SnO x /graphene anode material with multiple oxidation states for high-performance Li-ion batteries.

Tin and its oxides are promising anode materials owing to their high theoretical capacity, rich resource, and environmental benignity. To achieve low cost and green synthesis, a facile synthetic route of SnO x /graphene composites is proposed, using a simple galvanic replacement method to quickly obtain abundant foamed tin as raw material and ball milling method to realize a mechanochemical reaction between SnO x (0 ≤ x ≤ 2) and graphene. Under different annealing conditions, the foamed tin is converted to tin oxides with multiple oxidation states (Sn3O4, SnO, and SnO2). These unique components can greatly affect the electrochemical performance of the electrode in LIBs. The as-prepared electrode (SnO x -300/G) obtained by annealing foamed tin at 300 °C for 4 h and combining SnO x powders with graphene via ball milling shows great cycling stability, retaining a high capacity of 786 mA h g-1 at 0.1 A g-1 after 150 cycles, and its initial Coulombic efficiency can reach 84.03%. Thus, this facile synthesis can provide an environmentally friendly route for commercial production of high-performance energy storage materials.

Diblock copolymers directing construction of hierarchically porous metal-organic frameworks for enhanced-performance supercapacitors.

A rationally designed strategy is developed to synthesize hierarchically porous Fe-based metal-organic frameworks (P-Fe-MOF) via solution-based self-assembly of diblock copolymers. The well-chosen amphiphilic diblock copolymers (BCP) of polystyrene-block-poly(acrylic acid) (PS-b-PAA) exhibits outstanding tolerance capability of rigorous conditions (e.g. strong acidity or basicity, high temperature and pressure), steering the peripheral crystallization of Fe-based MOF by anchoring ferric ions with outer PAA block. Importantly, the introduction of BCP endows MOF materials with additional mesopores (∼40 nm) penetrating whole crystals, along with their inherent micropores and introduced macropores. The unique hierarchically porous architecture contributes to fast charge transport and electrolyte ion diffusion, and thus promotes their redox reaction kinetics processes. Accordingly, the resultant P-Fe-MOF material as a new electrode material for supercapacitors delivers the unprecedented highest specific capacitance up to 78.3 mAh g-1 at a current density of 1 A g-1, which is 9.8 times than that of Fe-based MOF/carbon nanotubes composite electrode reported previously. This study may inspire new design of porous metal coordination polymers and advanced electrode materials for energy storage and conversion field.

Few-Layer MoS2 Nanosheets Encapsulated in N-Doped Carbon Hollow Spheres as Long-Life Anode Materials for Lithium-Ion Batteries.

Two-dimensional molybdenum disulfide (MoS2 ) has been recognized as a promising anode material for lithium-ion batteries (LIBs) due to its high theoretical capacity, but its rapid capacity decay owing to poor conductivity, structure pulverization, and polysulfide dissolution presents significant challenges in practical applications. Herein, triple-layered hollow spheres in which MoS2 nanosheets are fully encapsulated between inner carbon and outer nitrogen-doped carbon (NC) were fabricated. Such an architecture provides high conductivity and efficient lithium-ion transfer. Moreover, the NC shell prevents aggregation and exfoliation of MoS2 nanosheets and thus maintains the integrity of the nanostructure during the charge/discharge process. As anode materials for LIBs, the C@MoS2 @NC hollow spheres deliver a high reversible capacity (747 mA h g-1 after 100 cycles at 100 mA g-1 ) and excellent long-cycle performance (650 mA h g-1 after 1000 cycles at 1.0 A g-1 ), which confirm its potential for high-performance LIBs.

Nickel skeleton three-dimensional nitrogen doped graphene nanosheets/nanoscrolls as promising supercapacitor electrodes.

A novel nickel skeleton 3D nitrogen doped graphene (N-GR/NF) superstructure with interconnected graphene nanosheets and nanoscrolls was synthesized using a facile two-step method. By varying the precursor concentration, the assembly of a graphene aerogel can be easily regulated, yielding different micro-structures and morphologies which accelerate the fast electron/ion transportation. The N-GR/NF composites demonstrate enhanced capacitance of 250 F g-1 at 5 A g-1, good rate performance (237 F g-1 at the current density of 12 A g-1) and cycle stability (90.9% retention after 5000 cycles) in 1 M KOH electrolyte. This study provides a new strategy for the microporous engineering of graphene gel, promising for further exploitation in various other applications.

Galvanic displacement assembly of ultrathin Co3O4 nanosheet arrays on nickel foam for a high-performance supercapacitor.

High-performance supercapacitors are very desirable for many portable electronic devices, electric vehicles and high-power electronic devices. Herein, a facile and binder-free synthesis method, galvanic displacement of the precursor followed by heat treatment, is used to fabricate ultrathin Co3O4 nanosheet arrays on nickel foam substrate. When used as a supercapacitor electrode the prepared Co3O4 on nickel foam exhibits a maximum specific capacitance of 1095 F g-1 at a current density of 1 A g-1 and good cycling stability of 71% retention after 2000 cycling tests. This excellent electrochemical performance can be ascribed to the high specific surface area of each Co3O4 nanosheet that comprises numerous nanoparticles.

InP nanopore arrays for photoelectrochemical hydrogen generation.

We report a facile and large-scale fabrication of highly ordered one-dimensional (1D) indium phosphide (InP) nanopore arrays (NPs) and their application as photoelectrodes for photoelectrochemical (PEC) hydrogen production. These InP NPs exhibit superior PEC performance due to their excellent light-trapping characteristics, high-quality 1D conducting channels and large surface areas. The photocurrent density of optimized InP NPs is 8.9 times higher than that of planar counterpart at an applied potential of +0.3 V versus RHE under AM 1.5G illumination (100 mW cm(-2)). In addition, the onset potential of InP NPs exhibits 105 mV of cathodic shift relative to planar control. The superior performance of the nanoporous samples is further explained by Mott-Schottky and electrochemical impedance spectroscopy ananlysis.

Visible light photocatalytic H2-production activity of wide band gap ZnS nanoparticles based on the photosensitization of grapheme.

Visible light photocatalytic H(2) production from water splitting is considered an attractive way to solve the increasing global energy crisis in modern life. In this study, a series of zinc sulfide nanoparticles and graphene (GR) sheet composites were synthesized by a two-step hydrothermal method, which used zinc chloride, sodium sulfide, and graphite oxide (GO) as the starting materials. The as-prepared ZnS-GR showed highly efficient visible light photocatalytic activity in hydrogen generation. The morphology and structure of the composites obtained by transmission electron microscope and x-ray diffraction exhibited a small crystallite size and a good interfacial contact between the ZnS nanoparticles and the two-dimensional (2D) GR sheet,which were beneficial for the photocatalysis. When the content of the GR in the catalyst was 0.1%, the ZG0.1 sample exhibited the highest H(2)-production rate of 7.42 µmol h(−1) g(−1), eight times more than the pure ZnS sample. This high visible-light photocatalytic H(2) production activity is attributed to the photosensitization of GR. Irradiated by visible light, the electrons photogenerated from GR transfer to the conduction band of ZnS to participate in the photocatalytic process. This study presents the visible-light photocatalytic activity of wide bandgap ZnS and its application in H(2) evolution.

Self-assembled synthesis of 3D Cu(In(1-x)Ga(x))Se2 nanoarrays by one-step electroless deposition into ordered AAO template.

Quaternary nanostructured Cu(In1 - xGax)Se2 (CIGS) arrays were successfully fabricated via a novel and simple solution-based protocol on the electroless deposition method, using a flexible, highly ordered anodic aluminium oxide (AAO) substrate. This method does not require electric power, complicated sensitization processes, or complexing agents, but provides nearly 100% pore fill factor to AAO templates. The field emission scanning electron microscopy (FE-SEM) images show that we obtained uniformly three-dimensional nanostructured CIGS arrays, and we can tailor the diameter and wall thicknesses of the nanostructure by adjusting the pore diameter of the AAO and metal Mo layer. Their chemical composition was determined by energy-dispersive spectroscopy analysis, which is very close to the stoichiometric value. The Raman spectroscopy, x-ray diffraction (XRD) pattern, and transmission electron microscopy (TEM) further confirm the formation of nanostructured CIGS with prominent chalcopyrite structure. The nanostructured CIGS arrays can support the design of low-cost, highlight-trapping, and enhanced carrier collection nanostructured solar cells.

Self-assembly of three-dimensional SrTiO3 microscale superstructures and their photonic effect.

3D SrTiO3 microscale superstructures (STOMSs) have been prepared via hydrothermal synthesis and multiple (five times) crystallization process. Branches and trunks on STOMSs show perfect corn-like structures, and each side of the trunks could be considered as grating-analogous structures. These well-ordered trunks along with gratings constitute 3D hybrid microstructures that contribute to light diffraction, and the colorful photonic effects of light diffraction are thought to be due to refractive index modulations in three dimensions. The colors of STOMSs can be tuned from yellow to cyan by changing the growth cycle. This special optical performance could broaden the application scope of SrTiO3.

Silicon nanowire array/Cu2O crystalline core-shell nanosystem for solar-driven photocatalytic water splitting.

P-type Cu2O nanocrystals were deposited on n-type silicon nanowire arrays (Si NWs) to form core-shell heterojunction arrays structure via a simple electroless deposition technique. Scanning electron microscopy, transmission electron microscope and x-ray diffraction were utilized to characterize the morphology and structure of the core-shell nanosystem. The reflectivity of the obtained core-shell structure measured by UV/vis spectrometry showed a comparatively low reflectivity in the visible-light region, which implied good optical absorption performance. The water splitting performance of the obtained Si NWs, planar Si/Cu2O structure and Si NW/Cu2O core-shell nanosystem were studied. Owing to the large specific surface area, heterojunctions formed between Cu2O nanocrystallites and Si NWs and the light trapping effect of the NW array structure, the photocatalytic performance of the Si NW/Cu2O core-shell nanosystem increased markedly compared with that of pure silicon NWs and a planar Si/Cu2O structure, which means excellent hydrogen production capacity under irradiation with simulated sunlight. In addition, the photocatalytic performance of the core-shell nanosystem was improved obviously after platinum nanoparticles were electrodeposited on it.

High-speed growth of TiO2 nanotube arrays with gradient pore diameter and ultrathin tube wall under high-field anodization.

Highly ordered TiO(2) nanotubular arrays have been prepared by two-step anodization under high field. The high anodizing current densities lead to a high-speed film growth (0.40-1.00 microm min(-1)), which is nearly 16 times faster than traditional fabrication of TiO(2) at low field. It was found that an annealing process of Ti foil is an effective approach to get a monodisperse and double-pass TiO(2) nanotubular layer with a gradient pore diameter and ultrathin tube wall (nearly 10 nm). A higher anodic voltage and longer anodization time are beneficial to the formation of ultrathin tube walls. This approach is simple and cost-effective in fabricating high-quality ordered TiO(2) nanotubular arrays for practical applications.

Anisotropic growth and formation mechanism investigation of 1D ZnO nanorods in spin-coating sol-gel process.

ZnO nanorods are fabricated on glass substrate by spin-coating sol-gel process using non-basic aged solution and annealing. Sample solutions reserved in room temperature for different time (one day, one month, two months and four months) are prepared for the experiment. The morphology study indicates that the aging time has direct influence on the final products. This is verified by the Transmission Electron Microscopy and Photon Correlation Spectroscopy study. Small crystalline nanoparticles would gradually nucleate and aggregate in the sol during the aging process. They act as nucleation site for the secondary crystal growth into nanorods during anneal. Both the size of crystalline particles in the sol and the size of nanorods will grow bigger as the aging time increases. The products' structure and optical property are further studied by X-ray diffraction spectroscopy, Photoluminescence and Raman spectroscopy. This work also helps to further clarify the formation mechanism of ZnO nanorods by solution-based method.

High-performance humidity sensors based on high-field anodized porous alumina films.

Improved humidity sensors based on porous anodized alumina (PAA) films were prepared via stable high-field anodization and subsequent isotropic chemical etching for appropriate times. The results reveal that sensitivity over a wide humidity range can be adjusted by changing the microstructure of the porous alumina layer, which can be explained in terms of the inhomogeneous distribution of anion impurities in the pore sidewall. The short response and recovery times obtained were ascribed to the ordered pore arrays and large pore size of the PAA films. This study has significance in tailoring the moisture sensitivity in the design of diverse sensors for practical applications.

The rational design of hierarchical MoS2 nanosheet hollow spheres sandwiched between carbon and TiO2@graphite as an improved anode for lithium-ion batteries.

Molybdenum disulfide (MoS2) shows high capacity but suffers from poor rate capability and rapid capacity decay, which greatly limit its practical applications in lithium-ion batteries. Herein, we successfully prepared MoS2 nanosheet hollow spheres encapsulated into carbon and titanium dioxide@graphite, denoted as TiO2@G@MoS2@C, via hydrothermal and polymerization approaches. In this hierarchical architecture, the MoS2 hollow sphere was sandwiched by graphite and an amorphous carbon shell; thus, TiO2@G@MoS2@C exhibited effectively enhanced electrical conductivity and withstood the volume changes; moreover, the aggregation and diffusion of the MoS2 nanosheets were restricted; this advanced TiO2@G@MoS2@C fully combined the advantages of a three-dimensional architecture, hollow structure, carbon coating, and a mechanically robust TiO2@graphite support, achieving improved specific capacity and long-term cycling stability. In addition, it exhibited the high reversible specific capacity of 823 mA h g-1 at the current density of 0.1 A g-1 after 100 cycles, retaining almost 88% of the initial reversible capacity with the high coulombic efficiency of 99%.

One-Step In Situ Self-Assembly of Cypress Leaf-Like Cu(OH)2 Nanostructure/Graphene Nanosheets Composite with Excellent Cycling Stability for Supercapacitors.

Transition metal hydroxides and graphene composite holds great promise to be the next generation of high performance electrode material for energy storage applications. Here we fabricate the cypress leaf-like Cu(OH)2 nanostructure/graphene nanosheets composite through one-step in situ synthesis process, employed as a new type of electrode material for high efficiency electrochemical energy storage in supercapacitors. A solution-based two-electrode system is applied to synthesize Cu(OH)2/graphene hybrid nanostructure, where anodic graphene nanosheets firmly anchor cathodic Cu(OH)2 nanostructure due to the electrostatic interaction. The in situ self-assembly of Cu(OH)2/graphene ensures good structural robustness and the cypress leaf-like Cu(OH)2 nanostructure prompt to form the open and porous morphology. The hybrid structure would facilitate charge transport and effectively mitigate the volume changes during long-term charging/discharging cycles. As a consequence, the Cu(OH)2/graphene composite exhibits the highest capacitance of 317 mF/cm2 at the current density of 1 mA/cm2 and superior cyclic stability with no capacitance decay over 20,000 cycles and remarkable rate capability at increased current densities.

NiO/Ni x Co3-x O4 porous ultrathin nanosheet/nanowire composite structures as high-performance supercapacitor electrodes.

The demand for a new generation of high-safety, long-lifespan, and high-capacity power sources increases rapidly with the growth of energy consumption in the world. Here we report a facile method for preparing architecture materials made of NiO/Ni x Co3-x O4 porous nanosheets coupled with NiO/Ni x Co3-x O4 porous nanowires grown in situ on nickel foams using a hydrothermal method without any binder followed by a heat treatment process. The nanosheet-shaped NiO/Ni x Co3-x O4 species in the nanosheet matrix function well as a scaffold and support for the dispersion of the Ni x Co3-x O4 nanowires, resulting in a relatively loose and open structure within the electrode matrix. Among all composite electrodes prepared, the one annealed in air at 300 °C displays the best electrochemical behavior, achieving a specific capacitance of 270 mF cm-2 at 5 mA cm-2 while maintaining excellent stability (retaining ≈ 89% of the max capacitance after 20 000 cycles), demonstrating its potential for practical application in power storage devices.

Fast Growth of Highly Ordered TiO2 Nanotube Arrays on Si Substrate under High-Field Anodization.

ABSTRACT: Highly ordered TiO2 nanotube arrays (NTAs) on Si substrate possess broad applications due to its high surface-to-volume ratio and novel functionalities, however, there are still some challenges on facile synthesis. Here, we report a simple and cost-effective high-field (90-180 V) anodization method to grow highly ordered TiO2 NTAs on Si substrate, and investigate the effect of anodization time, voltage, and fluoride content on the formation of TiO2 NTAs. The current density-time curves, recorded during anodization processes, can be used to determine the optimum anodization time. It is found that the growth rate of TiO2 NTAs is improved significantly under high field, which is nearly 8 times faster than that under low fields (40-60 V). The length and growth rate of the nanotubes are further increased with the increase of fluoride content in the electrolyte. GRAPHICAL ABSTRACT: Highly ordered TiO2 nanotube arrays (NTAs) on Si substrate have been fabricated by high-field anodization method. A high voltage (90-180 V) leads to a high growth rate of TiO2 NTAs (35-47 nm s-1), which is nearly 8 times faster than the growth rate under low fields (40-60 V). Furthermore, the current density-time curves recorded during the anodization provide a facial method to determine the optimal anodization parameters, leading to an easy obtaining of the desired nanotubes.

A one-step method to fabricate novel three-dimensional GaP nanopore arrays for enhanced photoelectrochemical hydrogen production.

Gallium phosphide nanopore arrays with unique three-dimensional interior architectures (3D GaP NPs) are fabricated by electrochemical etching in a neutral solution. As the photoanodes for photoelectrochemical (PEC) hydrogen production, the 3D GaP NPs exhibited a larger photocurrent density (5.65 mA cm-2 at 0 V vs. RHE, which is 58.3 and 2.3 times as large as that of the planar wafer and the NPs reported by our group in our previous work respectively) and a lower onset potential (-0.58 V vs. RHE, shifting negatively nearly 300 mV compared with its counterparts in the previous work). Besides the excellent light-trapping characteristics of the nanostructures, electrochemical impedance spectroscopy (EIS) further confirmed that the enhanced PEC performance was ascribed to the more efficient charge separation and transfer, and the increased surface area with the unique 3D NP arrays. Furthermore, the efficient charge separation may be attributed to the passivated surface states by the neutral solution.

Erratum to: A Facile Self-assembly Synthesis of Hexagonal ZnO Nanosheet Films and Their Photoelectrochemical Properties.

[This corrects the article DOI: 10.1007/s40820-015-0068-y.].

A Facile Self-assembly Synthesis of Hexagonal ZnO Nanosheet Films and Their Photoelectrochemical Properties.

Here, large-scale and uniform hexagonal zinc oxide (ZnO) nanosheet films were deposited onto indium tin oxide (ITO)-coated transparent conducting glass substrates via a facile galvanic displacement deposition process. Compared with other commonly used solution methods, this process avoids high temperature and electric power as well as supporting agents to make it simple and cost-effective. The as-fabricated ZnO nanosheet films have uniform hexagonal wurtzite structure. The photoelectrochemical (PEC) cell based on ZnO nanosheet film/ITO photoelectrode was also fabricated and its performance was improved by optimizing the solution concentration. A higher photocurrent density of ~500 µA cm-2 under AM 1.5 G simulated illumination of 100 mW cm-2 with zero bias potential (vs. Ag/AgCl electrode) was obtained, which may ascribe to the increased surface-to-volume ratio of disordered ZnO nanosheet arrays. Our developed method may be used to deposit other oxide semiconductors, and the ZnO nanosheet film/ITO PEC cell can be used to design low-cost optoelectronic and photoelectrochemical devices.