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.

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.

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%.

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.

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.

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.

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.

Synchronous exfoliation and assembly of graphene on 3D Ni(OH)2 for supercapacitors.

Nowadays, new approaches to fabricate high-performance electrode materials are of vital importance in the renewable energy field. Here, we present a facile synthesis procedure of 3D Ni(OH)2/graphene hybrids for supercapacitors via synchronous electrochemical-assisted exfoliation and assembly of graphene on 3D Ni(OH)2 networks. With the assistance of an electric field, the electrochemically exfoliated high-quality graphene can be readily, uniformly assembled on the surfaces of 3D Ni(OH)2. When serving as electrode materials for supercapacitors, the resulting 3D Ni(OH)2/graphene composites exhibited excellent specific capacitance (263 mF cm-2 at 2 mA cm-2), remarkable rate capability and super-long cycle life (retention of 94.1% even after 10 000 continuous charge-discharge cycles), which may be attributed to their highly porous, stable 3D architecture as well as uniform, firm anchoring of ultrathin graphene on their surfaces. Therefore, our approach provides a facile strategy for the large-scale synthesis of high-quality graphene based composites towards various applications.

Unique Three-Dimensional InP Nanopore Arrays for Improved Photoelectrochemical Hydrogen Production.

Ordered three-dimensional (3D) nanostructure arrays hold promise for high-performance energy harvesting and storage devices. Here, we report the fabrication of InP nanopore arrays (NPs) in unique 3D architectures with excellent light trapping characteristic and large surface areas for use as highly active photoelectrodes in photoelectrochemical (PEC) hydrogen evolution devices. The ordered 3D NPs were scalably synthesized by a facile two-step etching process of (1) anodic etching of InP in neutral 3 M NaCl electrolytes to realize nanoporous structures and (2) wet chemical etching in HCl/H3PO4 (volume ratio of 1:3) solutions for removing the remaining top irregular layer. Importantly, we demonstrated that the use of neutral electrolyte of NaCl instead of other solutions, such as HCl, in anodic etching of InP can significantly passivate the surface states of 3D NPs. As a result, the maximum photoconversion efficiency obtained with ∼15.7 µm thick 3D NPs was 0.95%, which was 7.3 and 1.4 times higher than that of planar and 2D NPs. Electrochemical impedance spectroscopy and photoluminescence analyses further clarified that the improved PEC performance was attributed to the enhanced charge transfer across 3D NPs/electrolyte interfaces, the improved charge separation at 3D NPs/electrolyte junction, and the increased PEC active surface areas with our unique 3D NP arrays.

Engineering MoSx/Ti/InP Hybrid Photocathode for Improved Solar Hydrogen Production.

Due to its direct band gap of ~1.35 eV, appropriate energy band-edge positions, and low surface-recombination velocity, p-type InP has attracted considerable attention as a promising photocathode material for solar hydrogen generation. However, challenges remain with p-type InP for achieving high and stable photoelectrochemical (PEC) performances. Here, we demonstrate that surface modifications of InP photocathodes with Ti thin layers and amorphous MoSx nanoparticles can remarkably improve their PEC performances. A high photocurrent density with an improved PEC onset potential is obtained. Electrochemical impedance analyses reveal that the largely improved PEC performance of MoSx/Ti/InP is attributed to the reduced charge-transfer resistance and the increased band bending at the MoSx/Ti/InP/electrolyte interface. In addition, the MoSx/Ti/InP photocathodes function stably for PEC water reduction under continuous light illumination over 2 h. Our study demonstrates an effective approach to develop high-PEC-performance InP photocathodes towards stable solar hydrogen production.

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.

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.

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.].

Plasma-Induced Oxygen Vacancies in Ultrathin Hematite Nanoflakes Promoting Photoelectrochemical Water Oxidation.

The incorporation of oxygen vacancies in hematite has been investigated as a promising route to improve oxygen evolution reaction activity of hematite photoanodes used in photoelectrochemical water oxidation. However, introducing oxygen vacancies intentionally in α-Fe2O3 for active solar water splitting through facile and effective methods remains a challenge. Herein, air plasma treatment is shown to produce oxygen vacancies in α-Fe2O3, and ultrathin α-Fe2O3 nanoflakes are used to investigate the effect of oxygen vacancies on the performance of photoelectrochemical oxygen oxidation. Increasing the plasma treatment duration and power is found to increase the density of oxygen vacancies and leads to a significant enhancement of the photocurrent response. The nanoflake photoanode with the optimized plasma treatment yields an incident photo-to-current conversion efficiency of 35.4% at 350 nm under 1.6 V vs RHE without resorting to any other cocatalysts, an efficiency far exceeding that of the pristine α-Fe2O3 nanoflakes (∼2.2%). Evidence for the presence of high density of oxygen vacancies confined in nanoflakes is clarified by X-ray photoelectron spectroscopy. The increased number of oxygen vacancies after plasma treatment resulting in an increased carrier density is interpreted as the main cause for the enhanced oxygen evolution reaction activity.

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.

Fast anodization fabrication of AAO and barrier perforation process on ITO glass.

Thin films of porous anodic aluminum oxide (AAO) on tin-doped indium oxide (ITO) substrates were fabricated through evaporation of a 1,000- to 2,000-nm-thick Al, followed by anodization with different durations, electrolytes, and pore widening. A faster method to obtain AAO on ITO substrates has been developed, which with 2.5 vol.% phosphoric acid at a voltage of 195 V at 269 K. It was found that the height of AAO films increased initially and then decreased with the increase of the anodizing time. Especially, the barrier layers can be removed by extending the anodizing duration, which is very useful for obtaining perforation AAO and will broaden the application of AAO on ITO substrates.