Synthesis of Uniform Layered Protonated Titanate Hierarchical Spheres and Their Transformation to Anatase TiO2 for Lithium‐Ion Batteries

Layered protonated titanates (LPTs), a class of interesting inorganic layered materials, have been widely studied because of their many unique properties and their use as precursors to many important TiO₂‐based functional materials. In this work, we have developed a facile solvothermal method to synthesize hierarchical spheres (HSs) assembled from ultrathin LPT nanosheets. These LPT hierarchical spheres possess a porous structure with a large specific surface area and high stability. Importantly, the size and morphology of the LPT hierarchical spheres are easily tunable by varying the synthesis conditions. These LPT HSs can be easily converted to anatase TiO₂ HSs without significant structural alteration. Depending on the calcination atmosphere of air or N₂, pure anatase TiO₂ HSs or carbon‐supported TiO₂ HSs, respectively, can be obtained. Remarkably, both types of TiO₂ HSs manifest excellent cyclability and rate capability when evaluated as anode materials for high‐power lithium‐ion batteries.     

One-pot hydrothermal synthesis of porous anatase TiO2 nanotube formed bundles for lithium ion battery anodes

Anatase phase of TiO₂ nanomaterial has been deemed a potential anode material for lithium ion battery (LIB) applications because of its remarkable electrochemical properties. However, TiO₂ anodes always suffer from intrinsic poor electrical conductivity and slow ion kinetics, which would restrict their practical usage. To address this issue, efficient control and design of the anatase crystal structure of TiO₂ material with desirable morphology is one of the critical approaches. In this work, a good lithium storage capability of 181 mA hr g⁻¹ at rate of 0.2C, high rate performance of 70 mA hr g⁻¹ at 20C, and excellent cyclability of 117 mA hr g⁻¹ with a capacity retention of 93% at 1C after 100 cycles and 84 mA hr g⁻¹ at 10C after 1,000 cycles are observed in an optimized porous anatase TiO₂ one-dimensional nanotube bundle nanomaterial fabricated through a simple hydrothermal process with post calcination treatment. These excellent electrochemical properties of the product can be ascribed to its anatase crystal phase, 1D nanostructure, and porous framework with a large surface area, which provide it with an efficient electrode/electrolyte contact area and a faster ion/electron diffusion pathway.     

Block copolymer‐directed synthesis of porous anatase for lithium‐ion battery electrodes

A templating method is developed to produce porous nanocrystalline anatase materials for negative electrodes in lithium‐ion batteries (LIBs). Amphiphilic diblock copolymers are used to generate template films with phase‐separated internal structure. Subsequent swelling with acidified titanium(IV) bis(ammonium lactato) dihydroxide (TALH) solution yielded structured hybrid films. Upon heating, the formation of TiO₂ nanocrystals is induced, resulting in a three‐dimensional mesoporous structure directed by the bulk morphology of the polymer template. In comparison to commercial nanosized anatase, the structured anatase shows significant performance improvements in lithium‐ion coin cell batteries in terms of capacity, stability, and rate capability. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1890–1896     

Unique Ordered TiO2 Superstructures with Tunable Morphology and Crystalline Phase for Improved Lithium Storage Properties

Unique ordered TiO₂ superstructures with tunable morphology and crystalline phase were successfully prepared by the use of different counterions. Dumbbell‐shaped rutile TiO₂ and nanorod‐like rutile mesocrystals constructed from ultrathin nanowires, and quasi‐octahedral anatase TiO₂ 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 TiO₂ superstructures with different morphologies and crystalline phases are also proposed based on a series of experimental results. The obtained TiO₂ 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 TiO₂ superstructures, which have a single‐crystal‐like and porous nature.     

Synthesis and electrochemical performance of TiO2–sulfur composite cathode materials for lithium–sulfur batteries

Titania–sulfur (TiO₂–S) composite cathode materials were synthesized for lithium–sulfur batteries. The composites were characterized and examined by X-ray diffraction, nitrogen adsorption/desorption measurements, scanning electron microscopy, and electrochemical methods, such as cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge–discharge tests. It is found that the mesoporous TiO₂ and sulfur particles are uniformly distributed in the composite after a melt-diffusion process. When evaluating the electrochemical properties of as-prepared TiO₂–S composite as cathode materials in lithium–sulfur batteries, it exhibits much improved cyclical stability and high rate performance. The results showed that an initial discharge specific capacity of 1,460 mAh/g at 0.2 C and capacity retention ratio of 46.6 % over 100 cycles of composite cathode, which are higher than that of pristine sulfur. The improvements of electrochemical performances were due to the good dispersion of sulfur in the pores of TiO₂ particles and the excellent adsorbing effect on polysulfides of TiO₂.     

Silver-coated TiO2 nanostructured anode materials for lithium ion batteries

Anatase TiO₂ nanoribbons/nanotubes (TiO₂-NRTs) have been synthesised successfully via a reflux method followed by drying in a vacuum oven, and then, silver-coated TiO₂ NRTs (Ag/TiO₂-NRTs) were prepared by coating silver particles onto the TiO₂-NRTs surface by the traditional silver mirror reaction. The physical properties of the synthesised products were examined in detail using X-ray diffraction, field emission gun scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy, respectively. The results indicated that the Ag nanoparticles were uniformly deposited on the surface of the TiO₂ nanoribbons/nanotubes. The electrochemical properties were investigated by a variety of techniques. The rate capability and cycle durability for the Ag/TiO₂-NRTs were improved compared with TiO₂-NRTs. It is speculated that the Ag-coated TiO₂ nanoribbons/nanotubes are an effective anode candidate for lithium ion batteries.     

Preparation and electrochemical properties of Ag-modified TiO2 nanotube anode material for lithium–ion battery

TiO₂ nanotubes prepared by using a hydrothermal process were firstly coated with silver nanoparticles as the anode materials for lithium–ion batteries by the traditional silver mirror reaction. The physical properties of the as-synthesized samples were investigated by X-ray diffraction and transmission electron microscopic. The as-prepared samples were used as negative materials for lithium–ion battery, whose charge–discharge properties, cyclic voltammetry, electrochemical impedance spectroscopy and cycle performance were examined in detail. The results showed that the Ag additive decreased the polarization of anode, and marvelously improved the high-rate discharge capacity and cycling stability of TiO₂ nanotubes.     

A Microwave Synthesis of Mesoporous NiCo2O4 Nanosheets as Electrode Materials for Lithium‐Ion Batteries and Supercapacitors

A facile microwave method was employed to synthesize NiCo₂O₄ nanosheets as electrode materials for lithium‐ion batteries and supercapacitors. The structure and morphology of the materials were characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy and Brunauer–Emmett–Teller methods. Owing to the porous nanosheet structure, the NiCo₂O₄ electrodes exhibited a high reversible capacity of 891 mA h g^?1 at a current density of 100 mA g^?1, good rate capability and stable cycling performance. When used as electrode materials for supercapacitors, NiCo₂O₄ nanosheets demonstrated a specific capacitance of 400 F g^?1 at a current density of 20 A g^?1 and superior cycling stability over 5000 cycles. The excellent electrochemical performance could be ascribed to the thin porous structure of the nanosheets, which provides a high specific surface area to increase the electrode–electrolyte contact area and facilitate rapid ion transport.     

Recent Progress in Preparation and Lithium‐ion Storage Properties of TiO2 Mesocrystals

TiO₂ nanostructures have been considered as promising anode materials in a new generation of lithiumion batteries due to their high safety, superior rate capability and excellent cyclic stability. In particular, TiO₂ mesocrystals, a new class of superstructured materials, have attracted a great deal of research interests due to the unique structure composed of crystallographically oriented nanocrystals, and thus showed improved lithium‐ion insertion performance. In this review, recent progress in preparation and lithium‐ion storage properties of TiO₂ mesocrystals are summarized. Two typical ways for synthesizing TiO₂ mesocrystals are described, namely, the oriented topotactic transformation and direct synthesis in solution. The additive‐free synthesis of TiO₂ mesocrystals and their lithium‐ion intercalation properties are highlighted and discussed.     

Carbon Nanofibers Decorated with Molybdenum Disulfide Nanosheets: Synergistic Lithium Storage and Enhanced Electrochemical Performance

Traditional lithium‐ion batteries that are based on layered Li intercalation electrode materials are limited by the intrinsically low theoretical capacities of both electrodes and cannot meet the increasing demand for energy. A facile route for the synthesis of a new type of composite nanofibers, namely carbon nanofibers decorated with molybdenum disulfide sheets (CNFs@MoS₂), is now reported. A synergistic effect was observed for the two‐component anode, triggering new electrochemical processes for lithium storage, with a persistent oxidation from Mo (or MoS₂) to MoS₃ in the repeated charge processes, leading to an ascending capacity upon cycling. The composite exhibits unprecedented electrochemical behavior with high specific capacity, good cycling stability, and superior high‐rate capability, suggesting its potential application in high‐energy lithium‐ion batteries.     

TiO2 Microboxes with Controlled Internal Porosity for High‐Performance Lithium Storage

Titanium dioxide (TiO₂) is considered a promising anode material for high‐power lithium ion batteries (LIBs) because of its low cost, high thermal/chemical stability, and good safety performance without solid electrolyte interface formation. However, the poor electronic conductivity and low lithium ion diffusivity of TiO₂ result in poor cyclability and lithium ion depletion at high current rates, which hinder them from practical applications. Herein we demonstrate that hierarchically structured TiO₂ microboxes with controlled internal porosity can address the aforementioned problems for high‐power, long‐life LIB anodes. A self‐templating method for the synthesis of mesoporous microboxes was developed through Na₂EDTA‐assisted ion exchange of CaTiO₃ microcubes. The resulting TiO₂ nanorods were organized into microboxes that resemble the microcube precursors. This nanostructured TiO₂ material has superior lithium storage properties with a capacity of 187 mAh g⁻¹ after 300 cycles at 1 C and good rate capabilities up to 20 C.     

Porous cobalt oxide (Co3O4) nanorods: Facile syntheses, optical property and application in lithium-ion batteries

We developed a facile synthetic route of porous cobalt oxide (Co₃O₄) nanorods via a microemulsion-based method in combination with subsequent calcination process. The porous structure was formed by controlled decomposition of the microemulsion-synthesized precursor CoC₂O₄ nanorods without destruction of the original morphology. The as-prepared Co₃O₄ nanorods, consisting of small nanoparticles with diameter of 80–150 nm, had an average diameter of 200 nm and a length of 3–5 μm. The morphology and structure of synthesized samples were characterized by transmission electron microscopy and scanning electron microscopy. The phase and composition were investigated by X-ray powder diffraction and X-ray photoelectron spectroscopy. The optical property of Co₃O₄ nanorods was investigated. Moreover, the porous Co₃O₄ nanorods exhibited high electrochemical performance when applied as cathode materials for lithium-ion batteries, which gives them good potential applications.     

作为锂离子电池负极材料的三维有序大孔SnO2的 制备及表征

通过聚苯乙烯(PS)胶晶模板法合成了三维有序大孔(3DOM) SnO2. 运用扫描电镜、热重分析、X射线衍射、电化学充放电等多种方法对其结构和性能进行了表征和研究. SEM图表明PS胶晶模板微球排列规整, 大小均匀(直径275±10 nm), 形成多层六方紧密堆积排列; 煅烧除去模板后的3DOM SnO2呈三维多孔网络结构, 具有圆型和六边形的孔隙形貌, 其孔径大小为(215±10) nm; 孔壁由SnO2纳米晶粒组成, 壁厚为20～30 nm. XRD图谱表明经过煅烧除去模板后, 形成了纯SnO2相. 当作为锂离子电池负极材料时, 3DOM SnO2表现出较好的充放电容量和库仑效率. 此外, 这种合成方法简单、经济, 可进一步应用于其它锂离子电池材料的合成.     

High lithium electroactivity of hierarchical porous rutile TiO2 nanorod microspheres

Here we report on the hierarchical porous rutile TiO₂ nanorod micospheres as an anode material for lithium-ion batteries. The resulting hierarchical porous rutile TiO₂ nanorod microspheres possessed much higher reversible capacity, cycling stability and rate capability than nanosized rutile TiO₂ previously reported in the literatures. These good electrochemical performances may be attributed to the facile diffusion of Li⁺ ions from outside through the porous channels into the TiO₂ nanorods in the microspheres and the high electrode–electrolyte contact area offered by hierarchical porous microspheres with a large specific surface area.     

TiO2 nanotube array film prepared by anodization as anode material for lithium ion batteries

TiO₂ array film fabricated by potentiostatic anodization of titanium is characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and charge–discharge measurements. The XRD results indicated that the TiO₂ array is amorphous, and after calcination at 500 °C, it has the anatase form. The pore size and wall thickness of TiO₂ nanotube arrays synthesized at different anodization voltages are highly dependent on the applied voltage. The electrochemical performance of the prepared TiO₂ nanotube array as an electrode material for lithium batteries was evaluated by galvanostatic charge–discharge measurement. The sample prepared at 20 V shows good cyclability but low discharge capacity of 180 mA h cm⁻³, while the sample prepared at 80 V has the highest discharge capacity of 340 mA h cm⁻³.     

Anatase TiO2 nanosheet: An ideal host structure for fast and efficient lithium insertion/extraction

Anatase TiO₂ nanosheets with largely exposed (0 0 1) facets have been synthesized by a modified method. Exploitation of these nanosheets as a host structure for reversible lithium insertion/extraction has been investigated. It is found that these TiO₂ nanosheets manifest much lower initial irreversible losses compared to other anatase TiO₂ nanostructures, and excellent cycling performance at a charge–discharge rate as high as 20 C. The superior reversible lithium storage capability can be attributed to the ultrathin nanosheet structure: a large exposed effective area and a very short diffusion path. It thus attests the promising use of these anatase TiO₂ nanosheets in high-power lithium–ion batteries.     

Simulated Sunlight-Driven Degradation of Rhodamine B by Porous Peanut-Like TiO2/BiVO4 Composite

Porous peanut-like TiO₂/BiVO₄ composite nanostructures were synthesized via a template-free hydrothermal process with bismuth nitrate, ammonium metavanadate and anatase TiO₂ as raw materials. The crystal structures, morphologies, and optical properties of the as-prepared samples were characterized by X-ray powder diffraction, transmission electron microscope, scanning electron microscopy, X-ray photoelectron spectroscopy and UV–visible absorption spectra. Simulated sun-light induced photocatalytic degradation of Rhodamine B by porous peanut-like TiO₂/BiVO₄ nanostructures in the absence and presence of H₂O₂ has been investigated, and the results show these porous composite nanostructures with higher photocatalytic activity than pure BiVO₄ and anatase TiO₂. When TiO₂/BiVO₄ heterostructures were used as the photocatalysts under simulated sun-light irradiation, BiVO₄ could act as a sensitizer to absorb the visible light. Meanwhile, coupling different band-gap semiconductors of TiO₂ and BiVO₄, the compound facilitate separation of the photogenerated carriers under the internal field induced by the different electronic band structures of semiconductors.     

层状钛硅酸盐化合物作为锂离子电池负极储能材料

锂离子二次电池是手提设备的重要电力来源。近年来,人们为了寻找更新颖更好的锂离子电极材料,开始研究晶形离子交换材料,这种材料具有开放孔道,能够让离子在多孔框架里自由的进出。一种具有层状结构的钛硅酸盐Na-JDF-L1(Na₄Ti₂Si₈O₂₂·4H₂O)经过离子交换后被用作锂离子负极材料。它在循环200次后放电容量保持在364 mAh·g^-1,并且库伦效率约为100%。通过将TiO₂引入Li(Na)-JDF-L1中,有效的提高了材料的首次库伦效率和倍率放电性能。     

层状钛硅酸盐化合物作为锂离子电池负极储能材料

锂离子二次电池是手提设备的重要电力来源。近年来, 人们为了寻找更新颖更好的锂离子电极材料, 开始研究晶形离子交换材料, 这种材料具有开放孔道, 能够让离子在多孔框架里自由的进出。一种具有层状结构的钛硅酸盐Na-JDF-L1(Na₄Ti₂Si₈O₂₂·4H₂O)经过离子交换后被用作锂离子负极材料。它在循环200次后放电容量保持在364 mAh·g^-1, 并且库伦效率约为100%。通过将TiO₂引入Li(Na)-JDF-L1中, 有效的提高了材料的首次库伦效率和倍率放电性能。     

Nb-doped rutile titanium dioxide nanorods for lithium-ion batteries

Rutile titanium dioxide is a promising negative electrode material for lithium-ion batteries due to low volume change on lithium-ion insertion, fast ion diffusion, and large surface area. However, the low theoretical capacity and conductivity of titanium dioxide has limited its application. In this work, rutile TiO₂ was synthesized using a batch hydrothermal method, and doped with Nb⁵⁺ (3.5 at%). <Potentiodynamic/galvanostatic > cycling in the range 1.0–3.0 V vs Li/Li⁺ was used to determine the Li-ion capacity of the doped and pristine TiO₂ material, and electrochemical cycling was used to measure the extent of conversion from the lithiated to de-lithiated state. The nanoscale structures of the pristine and doped materials were determined by powder X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy and Brunauer-Emmett-Teller surface area measurements. Cycling in the range 1.0–3.0 V vs Li/Li⁺ showed that Nb⁵⁺ doping into the structure resulted in higher charge capacities. After 100 cycles at 100 mA g⁻¹, the Nb-doped rutile TiO₂ maintained a capacity of ca. 390 mAh g⁻¹, 64% higher than undoped TiO₂. For electrochemical cycling in the range 0.05–3.0 V vs Li/Li⁺, the introduction of Nb⁵⁺ resulted in a higher conversion of rutile TiO₂ from the lithiated to de-lithiated state. The higher capacity of the doped TiO₂ is shown to be mainly due to the smaller particle size, optimized surface area, and orientation of the nanorods.