unit weight was ～1.7 times greater than that of the empty SWNTs due to its special tube internal structure. It was proved that the dominant reversible sites for lithium storage in empty SWNTs are the trigonal interstitial channels. Meanwhile, lithium can reversibly insert or extract the inner channels of the tubes after doping with ferrocene; the reversible capacity presented in the inner channels of Fc@SWNTs is about Li_1.13C₆.     

Direct large-scale synthesis of perovskite barium strontium titanate nano-particles from solutions

This paper reports a wet chemical synthesis technique for large-scale fabrication of perovskite barium strontium titanate nano-particles near room temperature and under ambient pressure. The process employs titanium alkoxide and alkali earth hydroxides as starting materials and involves very simple operation steps. Particle size and crystallinity of the particles are controllable by changing the processing parameters. Observations by X-ray diffraction, scanning electron microscopy and transmission electron microscopy TEM indicate that the particles are well-crystallized, chemically stoichiometric and ∼50 nm in diameter. The nanoparticles can be sintered into ceramics at 1150 °C and show typical ferroelectric hysteresis loops.     

Regenerable hydrogen storage in lithium amidoborane

Regenerable hydrogen storage of lithium amidoborane is firstly achieved through the routes of direct thermal dehydrogenation and subsequent chemical hydrogenation of its dehydrogenated products by treatment with hydrazine in liquid ammonia.     

Preparation and structural characterization of rare-earth doped lead lanthanum zirconate titanate ceramics

A new preparation route towards rare-earth (RE) doped polycrystalline lead lanthanum zirconate titanate (PLZT) ceramics (RE = Y³⁺, Nd³⁺, Yb³⁺), based on the use of doped lanthanum oxide or zirconia, is reported. Structural characterization by X-ray powder diffraction reveals that secondary phase formation can be substantially diminished in comparison to conventional preparation methods. The distribution of the rare-earth dopants was investigated as a function of concentration by static ²⁰⁷Pb spin echo NMR spectra, using Fourier Transformation of Carr–Purcell–Meiboom–Gill spin echo trains. For the Nd- and Yb-doped materials, the interaction of the ²⁰⁷Pb nuclei with the unpaired electron spin density results in significant broadening and shifting of the NMR signal, whereas these effects are absent in the diamagnetic Y³⁺ doped materials. Based on different concentration dependences of the NMR lineshape parameters, we conclude that the structural role of the Nd³⁺ dopants differs significantly from that of Yb³⁺. While the Nd³⁺ ions appear to be statistically distributed in the PLZT lattice, incorporation of Yb³⁺ into PLZT appears to be limited by the appearance of doped cubic zirconia as a secondary phase.     

Derivated titanate nanotubes and their hydrogen storage properties

Titanate nanotubes and their derivates, Pd-loaded and Co²⁺, Zn²⁺, Cu²⁺, and Ag⁺ ion-exchanged titanate nanotubes, were respectively prepared and characterized by XRD, HR-TEM, and EDS. Their hydrogen storage properties were investigated, and the results revealed that the derivated titanate nanotubes had better hydrogen storage characters. Pd-loaded titanate nanotubes exhibited the highest hydrogen storage capacity of 1.03 wt%, which is three times higher than that of raw titanate nanotubes. The ion-exchanged titanate nanotubes also showed enhanced capacity. Especially, Co-TiNT reached a storage capacity of 0.80 wt%. The reason why hydrogen storage capacity was enhanced in titanate nanotubes was a pilot study. These results indicated that oxide nanotubes provided some new opportunities for hydrogen energy applications.     

Chemical and electronic characterization of cobalt in a lanthanum perovskite. Effects of strontium substitution

Two different cobaltites, LaCoO₃ and La_0.5Sr_0.5CoO_3−δ, have been prepared and characterized by means of high energy Co K-edge and low energy O K-edge X-ray absorption spectroscopy (XAS). Even though half of the La(III) is substituted by Sr(II), little or no changes can be detected in the formal oxidation state of cobalt atoms. The presence of strontium cations induces two main effects in the chemical and electronic state of the perovskite. The charge balance with Sr(II) species is reached by the formation of oxygen vacancies throughout the network, which explains the well-known increase in the reactivity of this substituted perovskite. O K-edge XAS experiments show that the Sr(II) species induce the transitions of d electrons of cobalt cations from low to high spin configuration. We propose that this change in spin multiplicity is induced by two cooperative effects: the oxygen vacancies, creating five coordinated cobalt atoms, and the bigger size of Sr(II) cations, aligning the Co-O-Co atoms, and favoring the overlapping of π-symmetry cobalt and oxygen orbitals, reducing the splitting energy of e_g and t_2g levels.     

Electrochemical performance of lithium titanate anode fabricated using a water-based binder

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Study of the formation of perovskite type lanthanum ruthenates by heating their hydrous precursor

Emanation thermal analysis (ETA), differential thermal analysis (DTA), thermogravimetry (TG), evolved gas analysis with mass spectrometric detection (EGA-MS), and X-ray diffraction (XRD) were used to investigate the formation of perovskite type lanthanum ruthenates on heating their hydroxide precursor in argon from 20 to 1200 degrees C. The co-precipitated lanthanum-ruthenium mixed hydroxide containing a small amount of carbonates was used as a precursor. The mass loss corresponding to the release of water and CO(2) from the precursor was determined by TG and EGA (MS), respectively. The ETA characterized the exposure of sample surface after release of water and CO(2), as well as microstructure development corresponding to the crystallization and structure ordering of LaRuO(3) and La(3.5)Ru(4.0)O(13) perovskite phases. The obtained information on formation of phases and their transformation is useful for optimizing their synthesis protocols for achieving the desired physical properties, and to estimate the thermal stability of these materials to be used as catalysts.     

Theoretical study of two possible occupation sites for tritium atoms in lithium titanate

Tritium breeder materials are fundamental to the development of a fusion reactor. One of the materials under investigation is lithium titanate, which has a good thermal stability, high density of lithium and low activation under irradiation, which are the fundamental properties that are demanded from this type of materials. However, there are little data on physical and chemical properties, which are necessary in order to design a material with the best characteristics to be used in a fusion reactor. We present a theoretical investigation on possible occupation sites for tritium atoms in lithium titanate structure using ab initio Hartree–Fock method. Two possible substitutional Li sites were identified for a tritium atom: one in the titanium layer and the other in the lithium layer. This study showed that the tritium released would favorably occupy positions in lithium layers than in titanium layers. Tritium occupying sites in titanium layers would require more energy to release in comparison to lithium layers. An interesting relation is seen between these results and experimental data.     

Tunable lithium storage properties of metal lithium titanates by stoichiometric modulation

A simple stoichiometric modulation of Na_2 − 2xSr_xLi₂Ti₆O₁₄ was developed to achieve tunable electrochemical properties of the material. The concept was confirmed experimentally and theoretically using density functional theory (DFT) calculations. Both the operating potential and the amount of reversibly intercalated lithium ions were manipulated by simply changing the Na/Sr ratio. These unique characteristics originated from a gradual change in the electron density on the Ti atoms and the extra lithium insertion sites at SrLi₂Ti₆O₁₄. As a promising anode material for lithium-ion batteries, Na_2 − 2xSr_xLi₂Ti₆O₁₄ and its tunable electrochemical properties have significant importance in terms of the development of tailored electrodes with desirable electrochemical performance.     

Modification of LiCoO2 through rough coating with lithium lanthanum zirconium tantalum oxide for high-voltage performance in lithium ion batteries

Journal of Solid State Electrochemistry - In this study, the spray-drying technique was used to apply a 0.5 at%, 1 at%, and 1.25 at% of lithium lanthanum zirconium tantalum oxide...     

A mechanism for non-stoichiometry in the lithium amide/lithium imide hydrogen storage reaction

We demonstrate, through structural refinement from synchrotron X-ray diffraction data, that the mechanism of the transformation between lithium amide and lithium imide during hydrogen cycling in the important Li-N-H hydrogen storage system is a bulk reversible reaction that occurs in a non-stoichiometric manner within the cubic anti-fluorite-like Li-N-H structure.