Electrochemical lithium storage of sodium titanate nanotubes and nanorods

Layered hydrated sodium titanate nanotubes are synthesized via a hydrothermal reaction in alkaline solution. The as-prepared nanotubes are calcined at different temperatures (300-600 °C) in air. The microstructure of obtained samples is characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). It is observed that the calcined products maintain their parent tubular morphologies below 500 °C. After calcinations at 600 °C, the hollow tubular morphology could completely be converted to the short solid nanorod morphology. In the meanwhile, the monoclinic sodium hexatitanate as a main phase is formed in nanorods, coexisted with sodium trititanate as a residual phase. The electrochemical lithium storage of obtained samples is studied by galvanostatic method and cyclic voltammetry. It is demonstrated that the nanotubes calcined at 500 °C have relatively large reversible capacity, good reversibility and excellent high rate discharge capability. The lithium intercalation process is shown to have pseudocapacitive feature caused by their layered structure and open lithium insertion tunnels, which is in favor of the high rate charge/discharge capability of sodium titanate nanotubes.     

热处理对微乳液法制备纳米氧化镍的影响

微乳液法是近年来制备纳米颗粒的有效方法之一，具有装置简单，操作容易，微粒可控等优点。以氯化镍和氨水为原料，以Triton X-100／环己彬正己醇／水为反相微乳体系，成功制备出纳米氧化镍前驱体，然后对前驱体进行热处理，得到纳米氧化镍粉末，系统考察了热处理对纳米氧化镍颗粒形貌、粒径分布的影响。结果显示，利用微乳液法制备的氧化镍纳米颗粒大小、形态及分散性优于经热处理后的粉末；X射线衍射谱及透射电镜显示，热处理后的氧化镍粉末粒径随着热处理温度的升高而增大。     

Synthesis of 1D-MoS2/graphene nanotubes aided with sodium chloride for reversible lithium storage

A novel negative material consisting of graphene nanotubes and ultrathin MoS₂ is synthesized by a simple one-step hydrothermal method assisted with Sodium chloride. The MoS₂/Graphene electrodes deliver a specific capacity of 1350 mAh g^?1 under 0.1 A g^?1 and high rate capability (retaining 85.5% capacity from 0.1 A g^?1 to 0.8 A g^?1). A high remarkable capacity of 820 mAh g^?1 can still be recovered at 0.5 A g^?1 after 500 cycles, and the average coulombic efficiency was as high as 99.98% during the additional 500 cycles. The excellent Li-ion storage performance of MoS₂/Graphene nanotubes may be attributed to the ultra-thin MoS₂ flakes and curled graphene nanotubes. This structural feature has a strong adsorption capacity for lithium ions, which can provide a broad space for ion storage. A large number of active sites dispersed in the layered molybdenum disulfide promote the kinetics of the electrochemical reaction, empowering the ultra-thin layered molybdenum disulfide to get a higher theoretical capacity. In addition, the existence of the tubular structure alleviates volume expansion and provides a way for the rapid movement of electrons and diffusion of Li⁺ during repeated cycles.     

磁性Ni/NiO纳米颗粒的制备及其在蛋白分离上的应用

用1∶323的硝酸镍和尿素制备出前驱物Ni2+-oligomer,于450℃下热解2 h,得到平均粒径为2 nm的磁性Ni/NiO纳米颗粒;再利用Ni2+与组氨酸的特异性结合,将Ni/NiO纳米颗粒表面修饰上组氨酸,得到平均粒径为10 nm的磁性his-Ni/NiO纳米颗粒,在大肠杆菌体内进行蛋白吸附并在体外进行提纯。结果表明,his-Ni/NiO纳米颗粒洗脱下来的蛋白与大肠杆菌中的蛋白种类一致,该研究为蛋白分离和纯化提供了一条新思路。     

纳米氧化镍的制备与应用

纳米氧化镍具有优异的催化性能、电学性能,在催化剂、传感器及电池电极等方面得到了广泛的应用。综述了纳米氧化镍的制备方法及其优缺点,指出了纳米氧化镍在制备及其表面改性方面尚待解决的问题。     

Electrochemical synthesis of silica-doped high aspect-ratio titania nanotubes as nanobioceramics for implant applications

The preparation of silica-doped high aspect-ratio TiO₂ nanotubes and their apatite-forming ability were demonstrated in this study. The high aspect-ratio TiO₂ nanotube layers were produced by electrochemical anodic oxidation of Ti in chloride-containing electrolytes. Nanotubes were doped with different concentrations of silica particles through anodization in NaCl electrolyte containing different concentrations of water glass (24 g/L or 48 g/L Na₂SiO₃). The biomimetic apatite deposition behavior was evaluated under simulated body fluid (SBF) with an ion concentration nearly equal to human blood plasma. The experimental results collectively demonstrate the successful silica doping of the resultant nanotube layers with significant abundant OH groups on their surfaces. The results of hydroxyapatite (HA) growth on nanotubes clearly show that the silica doping greatly enhances the fast nucleation and growth of HA, especially for the tubes in their “as-formed” amorphous state, which usually require a long time for apatite induction. The nanotubes doped with high silica content combined with an anatase or a mixture of anatase and rutile led to the formation of very thick and continuous apatite layers with a thickness of ∼7 μm in 21 days. In contrast, to the tubes doped with a low concentration of silica (grown in an electrolyte containing 24 g/L Na₂SiO₃), the HA deposited in the form of closely packed spheroid particles and never developed into continuous films. This effect could be attributed to the critical active-site density (silanol groups, >Si-OH), which provides the sterochemical match for apatite growth. Finally, the results of this study provide, for the first time, evidence for the dependence of HA morphology/microstructure on the crystallographic structure and the density of active sites (>Si-OH groups).     

Optimal synthesis of mesostructured hollow titania nanotubes templated on CaCO3 nanoparticles

Approximate 10 µm length of mesostructured hollow titania nanotubes with intact configuration was successfully prepared by using needle-like calcium carbonate and octadecylamine as double templates at room temperature in nonaqueous system. During the whole preparation, two parameters i.e. tetrabutoxytitanium/calcium carbonate molar ratio and annealing temperature, were optimized to obtain titania nanotubes with well-defined tubular morphology and mesoporous structure in tube walls. The as-prepared samples were characterized by scanning electron microscopy, transmission electron microscopy, broad-angle X-ray diffraction, pore size distribution and Brunauer-Emmett-Teller. The results showed that under optimal experimental conditions i.e. tetrabutoxytitanium/calcium carbonate molar ratio (50 wt.%) and annealing temperature (773 K), the tube materials exhibited uniform tubular structure with a length of 8-15 µm and an inner diameter of ∼ 400 nm, a wall thickness of ∼ 40 nm, a surface area of 112.2 m²/g and a pore volume of 0.18 cm³/g. The optimized titania nanotubes were utilized as a carrier for the immobilized of ibuprofen via a simple adsorption method. It was found that the loaded drug presented good sustained release property in three release media, i.e. simulated body fluid, normal saline and pure water.     

Role of oxygen vacancies on the energy storage performance of battery-type NiO electrodes

In this study, the influence of the surface oxygen vacancies on the energy storage performance of electrodes based on nickel oxide (NiO) nanoparticles was investigated. NiO samples were synthesized by three facile and low-cost syntheses routes: nitrate calcination, citrate, and combustion methods. The concentration of surface defects in NiO powders was determined using XPS analyses, which showed a higher amount of oxygen vacancies for the sample obtained by nitrate calcination. According to the cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) curves, NiO-based electrodes were classified as battery-like. CV results suggest that redox reactions are diffusion-controlled processes with a faster diffusion rate for the sample obtained by the nitrate calcination method. This is in accordance with the GCD and electrochemical impedance spectroscopy (EIS) results, with higher specific capacity and higher electrical conductivity (lower equivalent series resistance) for the sample obtained by nitrate calcination. The results indicate that oxygen vacancies play an important role in the electrochemical performance of battery-type NiO electrodes.     

Simple self-assembly of SnS2 entrapped graphene aerogel and its enhanced lithium storage performance

In this work, SnS₂ nanoplates entrapped graphene aerogel has been successfully prepared by simple self-assembly of reduced graphene oxide obtained through mild chemical reduction. Structural and morphological investigations demonstrated that SnS₂ nanoplates are highly dispersed in the three dimensional (3D) porous graphene matrix. When served as anode material for lithium-ion batteries, the electrochemical properties of SnS₂/graphene aerogel (SnS₂/GA) were evaluated by galvanostatic discharge–charge tests, cyclic voltammetry and impedance spectroscopy measurement. Compared with pristine SnS₂, the SnS₂/GA nanocomposite achieved a much higher initial reversible capacity (1186 mAh g⁻¹), superior cyclic stability (1004 mAh g⁻¹ after 60 cycles, corresponding to 84.7% of the initial reversible capacity), as well as better rate capability (650 mAh g⁻¹ at a current density of 1000 mA g⁻¹). This significantly improved lithium storage performance can be attributed to the good integration of SnS₂ nanoplates with 3D porous graphene network, which can not only provide much more active sites and easy access for Li ions intercalation, but also prevent the aggregation of SnS₂ nanoplates and facilitate fast transportation of Li ions and surface electrons during the electrochemical process.     

Stabilizing the nanostructure of Pre-lithiated LiF nanoparticles modified SnO2@graphite nanosheets as a high performance anode material for lithium ions batteries

Graphite nanosheets coated by LiF/SnO₂ composites are designed to obtain a lithium ion anode material with excellent performance. LiF nanoparticles play a significant role in improving the electrochemical performance by inhibiting electrolyte decomposition and providing excess Li sources during cycling. The obtained LiF@SnO₂@C electrode shows an outstanding capacity of 951.9 mAhg^?1 at 0.2 Ag^-1 after 370 cycles and excellent long cycling performance of 650.0 mAhg^?1 at 1.0 Ag^-1 after 930 cycles. First-principles calculations demonstrate that F-doped SnO₂ (?2211.8 eV) has a lower free energy compared to SnO₂ (?1937.4 eV), resulting in a robust composite architecture that gives rise to high cycling stability.     

Enhanced electrochemical performance of ZrO2 modified LiNi0.6Co0.2Mn0.2O2 cathode material for lithium ion batteries

LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) cathode has been modified by incorporating ZrO₂ nanoparticles to improve its electrochemical performance. Compared to the pristine electrode, the cycling stability and rate capability of 0.5 wt% ZrO₂ modified-NCM622 have been improved significantly. The 0.5 wt% ZrO₂ modified-NCM622 cathode shows a capacity retention of 83.8% after 100 cycles at 0.1 C between 2.8 and 4.3 V, while that of the pristine NCM622 electrode is only 75.6%. When the current rate is set as 5C, the capacity retention of the 0.5 wt% ZrO₂-modified NCM622 is 10% higher than that of the pristine NCM622. Also, the rate capability of 0.5 wt% ZrO₂-modified NCM622 is better than that of the pristine NCM622 at various C-rates in a voltage range of 2.8–4.3 V. The enhanced electrochemical performances of the ZrO₂-modified NCM622 cathodes can be attributed to their high Li-ion conductivity and structural stability.     

The fabrication of white light-emitting diodes using the n-ZnO/NiO/p-GaN heterojunction with enhanced luminescence

Cheap and efficient white light-emitting diodes (LEDs) are of great interest due to the energy crisis all over the world. Herein, we have developed heterojunction LEDs based on the well-aligned ZnO nanorods and nanotubes on the p-type GaN with the insertion of the NiO buffer layer that showed enhancement in the light emission. Scanning electron microscopy have well demonstrated the arrays of the ZnO nanorods and the proper etching into the nanotubes. X-ray diffraction study describes the wurtzite crystal structure array of ZnO nanorods with the involvement of GaN at the (002) peak. The cathodoluminescence spectra represent strong and broad visible emission peaks compared to the UV emission and a weak peak at 425 nm which is originated from GaN. Electroluminescence study has shown highly improved luminescence response for the LEDs fabricated with NiO buffer layer compared to that without NiO layer. Introducing a sandwich-thin layer of NiO between the n-type ZnO and the p-type GaN will possibly block the injection of electrons from the ZnO to the GaN. Moreover, the presence of NiO buffer layer might create the confinement effect.     

负载硅钨杂多酸纳米银修饰电极的电化学性质研究

以硅钨杂多酸作为光催化还原剂制备了纳米银(SiW12-NS)。用PVP作偶联剂,将SiW12-NS修饰到玻碳电极表面,用循环伏安法(CV)研究其电化学行为。结果表明,修饰电极具有良好的电化学响应和电极稳定性,对BrO3-,NO2-具有良好的电催化还原性能。     

Electrochemical capacitance characterization of NiO with ordered mesoporous structure synthesized by template SBA-15

In this paper, NiO with ordered mesoporous structure was synthesized by replicating template SBA-15 and its electrochemical capacitance characterization was for the first time studied in 2 M KOH electrolyte solution. Electrochemical tests results indicated the ordered mesoporous structure can greatly increase the utilization of NiO, which is attribute to a large effective surface area due to the mesoporous structure. The capacitance of NiO with order mesoporous structure was about 120 F/g, about four times larger than that of NiO prepared by direct calcining Ni(NO₃)·6H₂O at 550 °C. On the other hand, the mesoporous NiO showed a good rate capability, which is due to that the ordered mesopores did not limit the ion motion within the pores.     

Eggplant as an appreciable bio-template for green synthesis of NiO nanoparticles: Study of physical and photocatalytic properties

In this study, we described a green, sustainable, and feasible method for synthesizing 5 nm NiO nanoparticles. Eggplant skin was chosen as an appropriate bio-template with a high potential to induce its structure into the desired metal oxide. Two approaches were used and compared to synthesize NiO bio-template: hydrothermal and sol-gel. The morphology and physical properties of the obtained NiO nanoparticles were evaluated using FESEM, TEM, XRD, BET, FT-IR, TGA, and UV–Vis analyses. All these methods confirm that the hydrothermal method is a better approach for synthesizing NiO bio-template nanoparticles than the sol-gel method. UV–Vis analysis revealed that the NiO nanoparticles produced by the hydrothermal method have a low bandgap of 2.88 eV, which is a key factor for photocatalytic applications.     

Assembling CoSn3 nanoparticles on multiwalled carbon nanotubes with enhanced lithium storage properties

CoSn(3) nanoparticles have been successfully assembled on noncovalently poly(diallyldimethylammonium chloride)-functionalized multiwalled carbon nanotubes (MWCNTs) via a chemical reduction method in a polyol system. The influences of the surface functionality and the reaction temperature on the synthesis of uniform CoSn(3)-MWCNTs nanohybrids have been investigated. The as-synthesized CoSn(3)-MWCNTs nanohybrids have been applied as anodes for lithium-ion batteries, and show better lithium storage performance compared to the bare CoSn(3) nanoparticles and MWCNTs. The combining of MWCNTs that can hinder the agglomeration and enhance the electronic conductivity of the active materials is responsible for the enhanced cyclic performance.     

Electrochemical lithium ion storage properties of single-walled carbon nanotubes containing organic molecules

The Li ion storage properties of single-walled carbon nanotube peapods containing one of three organic molecules (9,10-dichloroanthracene, β-carotene, coronene) were measured. It was found by electrochemical charge-discharge measurements that the reversible storage capacity of the SWCNTs significantly increased as a result of the inclusion, although unfortunately the samples are still not appropriate for the practical use as an anode material in Li ion battery because of the high irreversible capacity (>900 mAh/g). In the most effective case, the tube containing the organic molecule can store about 2.5 times more Li ions compared to an empty tube.     

Electrochemical characterization and reactivity of Pt nanoparticles supported on single-walled carbon nanotubes

Carbon nanotubes have been proposed as advanced metal catalyst support for electrocatalysis. In this paper, Pt nanoparticles supported on single-walled carbon nanotubes (SWCNTs)-Pt, were prepared using a solid-state reaction between the SWCNTs and two different Pt precursors, bis(dibenzylideneacetone)platinum [Pt(DBA)₂] or tri(dibenzylideneacetone)platinum [Pt(DBA)₃]. TEM images of the samples show Pt nanoparticles with a particle size around 2.5 nm with a high degree of dispersion on the SWCNTs. A detailed electrochemical characterization of the surface of the samples including irreversibly adsorbed adatoms of Bi and Ge as probe reactions has been carried out. It has been stated that SWCNTs-Pt samples subjected to the classical electrochemical activation induce a serious sintering of the Pt nanoparticles.     

Electrochemical storage of energy in carbon nanotubes and nanostructured carbons

Possibilities of electrochemical energy conversion using carbon nanotubes and related materials in various systems, such as lithium batteries, supercapacitors, hydrogen storage, are considered. It is shown that for these applications the electrochemical properties of multiwalled (MWNTs) and single walled (SWNTs) nanotubes are essentially dominated by their mesoporous character. During lithium insertion into nanotubular materials a high irreversible capacity C_irr (from 460 to 1080 mAh/g) has been observed after the first cycle with a tendency to further decomposition of electrolyte with cycling. Penetration of solvated lithium ions in the accessible mesopores is at the origin of this phenomenon; an almost linear dependence has been found between the mesopore volume and C_irr. Reversible capacity for lithium insertion C_rev ranged between 220 and 780 mAh/g; however, a great divergence (hysteresis) between insertion and extraction characteristics was observed independently on the kind of nanotubes and oxygen content. Amount of lithium stored by electrostatic attraction is negligible in comparison to real redox reactions which for thermodynamic reasons present linear variation of potential, especially during deinsertion (pseudocapacitive effects). During positive polarization, i.e., removal of lithium, resistivity of the electrode also gradually increases. Due to the open network of mesopores formed by the nanotubes entanglement, and consequently an easily accessible electrode-electrolyte interface, nanotubular materials are quite adapted for supercapacitor electrodes in various electrolytic solutions. High values of capacitance (80 F/g) have been obtained in 6 M KOH for materials with a surface area of only ca. 430 m²/g. Capacitance values have been enhanced either by additional oxygenated functionalisation of nanotubes (130 F/g) or by conducting polypyrrole (PPy) electrodeposition where the maximum values reached 170 F/g. The next domain of energy storage in the carbon nanostructures is the accumulation of hydrogen by the electrochemical decomposition of aqueous alkaline medium on a negatively polarized carbon electrode in ambient conditions. For SWNTs only moderate values (below 0.5 wt.% of H₂) have been found, while for activated carbons with highly developed surface area of 1500 m²/g, the amount of reversibly sorbed hydrogen was ca. 2 wt.%, noticeably larger than under dihydrogen pressure (only 0.4 wt.% for the same material at 70 bar and 273 K). The enhancement observed for the activated carbon is interpreted by the formation of nascent hydrogen during water reduction which penetrates easily in the available carbon nanopores. The values obtained by this method are comparable to those of metallic alloys, such as LaNi₅ for example.