Hollow Carbon Nanospheres with Developed Porous Structure and Retained N Doping for Facilitated Electrochemical Energy Storage.

Development of highly porous carbons with abundant surface functionalities and well-defined nanostructure is of significance for many important electrochemical energy storage systems. However, porous carbons suffer from a compromise between porosity, doped functionality, and nanostructure that have thus far restricted their performances. Here, we report the design of highly porous, nitrogen-enriched hollow carbon nanospheres (PN-HCNs) by an interfacial copolymerization strategy followed by NH3-assisted carbonization, and further demonstrate their significance and effectiveness in enhancing the electrochemical performances. The PN-HCN simultaneously delivers a large surface area (1237 m2 g-1) and high N functionalities (6.25 atom %) with a remarkable efficiency of the surface area increase to N loss ratio enabled by NH3 treatment while inheriting the hollow nanospherical structure. Accordingly, owing to the enhanced surface area and retained N doping, the prepared PN-HCN demonstrates outstanding electrochemical performances as a cathode host in lithium-sulfur batteries, including a near-to-theoretical capacity of 1620 mAh g-1, high rate capability and good cycling stability (789 mAh g-1 at 0.5C after 200 cycles). These results are superior to those of HCN without NH3 treatment. Also, PN-HCN exhibits superior capacitances (203 F g-1) and fast ion transport ability in supercapacitors. Our finding shows the simultaneous achievement of both highly porous structures and sufficient N functionalities for high-performance applications.

Green Synthesis of Hierarchically Porous Carbon Nanotubes as Advanced Materials for High-Efficient Energy Storage.

Hierarchically porous carbon nanomaterials with well-defined architecture can afford a promising platform for effectively addressing energy and environmental concerns. Herein, a totally green and straightforward synthesis strategy for the fabrication of hierarchically porous carbon nanotubes (HPCNTs) by a simple carbonization treatment without any assistance of soft/hard templates and activation procedures is demonstrated. A high specific surface area of 1419 m2 g-1 and hierarchical micro-/meso-/macroporosity can be achieved for the HPCNTs. The unique porous architecture enables the HPCNTs serving as excellent electrode/host materials for high-performance supercapacitors and Li-sulfur batteries. The design strategy may pave a new avenue for the rational synthesis of hierarchically porous carbon nanostructures for high-efficient energy storage applications.

Bilayer molecular assembly at a solid/liquid interface as triggered by a mild electric field.

The construction of a spatially defined assembly of molecular building blocks, especially in the vertical direction, presents a great challenge for surface molecular engineering. Herein, we demonstrate that an electric field applied between an STM tip and a substrate triggered the formation of a bilayer structure at the solid-liquid interface. In contrast to the typical high electric-field strength (10(9)  V m(-1) ) used to induce structural transitions in supramolecular assemblies, a mild electric field (10(5)  V m(-1) ) triggered the formation of a bilayer structure of a polar molecule on top of a nanoporous network of trimesic acid on graphite. The bilayer structure was transformed into a monolayer kagome structure by changing the polarity of the electric field. This tailored formation and large-scale phase transformation of a molecular assembly in the perpendicular dimension by a mild electric field opens perspectives for the manipulation of surface molecular nanoarchitectures.

Joint Metric Learning-Based Class-Specific Representation for Image Set Classification.

With the rapid advances in digital imaging and communication technologies, recently image set classification has attracted significant attention and has been widely used in many real-world scenarios. As an effective technology, the class-specific representation theory-based methods have demonstrated their superior performances. However, this type of methods either only uses one gallery set to measure the gallery-to-probe set distance or ignores the inner connection between different metrics, leading to the learned distance metric lacking robustness, and is sensitive to the size of image sets. In this article, we propose a novel joint metric learning-based class-specific representation framework (JMLC), which can jointly learn the related and unrelated metrics. By iteratively modeling probe set and related or unrelated gallery sets as affine hull, we reconstruct this hull sparsely or collaboratively over another image set. With the obtained representation coefficients, the combined metric between the query set and the gallery set can then be calculated. In addition, we also derive the kernel extension of JMLC and propose two new unrelated set constituting strategies. Specifically, kernelized JMLC (KJMLC) embeds the gallery sets and probe sets into the high-dimensional Hilbert space, and in the kernel space, the data become approximately linear separable. Extensive experiments on seven benchmark databases show the superiority of the proposed methods to the state-of-the-art image set classifiers.

Highly Lithiophilic Cobalt Nitride Nanobrush as a Stable Host for High-Performance Lithium Metal Anodes.

Lithium metal is considered to be a holy grail of the battery anode chemistry due to its large specific capacity. Nevertheless, the uncontrollable formation of lithium dendrites resulting from uneven lithium nucleation/growth and the associated safety risk and short cyclability severely impede the practical use of lithium metal anodes. Herein, we demonstrate a highly lithiophilic cobalt nitride nanobrush on a Ni foam (Co3N/NF) current collector as a stable three-dimensional (3D) framework to inhibit the dendrite formation of lithium. The 3D Co3N/NF nanobrush electrode could enable a low nucleation overpotential for homogeneous deposition of dendrite-free lithium. Compared to the CoO/NF counterpart and the bare Cu foil/Ni foam, the Co3N/NF nanobrush host is of great benefit for enhanced Coulombic efficiencies and longer lifespan at various current densities. The present work will offer a new insight for the exploration of the highly lithiophilic scaffold based on metal nitrides toward high-performance lithium metal anodes.

Graphene-Boosted, High-Performance Aqueous Zn-Ion Battery.

Given their low cost and eco-friendliness, rechargeable Zn-ion batteries (ZIBs) have received increasing attention as a device with great potential for large-scale energy storage. However, the development of ZIBs with high capacities and long lifespans is challenging because of the dendritic growth of Zn and the absence of suitable cathode materials. Herein, we report a novel rechargeable aqueous Zn-ion battery (AZIB) that consist of Zn coated with reduced graphene oxide as the anode and V3O7·H2O/rGO composite as the cathode. The new AZIB exhibits excellent cycle stability with a high capacity retention of 79% after 1000 cycles. Moreover, it can deliver a high power density of 8400 W kg-1 at 77 W h kg-1 and a high energy density of 186 W h kg-1 at 216 W kg-1, and the former is higher than those of previously reported AZIBs. Our work provides a new perspective in developing rechargeable ZIBs and would greatly accelerate the practical applications of rechargeable ZIBs.

Triaxial Nanocables of Conducting Polypyrrole@SnS2@Carbon Nanofiber Enabling Significantly Enhanced Li-Ion Storage.

Two-dimensional (2D) SnS2 materials represent a class of high-capacity candidates as anodes of Li-ion batteries (LIBs); however, they are limited by inferior rate and cycling performance. Herein, we demonstrate unique triaxial nanocables of conducting polypyrrole@SnS2@carbon nanofiber (PPy@SnS2@CNF) prepared via a facile combination of hydrothermal method and vapor-phase polymerization. The PPy@SnS2@CNF manifests a strong synergistic effect from its hierarchical nanoarchitecture, which provides enlarged electrode/electrolyte contact interfaces, highly electrical conductive pathways, sufficient electrolyte ingress/transport channels, and an intimate mechanical/electrochemical safeguard for fast electrode kinetics and good structural stability. When evaluated as binder-free anodes of LIBs, the ternary nanocomposite delivers an ultrahigh reversible capacity of 1165 mAh g-1 after 100 cycles and outstanding rate/cycling performance (880 mAh g-1 at 2000 mA g-1), which are among the best results of the previously reported SnS2 electrodes. This work may pave a rational avenue of developing 2D materials with hierarchical structures for highly efficient energy-storage systems.

Au/TiO2 Hollow Spheres with Synergistic Effect of Plasmonic Enhancement and Light Scattering for Improved Dye-Sensitized Solar Cells.

Au-decorated TiO2 hollow spheres (Au-THS) have been successfully synthesized via a facile one-pot solvothermal method. The Au-THS hybrid features unique hollow structure with a large specific surface area of 120 m2 g-1 and homogeneous decoration of Au nanoparticles, giving rise to enhanced light harvesting and charge generation/separation efficiency. When incorporated into the active layer of dye-sensitized solar cells (DSSCs), an improved power conversion efficiency of 7.3% is obtained, which is increased by 37.7% compared with the controlled P25 DSSC. The underlying mechanism to rationalize the efficiency enhancement can be mainly attributed to the strong synergistic effect of superior light scattering ability of the THS and the plasmonic-enhanced effect rendered by the Au nanoparticles.

Dual Functionalities of Carbon Nanotube Films for Dendrite-Free and High Energy-High Power Lithium-Sulfur Batteries.

As a promising Li-metal battery, Li-S battery has an ultrahigh theoretical energy density of 2600 Wh kg-1. However, most of the previous work has mainly focused on tackling the "polysulfide shuttle" originating from the S cathode, while the dendrite problem coming from the Li-metal anode has often been overlooked. Herein, to solve the issues arising from both the cathode and anode simultaneously, we propose a novel cell configuration for the first time by inserting CNT films on both sides of the separator in Li-S batteries, in which the cathode-side CNT film works as a shield to suppress the "polysulfide shuttle" and the anode-side CNT film acts as a powerful shield to prevent the Li dendrite growth. In the new cell configuration, the S/rGO cathode with a high S loading of about 4.0 mg cm-2 displays a high specific capacity (1336 mAh g-1 at 0.2 C), excellent rate ability (1070, 833, 656, and 444 mAh g-1 at 0.5, 1, 2, and 5 C, respectively), and sustainable cycling stability for 150 cycles with high Coulombic efficiency (>99%) at 1 C, while the Li metal anode displays an ultrasmooth surface. We believe this work will aid in developing other metal-based (e.g., Na, K, Zn, and Al) batteries.

Coaxial MoS2@Carbon Hybrid Fibers: A Low-Cost Anode Material for High-Performance Li-Ion Batteries.

A low-cost bio-mass-derived carbon substrate has been employed to synthesize MoS2@carbon composites through a hydrothermal method. Carbon fibers derived from natural cotton provide a three-dimensional and open framework for the uniform growth of MoS2 nanosheets, thus hierarchically constructing coaxial architecture. The unique structure could synergistically benefit fast Li-ion and electron transport from the conductive carbon scaffold and porous MoS2 nanostructures. As a result, the MoS2@carbon composites-when serving as anodes for Li-ion batteries-exhibit a high reversible specific capacity of 820 mAh·g-1, high-rate capability (457 mAh·g-1 at 2 A·g-1), and excellent cycling stability. The use of bio-mass-derived carbon makes the MoS2@carbon composites low-cost and promising anode materials for high-performance Li-ion batteries.

Highly Flexible Graphene/Mn3O4 Nanocomposite Membrane as Advanced Anodes for Li-Ion Batteries.

Advanced electrode design is crucial in the rapid development of flexible energy storage devices for emerging flexible electronics. Herein, we report a rational synthesis of graphene/Mn3O4 nanocomposite membranes with excellent mechanical flexibility and Li-ion storage properties. The strong interaction between the large-area graphene nanosheets and long Mn3O4 nanowires not only enables the membrane to endure various mechanical deformations but also produces a strong synergistic effect of enhanced reaction kinetics by providing enlarged electrode/electrolyte contact area and reduced electron/ion transport resistance. The mechanically robust membrane is explored as a freestanding anode for Li-ion batteries, which delivers a high specific capacity of ∼800 mAh g(-1) based on the total electrode mass, along with superior high-rate capability and excellent cycling stability. A flexible full Li-ion battery is fabricated with excellent electrochemical properties and high flexibility, demonstrating its great potential for high-performance flexible energy storage devices.

Toward Dendrite-Free Lithium Deposition via Structural and Interfacial Synergistic Effects of 3D Graphene@Ni Scaffold.

Owing to its ultrahigh specific capacity and low electrochemical potential, lithium (Li) metal is regarded as one of the most attractive anode materials for next-generation lithium batteries. Nevertheless, the commercialization of Li-metal-based rechargeable batteries (LiMBs) has been retarded by the uncontrollable growth of Li dendrites, as well as the resulting poor cycle stability and safety hazards. In this work, a 3D graphene@Ni scaffold has been proposed to accomplish dendrite-free Li deposition via structural and interfacial synergistic effects. Due to the intrinsic high surface area used to reduce the effective electrode current density and the surface-coated graphene working as an artificial protection layer to provide high cycle stability as well as suppress the growth of Li dendrites, the Coulombic efficiencies of Li deposition on 3D graphene@Ni foam after 100 cycles can be sustained as high as 96, 98, and 92% at the current densities of 0.25, 0.5, and 1.0 mA cm-2, respectively, which shows more excellent cycle stability than that of its planar Cu foil and bare Ni foam counterparts. The results obtained here demonstrate that the comprehensive consideration of multiaspect factors could be more help to enhance the performance of Li metal anode so as to achieve its real application in next-generation LiMBs.

In situ observation of electrolyte-concentration-dependent solid electrolyte interphase on graphite in dimethyl sulfoxide.

High lithium salt concentration strategy has been recently reported to be an effective method to enable various organic solvents as electrolyte of Li-ion batteries. Here, we utilize in situ atomic force microscopy (AFM) to investigate the interfacial morphology on the graphite electrode in dimethyl sulfoxide (DMSO)-based electrolyte of various concentrations. The significant differences in interfacial features of the graphite in electrolytes of different concentrations are revealed. In the concentrated electrolyte, stable films form primarily at the step edges and defects on the graphite surface after initial electrochemical cycling. On the other hand, in the dilute electrolyte, DMSO-solvated lithium ions constantly intercalate into graphite layers, and serious decomposition of solvent accompanied by structural deterioration of the graphite surface is observed. The in situ AFM results provide direct evidence for the concentration-dependent interface reactions between graphite electrode and DMSO-based electrolyte.

Catalytic Performance of Pt/Reduced Graphene Oxide Composites to Methanol Electrochemical Oxidation: Optimization of Mass-Specific Activity.

Series of catalysts made of Pt nanoparticles supported on reduced graphene oxides (Pt/RGO) were synthesized and tested in methanol oxidation reaction, aiming for optimizing the mass-specific activity of prepared Pt/RGO composites. The loading amount of Pt is controlled through setting different reaction time and determined precisely by atomic absorption spectrophotometer. The structure of Pt/RGO composites is characterized by X-ray diffraction, transmission electron microscopy and Raman spectroscopy. The electrochemical testing data reveal that the Pt/RGO-mass-specific activity, judged by current density and long-term stability, is maximized in the sample in which cooperation of the Pt loading amount and electrochemical active surface area (ECSA) per amount of Pt is best optimized. The performance of the catalyst with smallest Pt particles or highest Pt loading amount is dragged down by either too less Pt loading or poor ECSA per amount of Pt. The results in this research demonstrate that the mass-normalized activity of whole catalyst, which is associated with the anticipated power output per amount of catalyst, could be enhanced significantly by deliberate tuning of fabrication process.

Depression-like Behavior Induced by Nesfatin-1 in Rats: Involvement of Increased Immune Activation and Imbalance of Synaptic Vesicle Proteins.

Depression is a multicausal disorder and has been associated with metabolism regulation and immuno-inflammatory reaction. The anorectic molecule nesfatin-1 has recently been characterized as a potential mood regulator, but its precise effect on depression and the possible mechanisms remain unknown, especially when given peripherally. In the present study, nesfatin-1 was intraperitoneally injected to the rats and the depression-like behavior and activity of the hypothalamic-pituitary-adrenal (HPA) axis were evaluated. The plasma concentrations of nesfatin-1, interleukin 6 (IL-6), and C-reactive protein (CRP); and the hypothalamic expression levels of nesfatin-1, synapsin I, and synaptotagmin I mRNA were evaluated in nesfatin-1 chronically treated rats. The results showed that both acute and chronic administration of nesfatin-1 increased immobility in the forced swimming test (FST), and resulted in the hyperactivity of HPA axis, as indicated by the increase of plasma corticosterone concentration and hypothalamic expression of corticotropin-releasing hormone (CRH) mRNA. Moreover, after chronic nesfatin-1 administration, the rats exhibited decreased activity and exploratory behavior in the open field test (OFT) and increased mRNA expression of synapsin I and synaptotagmin I in the hypothalamus. Furthermore, chronic administration of nesfatin-1 elevated plasma concentrations of IL-6 and CRP, which were positively correlated with despair behavior, plasma corticosterone level, and the hypothalamic mRNA expression of synapsin I and synaptotagmin I. These results indicated that exogenous nesfatin-1 could induce the immune-inflammatory activation, which might be a central hug linking the depression-like behavior and the imbalanced mRNA expression of synaptic vesicle proteins in the hypothalamus.

Acute, but not chronic, stress increased the plasma concentration and hypothalamic mRNA expression of NUCB2/nesfatin-1 in rats.

Nesfatin-1, a newly discovered satiety peptide, has recently been reported to be involved in the stress response. Stress-induced expression of nesfatin-1 has been reported and few studies focus on its expression in the hypothalamus, which is the center of the stress response. To test our hypothesis that peripheral and hypothalamic nesfatin-1 overexpression should play an important role in the stress response and the associated hyperactivity of hypothalamic-pituitary-adrenal (HPA) axis, acute stress (AS) was induced using water avoidance stress (WAS), and chronic unpredictable mild stress (CUMS) was also induced using 3 consecutive weeks of 7 different stressors. The behavior of CUMS rats was evaluated by an open field test (OFT), sucrose preference test (SPT), and forced swimming test (FST). The activity of the HPA axis was detected by measurement of the plasma corticosterone concentration and hypothalamic mRNA expression of corticotropin-releasing-hormone (CRH). The plasma concentration and hypothalamic mRNA expression of nesfatin-1 were measured with an enzyme-linked immunosorbent assay (ELISA) and real-time fluorescent quantitative PCR, respectively. The results showed that both AS and CUMS increased the plasma corticosterone concentration and hypothalamic CRH mRNA expression. Depression-like behavior was induced in CUMS rats, as indicated by a decreased movement distance, frequency of rearing and grooming in the OFT, and sucrose preference index and increased immobility in the FST. Moreover, the AS rats showed increased plasma concentration and hypothalamic mRNA expression of nesfatin-1, which were positively correlated with the plasma corticosterone concentration and hypothalamic CRH expression, respectively. These results indicated that acute stress, but not chronic stress, increased the plasma concentration and hypothalamic mRNA expression of NUCB2/nesfatin-1 in rats.

Facet dependent SEI formation on the LiNi(0.5)Mn(1.5)O4 cathode identified by in situ single particle atomic force microscopy.

A facile protocol is developed for the direct observation and characterization of a single particle electrode during the lithium ion battery operation by using in situ AFM. The SEI formation on the LiNi0.5Mn1.5O4 particle cathode surface is found to be highly related to the exposed planes.

Single nanowire electrode electrochemistry of silicon anode by in situ atomic force microscopy: solid electrolyte interphase growth and mechanical properties.

Silicon nanowires (SiNWs) have attracted great attention as promising anode materials for lithium ion batteries (LIBs) on account of their high capacity and improved cyclability compared with bulk silicon. The interface behavior, especially the solid electrolyte interphase (SEI), plays a significant role in the performance and stability of the electrodes. We report herein an in situ single nanowire atomic force microscopy (AFM) method to investigate the interface electrochemistry of silicon nanowire (SiNW) electrode. The morphology and Young's modulus of the individual SiNW anode surface during the SEI growth were quantitatively tracked. Three distinct stages of the SEI formation on the SiNW anode were observed. On the basis of the potential-dependent morphology and Young's modulus evolution of SEI, a mixture-packing structural model was proposed for the SEI film on SiNW anode.