The influence of size on phase morphology and Li-ion mobility in nanosized lithiated anatase TiO2

Sustainable energy storage in the form of Li-ion batteries requires new and advanced materials in particular with a higher power density. Nanostructuring appears to be a promising strategy, in which the higher power density in nanosized materials is related to the dramatically shortened Li-ion diffusion paths. However, nanosizing materials also changes intrinsic material properties, which influence both ionic and electronic conductivity. In this work neutron diffraction is used to show that in addition to these two aspects, nanostructuring changes the phase behavior and morphology. Lithiated 40-nm TiO(2) anatase crystallites become single phase, either having the Li-poor original anatase phase, or the Li-rich Li-titanate phase, in contrast to microsized crystallites where these two phases coexist in equilibrium within one crystal particle. In addition, Li(x)TiO(2) compositions occur with stoichiometries that are not stable in micron-sized crystallites, indicating enhanced solid solution behavior. Reduced conduction electron densities at the sites of the Li ions are observed by NMR spectroscopy. This is accompanied by reduced spontaneous Li-ion mobility, suggesting a correlation between the electron density at the Li-ion site and the Li-ion mobility. The present results show that in the case of lithiated anatase TiO(2), significant effects on phase composition, morphology, and electronic configurations are induced, as well as slower intracrystallite Li diffusion.     

Two phase morphology limits lithium diffusion in TiO(2)(anatase): a (7)Li MAS NMR study.

7Li magic angle spinning solid-state nuclear magnetic resonance is applied to investigate the lithium local environment and lithium ion mobility in tetragonal anatase TiO(2) and orthorhombic lithium titanate Li(0.6)TiO(2). Upon lithium insertion, an increasing fraction of the material changes its crystallographic structure from anatase TiO(2) to lithium titanate Li(0.6)TiO(2). Phase separation occurs, and as a result, the Li-rich lithium titanate phase is coexisting with the Li-poor TiO(2) phase containing only small Li amounts approximately equal to 0.01. In both the anatase and the lithium titanate lattice, Li is found to be hopping over the available sites with activation energies of 0.2 and 0.09 eV, respectively. This leads to rapid microscopic diffusion rates at room temperature (D(micr) = 4.7 x 10(-12) cm(2)s(-1) in anatase and D(micr) = 1.3 x 10(-11) cm(2)s(-1) in lithium titanate). However, macroscopic intercalation data show activation energies of approximately 0.5 eV and smaller diffusion coefficients. We suggest that the diffusion through the phase boundary is determining the activation energy of the overall diffusion and the overall diffusion rate itself. The chemical shift of lithium in anatase is independent of temperature up to approximately 250 K but decreases at higher temperatures, reflecting a change in the 3d conduction electron densities. The Li mobility becomes prominent from this same temperature showing that such electronic effects possibly facilitate the mobility.     

On the homogeneity range of the κ phases in the Hf-Mo-{Si,P, S,Ge, As,Se} systems

A survey of the various two- and three-phase equilibria involving the κ phases in the subsolidus regions of the ternary Hf-Mo-{Si, P, S, Ge, As, Se} systems has been made. The κ phases have homogeneity ranges, accompanied by variations in the unit-cell volumes. The hexagonal κ-phase structure is composed of a transition metal sublattice with triangular prismatic and octahedral interstices. The nonmetal atoms may occupy one or both types of interstices. Phase-analytical and crystallographic results suggest a variable degree of hafnium substitution on the molybdenum sites in the metal sublattice as the major cause of the variations in composition observed. The κ phase in the Hf-Mo-S system exhibits a particularly large extension of the homogeneity range. This fact might be interpreted in terms of an enhanced thermodynamic stability of this phase, connected with the filling of both octahedral and triangular prismatic sites by sulfur in the structure, in contrast to the empty octahedral sites in the remaining κ phases.     

The crystal structures of the lithium-inserted metal oxides Li0.5TiO2 anatase,LiTi2O4 spinel,and Li2Ti2O4

The crystal structures of three lithium titanates by neutron diffraction powder profile analysis were determined. The tetragonal anatase form of TiO₂ becomes orthorhombic on ambient-temperature lithium insertion to Li_0.5TiO₂ due to the formation of TiTi bonds. The lithium partially occupies the highly distorted octahedral interstices in the anatase framework in fivefold-coordination with oxygen. Cubic LiTi₂O₄ formed by heating Li_0.5TiO₂ anatase has a normal spinel structure with Li in the tetrahedral sites. In Li₂Ti₂O₄ formed by reacting LiTi₂O₄ spinel with n-BuLi at ambient temperature, the titanium remains in the spinel positions but the lithium is displaced, filling all the available octahedral sites.     

Magnetism and structural chemistry of the n=2 Ruddlesden-Popper phase La3LiMnO7

Polycrystalline samples of the n=2 Ruddlesden-Popper phase La₃LiMnO₇ have been prepared and characterized. X-ray and neutron diffraction suggest that the structure is tetragonal with a disordered distribution of Li and Mn cations over the octahedral sites, but ⁶Li MAS NMR shows that the Li and Mn are 1:1 ordered locally. Electron microscopy shows that the stacking of the cation-ordered, perovskite-like bilayers along the crystallographic z-axis is disordered on the distance scale sampled by X-ray and neutron diffraction. Magnetometry data and neutron diffraction data collected at 2 K together suggest that the Mn cations within each structural domain order antiferromagnetically at 14 K, but that the disorder along z prevents the establishment of long-range magnetic order.     

Defect chemistry, surface structures, and lithium insertion in anatase TiO2

Atomistic simulation techniques are used to investigate the defect properties of anatase TiO(2) and Li(x)TiO(2) both in the bulk and at the surfaces. Interatomic potential parameters are derived that reproduce the lattice constants of anatase, and the energies of bulk defects and surface structures are calculated. Reduction of anatase involving interstitial Ti is found to be the most favorable defect reaction in the bulk, with a lower energy than either Frenkel or Schottky reactions. The binding energies of selected defect clusters are also presented: for the Ti(3+)-Li(+) defect cluster, the binding energy is found to be approximately 0.5 eV, suggesting that intercalated Li ions stabilize conduction band electrons. The Li ion migration path is found to run between octahedral sites, with an activation energy of 0.45-0.65 eV for mole fractions of lithium in Li(x)TiO(2) of x < or = 0.1. The calculated surface energies are used to predict the crystal morphology, which is found to be a truncated bipyramid in which only the (101) and (001) surfaces are expressed, in accord with the available microscopy data. Calculations of defect energies at the (101) surface suggest that single Ti(3+) defects and neutral Ti(3+)-Li(+) pairs tend to segregate to the surface.     

The effect of concentration on Li diffusivity and conductivity in rutile TiO2

Li transport characteristics are studied by means of density functional theory (DFT) and molecular dynamics (MD) simulations in order to investigate concentration effects on Li chemical diffusivity and conductivity in TiO(2) rutile. Our MD simulations predict one-dimensional diffusion of Li ions via jumps between the octahedral sites along the channels parallel to the c-axis. The diffusion barrier and diffusion coefficient (at room temperature) for the isolated Li, determined by means of DFT calculations, correspond to 60 meV and 9.1 × 10(-6) cm(2) s(-1), respectively. Such a small barrier suggests rapid mass transport along the channels. MD simulations are performed to evaluate the concentration dependent diffusivity profiles. The changes in Li energetics and dynamics are studied as a function of Li content, which is varied primarily between 10% and 50%. In addition, we consider a couple of compositions over 50% although this is above the intercalation limit. Our results suggest that Li diffusivity is strongly dependent on the Li?∶?TiO(2) ratio, and it decreases with increasing Li concentration. For instance, at room temperature, we find Li diffusivity for high concentrations (50% Li) to be three orders of magnitude slower than that for lower concentrations (10% Li). Our analyses on the energetics and dynamics suggest that the changes in the diffusivities originate from successive increases in the barriers with increasing concentration. The decrease in diffusivity as a function of increasing Li content is attributed to the fact that additional Li ions successively block the energetically preferred vacant sites along the channels. Our analyses also show that increasing Li concentration enhances the Li-Li repulsion within the channels, and as a result, diffusion is hindered. We also compare concentration-dependent diffusivities for Li diffusion in anatase, rutile and amorphous TiO(2). Interestingly, we find differing concentration dependence of the diffusivity in these chemically identical but structurally non-equivalent TiO(2) polymorphs. Our study suggests that these differences result from intrinsic structural characteristics of TiO(2) polymorphs, which ultimately contribute to intercalation limit, diffusivity, ionic conductivity, and the electrochemical performance in energy storage applications.     

Real time observation of the hydrothermal crystallization of barium titanate using in situ neutron powder diffraction.

The hydrothermal crystallization of barium titanate, BaTiO3, has been studied in situ by time-resolved powder neutron diffraction methods using the recently developed Oxford/ISIS hydrothermal cell. This technique has allowed the formation of the ferroelectric ceramic to be followed in a noninvasive manner in real time and under genuine reaction conditions. In a first set of experiments, Ba(OD)2-8D2O was reacted with two different titanium sources, either crystalline TiO2 (anatase) or amorphous TiO2-H2O in D2O, at 100-140 degrees C and the reaction studied using the POLARIS time-of-flight neutron powder diffractometer, at the ISIS Facility. In a second series of experiments, the reaction between barium chloride and crystalline TiO2 (anatase) in NaOD/D2O was studied at temperatures between 100 and 200 degrees C and at different deuterioxide concentrations using the constant-wavelength D20 neutron powder diffractometer at the Institut Laue Langevin. Quantitative growth and decay curves were determined from analysis of the integrated intensities of Bragg reflections of starting materials and product phases. In both sets of experiments the rapid dissolution of the barium source was observed, followed by dissolution of the titanium source before the onset of crystallization of barium titanate. Using a nucleation-growth model we are able to simulate the growth curve of barium titanate at three temperatures. Our results indicate the predominance of a homogeneous dissolution-precipitation mechanism for the hydrothermal formation of barium titanate, rather than other possible mechanisms that have been discussed in the literature. Analysis of the line widths of the Bragg reflections in the neutron diffraction data indicates that the particle size of the BaTiO3 product phase prepared from the amorphous TiO2-H2O is smaller than that prepared from crystalline TiO2 (anatase).     

表面相结结构在促进光催化电荷分离中的应用

二十世纪八十年代以来,特别是近十年,光催化研究在利用可再生能源太阳能的道路上飞速发展。越来越多的研究表明,相结结构的构筑是有效提高半导体光催化剂性能的重要策略。其中, TiO2作为重要的模型光催化剂,其相关研究成果呈现出指数增长的趋势。本综述围绕TiO2模型光催化剂,主要介绍TiO2表面相结的研究成果,包括TiO2表面相的表征、锐钛矿：金红石TiO2相结用于光催化产氢研究、TiO2相结在光催化中作用的最新认识等。在表征方面,通过表面灵敏的紫外拉曼光谱研究了TiO2相变过程中表面相结构的变化,结合可见拉曼以及XRD表征揭示了TiO2独特的相变过程,即相变始于锐钛矿粒子的界面处,小粒子逐渐团聚为大粒子,致其相变从大粒子体相开始最终扩展到整个粒子。使用CO, CO2探针红外光谱,根据锐钛矿和金红石表面吸附物种的差异,进一步证实了锐钛矿：金红石表面相结结构,为紫外拉曼光谱的表面表征特性提供坚实证据。同时,利用发光光谱观察到锐钛矿晶相的可见发光带和金红石晶相的近红外发光带,并基于此给出了TiO2材料表面相结结构的荧光表征新方法。此外荧光光谱还提供了锐钛矿、金红石相中载流子动力学信息,揭示了束缚态在光催化中的作用。在光催化应用方面,观察到混相结构TiO2较单独锐钛矿及金红石相具有更高的光催化产氢活性,通过在较大金红石颗粒上担载纳米锐钛矿粒子,证明了相结结构在提高光催化活性中的核心作用,并首次提出了锐钛矿：金红石表面异相结结构概念,推断其对电荷分离的促进作用是最终提高反应活性的原因。之后将此概念应用到改善商品TiO2(P25)光催化活性中,通过可控热处理精细调控P25的表面相结构,在光催化重整生物质衍生物产氢实验中,成功将P25光催化产氢活性提高3?5倍。之后发展了新的TiO2表面控制方法,通过加入Na2SO4等相变控制剂,延缓了TiO2从锐钛矿向金红石的相变过程,在较高温度下实现TiO2相结结构的调控,最终可将P25光催化重整甲醇制氢的活性提高6倍,同时通过高分辨电镜清晰观察到锐钛矿：金红石相结的原子层生长接触。在相结作用机理方面,多种时间分辨光谱技术以及理论计算被用作探索锐钛矿：金红石相结处的电子转移机理。通过时间分辨红外光谱对TiO2表面相结结构作用的研究,特别是利用锐钛矿、金红石不同的瞬态吸收光谱特征,证明了锐钛矿：金红石相结处的载流子转移过程,存在锐钛矿向金红石的电子转移过程。模型光催化剂TiO2相结的研究成果,加深了对光催化机理的认识,促进新型高效光催化体系的设计合成。     

Dispersion and Structure Studies of Molybdenum Oxide on Anatase TiO2

X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS) were used to characterize the structure of the mixture of molybdenum oxide and anatase calcined at 723 K. The resuits indicate that molybdenum oxide can disperse onto the surface of anatase (TiO2) and the dispersion threshold is 11.2 mg in per gram of MoO3 or 4.8 Mo atoms/nm^2 TiO2. When the coment of MoO3 is below the dispersion threshold, MoO3 species is in highly dispersed state interacting strongly with TiO2 support and in discrete tetrahedral coordination. [MoO4], on the surface of TiO2. When the MoO3 loading is above this value, MoO3 exists in both dispersed phase and crystalline phase. MoO3 in dispersed phase is still a discrete [MoO4] tetrahedron; MoO3 in crystal phase is in octahedral coordination.     

UV Raman spectroscopic study on TiO2. I. Phase transformation at the surface and in the bulk

Phase transformation of TiO2 from anatase to rutile is studied by UV Raman spectroscopy excited by 325 and 244 nm lasers, visible Raman spectroscopy excited by 532 nm laser, X-ray diffraction (XRD), and transmission electron microscopy (TEM). UV Raman spectroscopy is found to be more sensitive to the surface region of TiO2 than visible Raman spectroscopy and XRD because TiO2 strongly absorbs UV light. The anatase phase is detected by UV Raman spectroscopy for the sample calcined at higher temperatures than when it is detected by visible Raman spectroscopy and XRD. The inconsistency in the results from the above three techniques suggests that the anatase phase of TiO2 at the surface region can remain at relatively higher calcination temperatures than that in the bulk during the phase transformation. The TEM results show that small particles agglomerate into big particles when the TiO2 sample is calcined at elevated temperatures and the agglomeration of the TiO2 particles is along with the phase transformation from anatase to rutile. It is suggested that the rutile phase starts to form at the interfaces between the anatase particles in the agglomerated TiO2 particles; namely, the anatase phase in the inner region of the agglomerated TiO2 particles turns out to change into the rutile phase more easily than that in the outer surface region of the agglomerated TiO2 particles. When the anatase particles of TiO2 are covered with highly dispersed La2O3, the phase transformation in both the bulk and surface regions is significantly retarded, owing to avoiding direct contact of the anatase particles and occupying the surface defect sites of the anatase particles by La2O3.     

二氧化钛系列光催化剂的拉曼光谱

采用溶胶-凝胶法制备了TiO₂粉体和薄膜光催化剂.使用FT-Raman光谱和激光共聚焦拉曼光谱研究了粉体和薄膜的拉曼光谱,探讨了热处理条件、Fe³⁺掺杂和以硅胶为载体的薄膜化所引起的TiO₂结构变化.结果表明,TiO₂在350℃存在由无定形向锐钛矿相的转变,600℃下存在锐钛矿相向金红石相的转变,750℃下完全转变为金红石相;掺杂会引起TiO₂的晶格畸变,导致拉曼谱峰宽化;以硅胶为载体的TiO₂负载薄膜的部分拉曼谱峰与粉体相比,有一定的位移和宽化.     

EPR investigation of TiO2 nanoparticles with temperature-dependent properties

An in situ electron paramagnetic resonance (EPR) study has been carried out for anatase (Hombikat UV100) and rutile TiO(2) nanoparticles at liquid helium (He) temperature (4.2 K) under UV irradiation. Rutile titania was synthesized by ultrasonic irradiation with titanium tetrachloride (TiCl(4)) as the precursor. XRD and Raman results evidence the crystallinity of titania phases. The nature of trapped electrons and holes has been investigated by EPR spectroscopy under air and vacuum conditions. Illumination of TiO(2) powder (anatase and rutile) at 4.2 K resulted in the detection of electrons being trapped at Ti(4+) sites within the bulk and holes trapped at lattice oxide ions at the surface. The stability of electron traps was very sensitive to temperature in both phases of TiO(2). The annealing kinetics of the EPR detected radicals has been studied from 4.2 K to ambient temperature and also for calcined titania particles from 523 to 1273 K.     

The structures of lithium-inserted metal oxides: LiReO3 and Li2ReO3

The crystal structures of LiReO₃ and Li₂ReO₃, obtained by Li insertion into ReO₃, were determined by neutron diffraction powder profile analysis. For both phases, the ReO₃ host lattice, made exclusively of corner-shared octahedra, was altered significantly on Li insertion without breaking bonds. The original 12-coordinated perovskite-like cavity was changed into two octahedral sites, which are occupied by the lithium ions.     

Extensive migration of Ni and Mn by lithiation of ordered LiMg0.1Ni0.4Mn(1.5)O4 spinel

Li(x)Mg(0.1)Ni(0.4)Mn(1.5)O(4) spinel (P4(3)32) was chemically and electrochemically lithiated in the range 1 < x 相似文献   

Unique Ordered TiO(2) Superstructures with Tunable Morphology and Crystalline Phase for Improved Lithium Storage Properties

Unique ordered TiO(2) superstructures with tunable morphology and crystalline phase were successfully prepared by the use of different counterions. Dumbbell-shaped rutile TiO(2) and nanorod-like rutile mesocrystals constructed from ultrathin nanowires, and quasi-octahedral anatase TiO(2) mesocrystals built from tiny nanoparticle subunits were achieved. Interestingly, the obtained anatase mesocrystals have a fine microporous structure and a large surface area. The influence of the counterions in the reaction system is discussed and possible mechanisms responsible for the formation of the unique ordered TiO(2) superstructures with different morphologies and crystalline phases are also proposed based on a series of experimental results. The obtained TiO(2) superstructures were used as anode materials in lithium ion batteries, and exhibited higher capacity and improved rate performance; this is attributed to the intrinsic characteristics of the mesoscopic TiO(2) superstructures, which have a single-crystal-like and porous nature.     

Large impact of particle size on insertion reactions. A case for anatase Li(x)TiO2

Insertion reactions are of key importance for Li ion and hydrogen storage materials and energy storage devices. The particle size dependence of insertion reactions has been investigated for lithiated anatase TiO2, revealing progressively increasing Li capacity and Li-ion solubility for decreasing particle sizes, strongly deviating from the expected Li-rich and Li-poor phase separation as occurs in the bulk material. The phase diagram alters significantly, changing the materials properties already at sizes as large as 40 nm. A rationale is found in the surface strain that occurs between the different intercalated phases, which becomes energetically too costly in small particles. In particular the observed particle size-induced solid solution behavior is expected to have fundamental and practical implications for two-phase lithium or hydrogen insertion reactions.     

The role of crystal phase in determining photocatalytic activity of nitrogen doped TiO2

Two series of nitrogen doped TiO(2) samples with different ratios of anatase to rutile phases were prepared by milling the mixture of P25 TiO(2) and C(6)H(12)N(4) in air and gaseous NH(3) atmosphere, respectively. Compared to air, NH(3) atmosphere plays an important role in delaying the crystallite transformation from anatase to rutile in the mechanochemical reaction of TiO(2) and C(6)H(12)N(4). In contrast to the previously reported results for pure TiO(2), it is found that nitrogen doped TiO(2) with higher content of rutile phase demonstrates higher photocatalytic activity in photodegrading pollutant Rhodamine B under both UV light and visible light irradiation (lambda>420 nm), and the amount of the surface-adsorbed water and hydroxyl groups on nitrogen doped TiO(2) have little correlations with their crystallite phases (anatase or rutile) and photocatalytic activity. The more abundant surface states characterized by photoluminescence spectroscopy together with the lowered valence band maximum of rutile TiO(2) by nitrogen doping are considered as the key factors for the higher activity of nitrogen doped TiO(2) with higher content of rutile phase.     

Surface-mediated growth of transparent, oriented, and well-defined nanocrystalline anatase titania films

A new, surface-mediated method to grow transparent, oriented, and well-defined nanocrystalline anatase TiO2 films has been developed. The morphology of crystals is tunable from octahedral pyramids to truncate octahedral pyramids. These novel nanocrystalline films could have implications not only for practical applications but also for understanding the structure and orientation dependent properties of the important anatase material.     

单分散TiO2亚微米球的制备与表征

采用乙腈与乙醇混合溶剂体系制备出了单分散的亚微米级TiO2球形胶体颗粒, 并对乙腈相对含量以及实验温度等参数的影响进行了研究. 结果表明5 ℃下乙腈相对含量为70%时可制得高质量的单分散胶体颗粒. 通过TEM、SEM、粒度分析等表征手段, 表明所得胶体颗粒平均直径约为540 nm, 标准偏差在5%以内, 颗粒的多分布系数为0.013, TG-DSC分析表明胶体颗粒为含水量很少的水合TiO2; XRD分析表明单分散TiO2胶体颗粒在600 ℃高温烧结由无定型转变为锐钛矿型, 在900 ℃高温烧结则开始出现金红石型.