Visualizing interfacial collective reaction behaviour of Li-S batteries.

Benefiting from high energy density (2,600 Wh kg-1) and low cost, lithium-sulfur (Li-S) batteries are considered promising candidates for advanced energy-storage systems1-4. Despite tremendous efforts in suppressing the long-standing shuttle effect of lithium polysulfides5-7, understanding of the interfacial reactions of lithium polysulfides at the nanoscale remains elusive. This is mainly because of the limitations of in situ characterization tools in tracing the liquid-solid conversion of unstable lithium polysulfides at high temporal-spatial resolution8-10. There is an urgent need to understand the coupled phenomena inside Li-S batteries, specifically, the dynamic distribution, aggregation, deposition and dissolution of lithium polysulfides. Here, by using in situ liquid-cell electrochemical transmission electron microscopy, we directly visualized the transformation of lithium polysulfides over electrode surfaces at the atomic scale. Notably, an unexpected gathering-induced collective charge transfer of lithium polysulfides was captured on the nanocluster active-centre-immobilized surface. It further induced an instantaneous deposition of nonequilibrium Li2S nanocrystals from the dense liquid phase of lithium polysulfides. Without mediation of active centres, the reactions followed a classical single-molecule pathway, lithium polysulfides transforming into Li2S2 and Li2S step by step. Molecular dynamics simulations indicated that the long-range electrostatic interaction between active centres and lithium polysulfides promoted the formation of a dense phase consisting of Li+ and Sn2- (2 < n ≤ 6), and the collective charge transfer in the dense phase was further verified by ab initio molecular dynamics simulations. The collective interfacial reaction pathway unveils a new transformation mechanism and deepens the fundamental understanding of Li-S batteries.

Unveiling Atom Migration Abilities Affected Anode Performance of Sodium-Ion Batteries.

In sodium-ion batteries (SIBs), the low initial coulombic efficiency (ICE) is commonly induced by irreversible phase conversion and difficult desodiation, especially on transition metal compounds (TMCs). Yet the underlying physicochemical mechanism of poor reaction reversibility is still a controversial issue. Herein, by using in situ transmission electron microscopy and in situ X-ray diffraction, we demonstrate the irreversible conversion of NiCoP@C is caused by the rapid migration of P in carbon layer and preferential formation of isolated Na3 P during discharge. By modifying the carbon coating layer, the migration of Ni/Co/P atoms is inhibited, thus the improvement of ICE and cycle stability is realized. The inhibiting of fast atom migration which induces component separation and rapid performance degradation might be applied to a wide range of electrode materials, and guides the development of advanced SIBs.

Ultrasmall Abundant Metal-Based Clusters as Oxygen-Evolving Catalysts.

The oxygen evolution reaction is a crucial step in water electrolysis to develop clean and renewable energy. Although noble metal-based catalysts have demonstrated high activity for the oxygen evolution reaction, their application is limited by their high cost and low availability. Here we report the use of a molecule-to-cluster strategy for preparing ultrasmall trimetallic clusters by using the polyoxometalate molecule as a precursor. Ultrafine (0.8 nm) transition-metal clusters with controllable chemical composition are obtained. The transition-metal clusters enable highly efficient oxygen evolution through water electrolysis in alkaline media, manifested by an overpotential of 192 mV at 10 mA cm-2, a low Tafel slope of 36 mV dec-1, and long-term stability for 30 h of electrolysis. We note, however, that besides the excellent performance as an oxygen evolution catalyst, our molecule-to-cluster strategy provides a means to achieve well-defined transition-metal clusters in the subnanometer regime, which potentially can have an impact on several other applications.

Three-dimensional nanotubes composed of carbon-anchored ultrathin MoS2 nanosheets with enhanced lithium storage.

MoS2 nanotubes (denoted as MoS2 NTs) assembled from well-aligned amorphous carbon-modified ultrathin MoS2 nanosheets (denoted as MoS2 NT@C) were successfully fabricated via a facile solvothermal method combined with subsequent annealing treatment. With the assistance of octylamine as a solvent and carbon source, interconnected MoS2 nanosheets (denoted as MoS2 NSs) can assemble into hierarchical MoS2 NTs. Such a hybrid nanostructure can effectively facilitate charge transport and accommodate volume variation upon prolonged charge/discharge cycling for reversible lithium storage. As a result, the MoS2 NT@C composite manifests a very stable high reversible capacity of around 1351 mA h g(-1) at a current density of 100 mA g(-1); even after 150 cycles, the electrode reaches a capacity of 1106 mA h g(-1) and it retains a reversible capacity of 650 mA h g(-1) after the 10th cycle at a current density of 3 A g(-1), all of which indicate that the MoS2 NT@C nanocomposite is a promising negative electrode material for high-energy lithium ion batteries.

Observing ion diffusion and reciprocating hopping motion in water.

When an ionic crystal dissolves in solvent, the positive and negative ions associated with solvent molecules release from the crystal. However, the existing form, interaction, and dynamics of ions in real solution are poorly understood because of the substantial experimental challenge. We observed the diffusion and aggregation of polyoxometalate (POM) ions in water by using liquid phase transmission electron microscopy. Real-time observation reveals an unexpected local reciprocating hopping motion of the ions in water, which may be caused by the short-range polymerized bridge of water molecules. We find that ion oligomers, existing as highly active clusters, undergo frequent splitting, aggregation, and rearrangement in dilute solution. The formation and dissociation of ion oligomers indicate a weak counterion-mediated interaction. Furthermore, POM ions with tetrahedral geometry show directional interaction compared with spherical ions, which presents structure-dependent dynamics.

A "Biconcave-Alleviated" Strategy to Construct Aspergillus niger-Derived Carbon/MoS2 for Ultrastable Sodium Ion Storage.

Two-dimensional layered materials commonly face hindered electron transfer and poor structure stability, thus limiting their application in high-rate and long-term sodium ion batteries. In the current study, we adopt finite element simulation to guide the rational design of nanostructures. By calculating the von Mises stress distribution of a series of carbon materials, we find that the hollow biconcave structure could effectively alleviate the stress concentration resulting from expansion. Accordingly, we propose a biconcave-alleviated strategy based on the Aspergillus niger-derived carbon (ANDC) to construct ANDC/MoS2 with a hollow biconcave structure. The ANDC/MoS2 is endowed with an excellent long-term cyclability as an anode of sodium ion batteries, delivering a discharge capacity of 496 mAh g-1 after 1000 cycles at 1 A g-1. A capacity retention rate of 94.5% is achieved, an increase of almost seven times compared with the bare MoS2 nanosheets. Even at a high current density of 5 A g-1, a reversible discharge capacity around 400 mAh g-1 is maintained after 300 cycles. ANDC/MoS2 could also be used for efficient lithium storage. By using in situ TEM, we further reveal that the hollow biconcave structure of ANDC/MoS2 has enabled stable and fast sodiation/desodiation.

Fabrication of WS2-nanoflowers@rGO composite as an anode material for enhanced electrode performance in lithium-ion batteries.

In this paper, we descried a simple method to fabricate three-dimensional (3D) composite materials, WS2-nanoflowers @ reduced graphene oxide (WS2-NF@rGO), in which rGO crossed-link the isolated WS2-NF to construct a 3D conductive network and provided protection against the volume changes of WS2 during electrochemical processes simultaneously. This unique structure of the WS2-NF@rGO composite could not only promote both ion and electron diffusion, but also enhance the electrode stability, thus obtaining a high-capacity and long-cycle anode material for lithium-ion batteries. As a result, the WS2-NF@rGO exhibited a reversible capacity of 730mAhg-1 after 150 cycles at 100mAg-1 and maintained a capacity of higher than 260mAhg-1 at 2Ag-1, thus exhibiting great potential as an anode material for lithium storage.

Porous carbon derived from Sunflower as a host matrix for ultra-stable lithium-selenium battery.

A novel porous carbon material using the spongy tissue of sunflower as raw material is reported for the first time. The obtained porous carbon has an extremely high surface area of 2493.0m2g-1, which is beneficial to focus on encapsulating selenium in it and have an inhibiting effect about diffusion of polyselenides over the charge/discharge processes used as the host matrix for Li-Se battery. The porous carbon/Se composite electrode with 63wt% selenium delivers a high specific capacitance of 319mAhg-1 of the initial capacity, and maintains 290mAhg-1, representing an extremely high capacity retention of 90.9% after 840 cycles with the rate of 1C.

Aspergillus flavus Conidia-derived Carbon/Sulfur Composite as a Cathode Material for High Performance Lithium-Sulfur Battery.

A novel approach was developed to prepare porous carbon materials with an extremely high surface area of 2459.6 m(2)g(-1) by using Aspergillus flavus conidia as precursors. The porous carbon serves as a superior cathode material to anchor sulfur due to its uniform and tortuous morphology, enabling high capacity and good cycle lifetime in lithium sulfur-batteries. Under a current rate of 0.2 C, the carbon-sulfur composites with 56.7 wt% sulfur loading deliver an initial capacity of 1625 mAh g(-1), which is almost equal to the theoretical capacity of sulfur. The good performance may be ascribed to excellent electronic networks constructed by the high-surface-area carbon species. Moreover, the semi-closed architecture of derived carbons can effectively retard the polysulfides dissolution during charge/discharge, resulting in a capacity of 940 mAh g(-1) after 120 charge/discharge cycles.

Facile Synthesis of Novel Networked Ultralong Cobalt Sulfide Nanotubes and Its Application in Supercapacitors.

Ultralong cobalt sulfide (CoS(1.097)) nanotube networks are synthesized by a simple one-step solvothermal method without any surfactant or template. A possible formation mechanism for the growth processes is proposed. Owing to the hollow structure and large specific area, the novel CoS(1.097) materials present outstanding electrochemical properties. Electrochemical measurements for supercapacitors show that the as-prepared ultralong CoS(1.097) nanotube networks exhibit high specific capacity, good capacity retention, and excellent Coulombic efficiency.

Synthesis of novel book-like K0.23V2O5 crystals and their electrochemical behavior in lithium batteries.

A novel book-like K0.23V2O5 crystal is obtained by a simple hydrothermal method and is explored as a cathode material for Li-ion batteries for the first time. It exhibits a high reversible capacity (of ca. 244 mA h g(-1) at a current density of 50 mA g(-1)), along with a good rate capability (80 mA h g(-1) at a current density of 1800 mA g(-1)) and a good capacity retention (185.3 mA h g(-1) after 100 cycles).

Fabrication of CeO2 nanoparticle-modified silk for UV protection and antibacterial applications.

To endow silk with UV-shielding ability and antibacterial activity, CeO2 nanoparticles were immobilized on silk surface via a dip-coating approach without changing silk structure. Surface density of the nanoparticles could be easily adjusted by controlling the number of dip-coating cycle. Enhanced thermal stability of the modified silk is exhibited in thermogravimetric analysis (TGA) and derivative thermogravimetric analysis (DTG). The excellent UV-protection ability and antibacterial property of the CeO2 nanoparticle-coated silk are demonstrated in UV-vis diffuse reflectance spectroscopy and colony-forming capability test, respectively. Based on the data, it can be concluded that CeO2 nanoparticles could be used as a very promising coating material to modify silk for UV-protection and antibacterial applications.