Search

Most of the currently developed sodium-ion batteries (SIBs) have potential safety hazards due to the use of highly volatile and flammable alkyl carbonate electrolytes. To overcome this challenge, we report an electrochemically compatible and nonflammable electrolyte, tris(2,2,2-trifluoroethyl) phosphate (TFEP) with low-concentration sodium bis(fluorosulfonyl)imide (0.9 M), which is designed not only to match perfectly with the hard carbon (HC) anode but also to enhance the thermal stability of SIBs. Experimental results and theoretical calculations reveal that TFEP molecules have a significantly low barrier to decompose before Na + inserts into HC, forming a stable inorganic solid-electrolyte interface layer, thus improving the electrochemical and structural stabilities of HC anodes. An HC/Na 3 V 2 (PO 4 ) 3 full cell using TFEP electrolyte shows a high capacity retention of 89.2% after 300 cycles and a dramatically reduced exothermic heat at elevated temperature, implying its potential application for safe and low-cost larger-scale energy storage., (Copyright © 2018 The Author(s). Published by Elsevier Inc. All rights reserved.)

Exceptional performance reported for battery materials and devices in the scientific literature is often measured under conditions that are not aligned with practical applications. Aiming to bridge the gap between academia and industry, this Comment advocates the best practices for gauging performance and proposes guidelines on measurements with respect to a list of key metrics such as capacity, cyclability, Coulombic efficiency and electrolyte consumption.

Electrolytes as an important part of sodium-ion batteries have a pivotal role for capacity, rate, and durability of electrode materials. On account of the high reduction activity of sodium metal with organic solvents, it is very important to optimize the electrolyte component to realize high stability on Na metal and hard carbon anodes. Herein, chemical and electrochemical stability of propylene carbonate (PC)-based electrolytes on sodium metal and hard carbon anodes is investigated systematically. The results demonstrate that whether using NaClO 4 or NaPF 6 , the PC-based electrolytes are not stable on Na metal, but adding of FEC can immensely enhance the stability of the electrolyte because of the compact solid electrolyte interphase film formed. The electrolytes containing FEC also exhibit high electrochemical compatibility on hard carbon anodes, showing high reversible capacity and excellent cycling performance. A reaction mechanism based on the Na + induction effect is proposed by spectrum and electrochemical measurements. This study can provide a new insight to optimize and develop stable PC-based electrolytes and be helpful for understanding the other electrolyte systems.

Nonflammable phosphate electrolytes are in principle able to build intrinsically safe Na-ion batteries, but their electrochemical incompatibility with anodic materials, especially hard carbon anode, restricts their battery applications. Here, we propose a new strategy to enable high-capacity utilization and cycle stability of hard carbon anodes in the nonflammable phosphate electrolyte by using low-cost Na + salt with a high molar ratio of salt/solvent combined with an solid electrolyte interphase film-forming additive. As a result, the carbon anode in the trimethyl phosphate (TMP) electrolyte with a high molar ratio of [NaClO 4 ]/[TMP] and 5% fluoroethylene carbonate additive demonstrates a high reversible capacity of 238 mAh g -1 , considerable rate capability, and long-term cycling life with 84% capacity retention over 1500 cycles. More significantly, this work provides a promising route to build intrinsically safe and low-cost sodium-ion batteries for large-scale energy storage applications.

A rechargeable aqueous Zn/Mn battery is a promising device for large-scale energy storage because of its abundant resources, low cost, and high safety. However, its application is plagued by a poor life cycle because of the electrochemical instability of MnO 2 in aqueous electrolytes. Here, an alkaline Zn-Na 0.44 MnO 2 dual-ion battery (denoted AZMDIB) is developed for the first time using Na 0.44 MnO 2 as the cathode, a zinc metal sheet as the anode, and a 6 M NaOH aqueous solution as the electrolyte. When the discharge cutoff voltage is lowered to 0.3 V (vs Zn/Zn 2+ ), the Na 0.44 MnO 2 cathode delivers a high capacity of 345.5 mA h g -1 but with a poor cycling performance. The charge-discharge mechanism and structural evolution of the Na 0.44 MnO 2 cathode in an extended potential window (1.95-0.3 V) are also explored. The Na 0.44 MnO 2 electrode experiences two different electrochemical processes: Na + ions insert/extract reversibly in the potential range of 1.95-1.1 V, and a phase transition occurs from Na 0.559 MnO 2 to Mn(OH) 2 below 1.1 V. The latter irreversible reaction is probably due to proton insertion, leading to a severe capacity fade. Nevertheless, in a narrower voltage range (2.0-1.1 V), the AZMDIB full cell exhibits a high reversible capacity (80.2 mA h g -1 at 0.5 C), high rate capability (32 mA h g -1 at 50 C), and excellent cycling stability (73% capacity retention over 1000 cycles at 10 C). Benefiting from the merits of environmental friendliness, cost-effectiveness, and high electrochemical performance, the rechargeable AZMDIB is a promising contender for grid-scale energy storage applications.

Batteries and electrochemical capacitors play very important roles in the portable electronic devices and electric vehicles and have shown promising potential for large-scale energy storage applications. However, batteries or capacitors alone cannot meet the energy and power density requirements because rechargeable batteries have a poor power property, whereas supercapacitors offer limited capacity. Here, a novel symmetric sodium-ion capacitor (NIC) is developed based on low-cost Na 0.44 MnO 2 nanorods. The Na 0.44 MnO 2 with unique nanoarchitectures and iso-oriented feature offers shortened diffusion path lengths for both electronic and Na + transport and reduces the stress associated with Na + insertion and extraction. Benefiting from these merits, the symmetric device achieves a high power density of 2432.7 W kg -1 , an improved energy density of 27.9 Wh kg -1 , and a capacitance retention of 85.2% over 5000 cycles. Particularly, the symmetric NIC based on Na 0.44 MnO 2 permits repeatedly reverse-polarity characteristics, thus simplifying energy management system and greatly enhancing the safety under abuse condition. This cost-effective, high-safety, and high-performance symmetric NIC can balance the energy and power density between batteries and capacitors and serve as an electric power source for future low-maintenance large-scale energy storage systems.

Grid-scale energy storage batteries with electrode materials made from low-cost, earth-abundant elements are needed to meet the requirements of sustainable energy systems. Sodium-ion batteries (SIBs) with iron-based electrodes offer an attractive combination of low cost, plentiful structural diversity and high stability, making them ideal candidates for grid-scale energy storage systems. Although various iron-based cathode and anode materials have been synthesized and evaluated for sodium storage, further improvements are still required in terms of energy/power density and long cyclic stability for commercialization. In this Review, progress in iron-based electrode materials for SIBs, including oxides, polyanions, ferrocyanides, and sulfides, is briefly summarized. In addition, the reaction mechanisms, electrochemical performance enhancements, structure-composition-performance relationships, merits and drawbacks of iron-based electrode materials for SIBs are discussed. Such iron-based electrode materials will be competitive and attractive electrodes for next-generation energy storage devices., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The growth and proliferation of Li dendrites during repeated Li cycling has long been a crucial issue that hinders the development of secondary Li-metal batteries. Building a stable and robust solid state electrolyte interphase (SEI) on the Li-anode surface is regarded as a promising strategy to overcome the dendrite issues. In this work, we report a simple strategy to engineer the interface chemistry of Li-metal anodes by using tiny amounts of dimethyl sulfate (DMS, C 2 H 6 SO 4 ) as the SEI-forming additive. With the preferential reduction of DMS, an SEI layer composed of Li 2 S/Li 2 O forms on the Li surface. This inorganic SEI layer features high structural modulus and low interfacial resistant, enabling a dense and dendrite-free Li deposition as evidenced by scanning electron microscopy, atomic force microscopy, and in situ optical images. In addition, this SEI layer can prevent the deposited Li from direct contact with corrosive electrolytes, thus rendering an improved cycling stability of Li anodes with an average Coulombic efficiency of 97% for up to 150 cycles. When the DMS additive is introduced into a Li/NCM full cell, the cycle life of Li-metal batteries can be also improved significantly. This work demonstrates a feasible route to suppress Li dendrite growth by designing appropriate film-forming additives to regulate the interfacial properties of the SEI layer, and also the sulfonyl-based derivatives revealed in this work represent a large variety of new film-forming molecules, providing a broad selectivity for constructing high efficiency and cycle-stable Li anodes to address the intrinsic problems of rechargeable Li-metal batteries.

Development of intrinsically safe and long lifespan sodium-ion batteries (SIBs) is urgently needed for large-scale energy storage applications. However, most of the currently developed SIBs suffer from insufficient cycle life and potential unsafety. Herein, we construct an all-phosphate sodium-ion battery (AP-SIB) using a Na 3 V 2 (PO 4 ) 3 cathode, NaTi 2 (PO 4 ) 3 anode, and nonflammable trimethyl phosphate (TMP) electrolyte. The AP-SIB exhibits not only high safety, high rate performance, and ultralong cycle life but also zero-strain characteristics due to the inverse volume change of the phosphate cathode and anode during charge and discharge cycles, offering a safer and cycle-stable Na-ion technology for electric storage applications.

The separator is a critical component of lithium-ion batteries (LIBs), which not only allows ionic transport while it prevents electrical contact between electrodes but also plays a key role for thermal safety performance of LIBs. However, commercial separators for LIBs are typically microporous polyolefin membranes that pose challenges for battery safety, due to shrinking and melting at elevated temperature. Here, we demonstrate a strategy to improve the thermal stability and electrolyte affinity of polyethylene (PE) separators. By simply grafting the vinylsilane coupling reagent on the surface of the PE separator by electron beam irradiation method and subsequent hydrolysis reaction into the Al 3+ solution, an ultrathin Al 2 O 3 layer is grafted on the surface of the porous polymer microframework without sacrificing the porous structure and increasing the thickness. The as-synthesized Al 2 O 3 ceramic-grafted separator (Al 2 O 3 -CGS) shows almost no shrinkage at 150 °C and decreases the contact angle of the conventional electrolyte compared with the bare PE separator. Notably, the full cells with the Al 2 O 3 -CGSs exhibit better cycling performance and rate capability and also provide stable open circuit voltage even at 170 °C, indicating its promising application in LIBs with high safety and energy density.

LiV 3 O 8 nanorods with controlled size are successfully synthesized using a nonionic triblock surfactant Pluronic-F127 as the structure directing agent. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy techniques are used to characterize the samples. It is observed that the nanorods with a length of 4-8 µm and diameter of 0.5-1.0 µm distribute uniformly. The resultant LiV 3 O 8 nanorods show much better performance as cathode materials in lithium-ion batteries than normal LiV 3 O 8 nanoparticles, which is associated with the their unique micro-nano-like structure that can not only facilitate fast lithium ion transport, but also withstand erosion from electrolytes. The high discharge capacity (292.0 mAh g -1 at 100 mA g -1 ), high rate capability (138.4 mAh g -1 at 6.4 A g -1 ), and long lifespan (capacity retention of 80.5% after 500 cycles) suggest the potential use of LiV 3 O 8 nanorods as alternative cathode materials for high-power and long-life lithium ion batteries. In particular, the synthetic strategy may open new routes toward the facile fabrication of nanostructured vanadium-based compounds for energy storage applications., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Great progress has been made on the cyclability and material utilization in recent development of lithium-sulfur (Li-S) batteries; however, most of the sulfur electrodes reported so far have a considerable low loading of sulfur (60%), which causes a substantial decrease in energy density and is therefore difficult for application in batteries. To deal with this issue, we fabricate a novel sulfur composite with a coaxial three-layered structure, in which sulfur is deposited on carbon fibers and coated with poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS), thus enabling a high sulfur loading of 70.8 wt % without the expense of its electrochemical performance. Benefiting from the rigid conductive framework of carbon fibers and flexible buffering matrix of the polymer for blocking the diffusion loss of discharge intermediates, the as-fabricated composite electrode exhibits a high initial reversible capacity of 1272 mA h g -1 (based on the total mass of the composite), a stable cyclability with a retained capacity of 807 mA h g -1 after 200 cycles, and a high Coulombic efficiency of ∼99% upon extended cycling, offering a new selection for practical application in Li-S batteries.

High voltage, high rate, and cycling-stable cathodes are urgently needed for development of commercially viable sodium ion batteries (SIBs). Herein, we report a facile spray-drying method to synthesize graphene-scaffolded Na 3 V 2 (PO 4 ) 3 microspheres (NVP@rGO), in which nanocrystalline Na 3 V 2 (PO 4 ) 3 is embedded in graphene sheets to form porous microspheres. Benefiting from the highly conductive graphene framework and porous structure, the NVP@rGO material exhibits a high reversible capacity (115 mAh g -1 at 0.2 C), long-term cycle life (81% of capacity retention up to 3000 cycles at 5 C), and excellent rate performance (44 mAh g -1 at 50 C). The electrochemical properties of a full Na-ion cell with the NVP@rGO cathode and Sb/C anode are also investigated. The present results suggest promising applications of the NVP@rGO material as a high performance cathode for sodium ion batteries.

Sodium ion batteries (SIBs) have been considered as a promising alternative for the next generation of electric storage systems due to their similar electrochemistry to Li-ion batteries and the low cost of sodium resources. Exploring appropriate electrode materials with decent electrochemical performance is the key issue for development of sodium ion batteries. Due to the high structural stability, facile reaction mechanism and rich structural diversity, phosphate framework materials have attracted increasing attention as promising electrode materials for sodium ion batteries. Herein, we review the latest advances and progresses in the exploration of phosphate framework materials especially related to single-phosphates, pyrophosphates and mixed-phosphates. We provide the detailed and comprehensive understanding of structure-composition-performance relationship of materials and try to show the advantages and disadvantages of the materials for use in SIBs. In addition, some new perspectives about phosphate framework materials for SIBs are also discussed. Phosphate framework materials will be a competitive and attractive choice for use as electrodes in the next-generation of energy storage devices.

Yolk-shell TiO 2 @C nanocomposites have been synthesized successfully through a simple self-catalyzing solvothermal method. The structural and morphological characterizations reveal that TiO 2 @C nanocomposite has a yolk-shell microsphere morphology with diameters of 1-2 μm, and both yolk and shell are composed of TiO 2 nanoparticles (∼10 nm). The as-prepared yolk-shell TiO 2 @C composites exhibit superior sodium storage properties, with a specific capacity of 210 mAh g -1 , an outstanding cycle life of 85% capacity retention of 2000 cycles and extraordinary rate performance at 40 C rate. All the results indicate that the yolk-shell TiO 2 @C nanocomposite can be suggested as a promising anode material for high-performance sodium-ion batteries.

Silicon (Si) has been regarded as a promising high-capacity anode material for developing advanced lithium-ion batteries (LIBs), but the practical application of Si anodes is still unsuccessful mainly due to the insufficient cyclability. To deal with this issue, we propose a new route to construct a dual core-shell structured Si@SiO x @C nanocomposite by direct pyrolysis of poly(methyl methacrylate) (PMMA) polymer on the surface of Si nanoparticles. Since the PMMA polymers can be chemically bonded on the nano-Si surface through the interaction between ester group and Si surface group, and thermally decomposed in the subsequent pyrolysis process with their alkyl chains converted to carbon and the residue oxygen recombining with Si to form SiO x , the dual core-shell structure can be conveniently formed in a one-step procedure. Benefiting from the strong buffering effect of the SiO x interlayer and the efficient blocking action of dense outer carbon layer in preventing electrolyte permeation, the obtained nanocomposite demonstrates a high capacity of 1972 mA h g -1 , a stable cycling performance with a capacity retention of >1030 mA h g -1 over 500 cycles, and particularly a superiorly high Coulombic efficiency of >99.5% upon extended cycling, exhibiting a great promise for practical uses. More importantly, the synthetic method proposed in this work is facile and low cost, making it more suitable for large-scale production of high capacity anode for advanced LIBs.

Low cost and high performance Li-ion batteries have been extensively pursued for grid-scale energy storage applications; however, their development has been impeded for a long time due to the lack of qualified cathode materials with not only decent electrochemical performance but also resource abundance and low price. In this paper, we report Prussian-blue type FeFe(CN)6 nanocrystals with well-controlled lattice defects and perfect nanocubic morphology, which can exhibit a high Li-storage capacity of 160 mAh g(-1), a strong rate performance at 24 C, and a superior cycle stability with 90% capacity retention over 300 cycles. This low defect lattice and its excellent Li-insertion performance might provide a new insight into the design of advanced Li-ion battery materials and also a competitive alternative to the presently developed Li(+) insertion cathodes to develop low cost and high performance Li-ion batteries for grid-scale energy storage applications.

The effect of the cutoff voltages on the working voltage decay and cyclability of the lithium-rich manganese-based layered cathode (LRMO) was investigated by electrochemical measurements, electrochemical impedance spectroscopy, ex situ X-ray diffraction, transmission electron microscopy, and energy dispersive spectroscopy line scan technologies. It was found that both lower (2.0 V) and upper (4.8 V) cutoff voltages cause severe voltage decay with cycling due to formation of the spinel phase and migration of the transition metals inside the particles. Appropriate cutoff voltage between 2.8 and 4.4 V can effectively inhibit structural variation as the electrode demonstrates 92% capacity retention and indiscernible working voltage decay over 430 cycles. The results also show that phase transformation not only on high charge voltage but also on low discharge voltage should be addressed to obtain highly stable LRMO materials.

Nanosized TiO2 is now actively developed as a low-cost and potentially high capacity anode material of Na-ion batteries, but its poor capacity utilization and insufficient cyclability remains an obstacle for battery applications. To overcome these drawbacks, we synthesized electrospun TiO2/C nanofibers, where anatase TiO2 nanocrystals with a diameter of ∼12 nm were densely embedded in the conductive carbon fibers, thus preventing them from aggregating and attacking by electrolyte. Due to its abundant active surfaces of well-dispersed TiO2 nanocrytals and high electronic conductivity of the carbon matrix, the TiO2/C anode shows a high redox capacity of ∼302.4 mA h g(-1) and a high-rate capability of 164.9 mAh g(-1) at a very high current of 2000 mA g(-1). More significantly, this TiO2/C anode can be cycled with nearly 100% capacity retention over 1000 cycles, showing a sufficiently long cycle life for battery applications. The nanofibrous architecture of the TiO2/C composite and its superior electrochemical performance may provide new insights for development of better host materials for practical Na-ion batteries.

Sodium-ion batteries are now considered as a low-cost alternative to lithium-ion technologies for large-scale energy storage applications; however, their safety is still a matter of great concern for practical applications. In this paper, a safer sodium-ion battery is proposed by introducing a nonflammable phosphate electrolyte (trimethyl phosphate, TMP) coupled with NaNi 0.35 Mn 0.35 Fe 0.3 O 2 cathode and Sb-based alloy anode. The physical and electrochemical compatibilities of the TMP electrolyte are investigated by igniting, ionic conductivity, cyclic voltammetry, and charge-discharge measurements. The results exhibit that the TMP electrolyte with FEC additive is completely nonflammable and has wide electrochemical window (0-4.5 V vs. Na/Na + ), in which both the Sb-based anode and NaNi 0.35 Mn 0.35 Fe 0.3 O 2 cathode show high reversible capacity and cycling stability, similarly as in carbonate electrolyte. Based on these results, a nonflammable sodium-ion battery is constructed by use of Sb anode, NaNi 0.35 Mn 0.35 Fe 0.3 O 2 cathode, and TMP + 10 vol% FEC electrolyte, which works very well with considerable capacity and cyclability, demonstrating a promising prospect to build safer sodium-ion batteries for large-scale energy storage applications.

Conversion reaction electrode materials (CREMs) have gained significant interest in lithium-ion batteries (LIBs) owing to their high theoretical gravimetric capacity. However, traditional CREMs-based electrodes, with large strain arising from Li(+) intercalation/deintercalation causes pulverization or electrical breakdown and cracking of the active materials which leads to structural collapse, limiting performance. Therefore, in order to construct electrodes with a strong tolerance to the strain incurred during the conversion reaction process, we design a coral-like three-dimensional (3D) hierarchical heterostructure by using cross-linked nanoflakes interspersed with nanoparticles (NPs) standing vertically on graphene foam (GF). The coral-like 3D hierarchical heterostructures can efficiently disperse the strain from both internal and external forces as well as increase the specific surface area for enhanced electrochemical reactions. These features lead to long-cycle stability and excellent flexibility in LIBs. Fe3O4 NPs and CoO NFs are utilized as a model system to demonstrate our strategy. The as-prepared coral-like hierarchical electrode is studied as an anode in LIBs for the first time and is shown to deliver a high reversible specific gravimetric capacity of ∼1200 mA h g(-1) at a rate of 0.5 A g(-1) for 400 cycles. In addition, our batteries can even power a green light-emitting diode when bent to high degrees confirming the excellent flexibility of the material.

Prussian blue and its analogues have received particular attention as superior cathodes for Na-ion batteries due to their potential 2-Na storage capacity (∼170 mAh g(-1)) and low cost. However, most of the Prussian blue compounds obtained from the conventional synthetic routes contain large amounts of Fe(CN)6 vacancies and coordinated water molecules, which leads to the collapse of cyano-bridged framework and serious deterioration of their Na-storage ability. Herein, we propose a facile citrate-assisted controlled crystallization method to obtain low-defect Prussian blue lattice with greatly improved Na-storage capacity and cycling stability. As an example, the as-prepared Na2CoFe(CN)6 nanocrystals demonstrate a reversible 2-Na storage reaction with a high specific capacity of 150 mAh g(-1) and a ∼ 90% capacity retention over 200 cycles, possibly serving as a low cost and high performance cathode for Na-ion batteries. In particular, the synthetic strategy described in this work may be extended to other coordination-framework materials for a wide range of energy conversion and storage applications.

Graphene-wrapped organic nanoflowers are synthesized from ultrasonic treatment of a simple microsized disodium salt (Na212H6O4) and graphene, which demonstrates a greatly enhanced electrochemical capacity, rate capability and cycling stability as organic Na(+) storage anode. This work suggests an effective architecture to make organic materials electrochemically energetic and stable for energy storage applications., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Antimony/carbon (Sb@C) microspheres are initially synthesized via a facile self-catalyzing solvothermal method, and their applicability as anode materials for sodium-ion batteries is investigated. The structural and morphological characterizations reveal that Sb@C microspheres are composed of Sb nanoparticles (∼20 nm) homogeneously encapsulated in the C matrix. The self-catalyzing solvothermal mechanism is verified through comparative experiments by using different raw materials. The as-prepared Sb@C microspheres exhibit superior sodium storage properties, demonstrating a reversible capacity of 640 mAh g(-1), excellent rate performance, and an extended cycling stability of 92.3% capacity retention over 300 cycles, making them promising anode materials for sodium-ion batteries.

The safety concern is a critical obstacle to large-scale energy storage applications of lithium-ion batteries. A thermostable separator is one of the most effective means to construct the safe lithium-ion batteries. Herein, we demonstrate a novel ceramic (SiO2)-grafted PE separator prepared by electron beam irradiation. The separator shows similar thickness and pore structure to the bare separator, while displaying strong dimensional thermostability, as the shrinkage ratio is only 20% even at an elevated temperature of 180 °C. Besides, the separator is highly electrochemically inert, showing no adverse effect on the energy and power output of the batteries. Considering the excellent electrochemical and thermal stability, the SiO2-grafted PE separator developed in this work is greatly beneficial for constructing safer lithium-ion batteries.

Hierarchical carbon framework wrapped Na3 V2 (PO4 )3 (HCF-NVP) is successfully synthesized through chemical vapor deposition on pure Na3 V2 (PO4 )3 particles. Electrochemical experiments show that the HCF-NVP electrode can deliver a large reversible capacity (115 mA h g(-1) at 0.2 C), superior high-rate rate capability (38 mA h g(-1) at 500 C), and ultra-long cycling stability (54% capacity retention after 20 000 cycles)., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Olivine NaFePO4/C microsphere cathode is prepared by a facile aqueous electrochemical displacement method from LiFePO4/C precursor. The NaFePO4/C cathode shows a high discharge capacity of 111 mAh g(-1), excellent cycling stability with 90% capacity retention over 240 cycles at 0.1 C, and high rate capacity (46 mAh g(-1) at 2 C). The excellent electrochemical performance demonstrates that the aqueous electrochemical displacement method is an effective and promising way to prepare NaFePO4/C material for Na-based energy storage applications. Moreover, the Na2/3FePO4 intermediate is observed for the first time during the Na intercalation process through conventional electrochemical techniques, corroborating an identical two-step phase transition reaction both upon Na intercalation and deintercalation processes. The clarification of the electrochemical reaction mechanism of olivine NaFePO4 could inspire more attention on the investigation of this material for Na ion batteries.

Magnetite (Fe3O4) is an attractive electrode material due to its high theoretical capacity, eco-friendliness, and natural abundance. However, its commercial application in lithium-ion batteries is still hindered by its poor cycling stability and low rate capacity resulting from large volume expansion and low conductivity. We present a new approach which makes use of supercritical carbon dioxide to efficiently anchor Fe3O4 nanoparticles (NPs) on graphene foam (GF), which was obtained by chemical vapor deposition in a single step. Without the use of any surfactants, we obtain moderately spaced Fe3O4 NPs arrays on the surface of GF. The particle size of the Fe3O4 NPs exhibits a narrow distribution (11 ± 4 nm in diameter). As a result, the composites deliver a high capacity of about 1200 mAh g(-1) up to 500 cycles at 1 C (924 mAh g(-1)) and about 300 mAh g(-1) at 20 C, which reaches a record high using Fe3O4 as anode material for lithium-ion batteries.

A photoassisted oxygen reduction reaction (ORR) through I(-)/I3(-) redox couple was investigated for proton exchange membrane (PEM) fuel cell cathode reaction. The I(-)/I3(-)-based liquid cathode was used to replace conventional oxygen cathode, and its discharge product I(-) was regenerated to I3(-) by photocatalytic oxidation with the participation of oxygen. This new and innovative approach may provide a strategy to eliminate the usage of challenging ORR electrocatalysts, resulting in an avenue for developing low-cost and high-efficiency PEM fuel cells.

A honeycomb layered Na3Ni2SbO6 is synthesized as a cathode for sodium-ion batteries. This new host material exhibits a high capacity of 117 mA h g(-1), a remarkable cyclability with 70% capacity retention over 500 cycles at a 2C rate, and a superior rate capability with >75% capacity delivered even at a very high rate of 30 C (6000 mA g(-1)). These results open a new perspective to develop high-capacity and high-rate Na-ion batteries for widespread electric-energy-storage applications., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

FePO4 nanospheres are synthesized successfully through a simple chemically induced precipitation method. The nanospheres present a mesoporous amorphous structure. Electrochemical experiments show that the FePO4/C electrode demonstrates a high initial discharging capacity of 151 mAh g(-1) at 20 mA g(-1), stable cyclablilty (94% capacity retention ratio over 160 cycles), as well as high rate capability (44 mAh g(-1) at 1000 mA g(-1)) for Na-ion storage. The superior electrochemical performance of the FePO4/C nanocomposite is due to its particular mesoporous amorphous structure and close contact with the carbon framework, which significantly improve the ionic and electronic transport and intercalation kinetics of Na ions.

Si has been considered as a promising alternative anode for next-generation lithium ion batteries (LIBs), but the commercial application of Si anodes is still limited due to their poor cyclability. In this paper, we propose a new strategy to enhance the long-term cyclability of Si anode by embedding nano-Si particles into a Li(+)-conductive polymer to form a Si/polymer composite with core-shell structure, in which nano-Si cores act as active Li-storage phase and the polymeric matrix serves not only as a strong buffer to accommodate the volume change, but also as a protection barrier to prevent the direct contact of Si surface with electrolyte, so as to maintain the mechanical integrity of Si anode and suppress the repeated destruction and construction of solid electrolyte interphase (SEI) on the Si surface. To realize this strategy, we synthesize a Si/PPP (polyparaphenylene) composite simply by ball-milling the Si nanoparticles with PPP polymer that has n-doping activity. Our experimental results demonstrate that the thus-prepared Si/PPP composite exhibits a high capacity of 3184 mA h g(-1) with an initial coulombic efficiency of 78%, an excellent rate capability with a considerably high capacity of 1670 mA h g(-1) even at a very high rate of 16 A g(-1), and a long-term cyclability with 60% capacity retention over 400 cycles, showing a great prospect for battery application. In addition, this structural design could be adopted to other Li-storable metals or alloys for developing cycle-stable anode materials for Li-ion batteries.

Room-temperature Na-ion batteries have attracted great interest as a low cost and environmentally benign technology for large scale electric energy storage, however their development is hindered by the lack of suitable anodic host materials. In this paper, we described a green approach for the synthesis of Sn4P3/C nanocomposite and demonstrated its excellent Na-storage performance as a novel anode of Na-ion batteries. This Sn4P3/C anode can deliver a very high reversible capacity of 850 mA h g(-1) with a remarkable rate capability with 50% capacity output at 500 mA g(-1) and can also be cycled with 86% capacity retention over 150 cycles due to a synergistic Na-storage mechanism in the Sn4P3 anode, where the Sn nanoparticles act as electronic channels to enable electrochemical activation of the P component, while the elemental P and its sodiated product Na3P serve as a host matrix to alleviate the aggregation of the Sn particles during Na insertion reaction. This mechanism may offer a new approach to create high capacity and cycle-stable alloy anodes for Na-ion batteries and other electrochemical energy storage applications.

A Na-host cathode is developed by grafting the polypyrrole chains with ionizable sodium sulfonate. Due to the immobile p-doping of organic anions, the self-doped polymer can act as a Na-host for reversible Na insertion-extraction reaction, thus offering a low cost and renewable organic cathode for Na ion battery applications.

Turning on your P/C: An amorphous phosphorus/carbon (a-P/C) composite was synthesized using simple mechanical ball milling of red phosphorus and conductive carbon powders. This material gave an extraordinarily high sodium ion storage capacity of 1764 mA h g(-1) (see graph) with a very high rate capability, showing great promise as a high capacity and high rate anode material for sodium ion batteries., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Current battery systems have severe cost and resource restrictions, difficultly to meet the large scale electric storage applications. Herein, we report an all-organic Na-ion battery using p-dopable polytriphenylamine as cathode and n-type redox-active poly(anthraquinonyl sulphide) as anode, excluding the use of transition-metals as in conventional electrochemical batteries. Such a Na-ion battery can work well with a voltage output of 1.8 V and realize a considerable specific energy of 92 Wh kg(-1). Due to the structural flexibility and stability of the redox-active polymers, this battery has a superior rate capability with 60% capacity released at a very high rate of 16 C (3200 mA g(-1)) and also exhibit an excellent cycling stability with 85% capacity retention after 500 cycles at 8 C rate. Most significantly, this type of all-organic batteries could be made from renewable and earth-abundant materials, thus offering a new possibility for widespread energy storage applications.

An amorphous phosphorus/carbon nanocomposite demonstrates a reversible 3-Li storage capacity of 2355 mAh g(-1) with an excellent capacity retention of 90% over 100 cycles and a superior power capability with 62% of its capacity realizable at a very high rate of 8000 mA g(-1), possibly serving as a high capacity and high rate alternative anode for next-generation Li-ion batteries.

Si-based alloy materials have received great attention as an alternative anode for high capacity and safe Li-ion batteries, but practical implementation of these materials is hindered by their poor electrochemical utilization and cyclability. To tackle this problem, we developed a core-shelled FeSi2/Si@C nanocomposite by a direct ball-milling of Fe and Si powders. Such a nanostructured composite can effectively buffer the volumetric change by alloying active Si phase with inactive FeSi2 matrix in its inner cores and prevent the aggregation of the active Si particles by outer graphite shells, so as to improve the cycling stability of the composite material. As a result, the FeSi2/Si@C composite exhibits a high Li-storage capacity of ∼1010 mA g(-1) and an excellent cyclability with 94% capacity retention after 200 cycles, showing a great promise for battery applications. More significantly, the synthetic method developed in this work possesses several advantages of low cost, zero emission, and operational simplicity, possibly to be extended for making other Li-storage alloys for large-scale applications in Li-ion batteries.

A Sb/C nanocomposite was synthesized and found to deliver a reversible 3 Na storage capacity of 610 mA h g(-1), a strong rate capability at a very high current of 2000 mA g(-1) and a long-term cycling stability with 94% capacity retention over 100 cycles, offering practical feasibility as a high capacity and cycling-stable anode for room temperature Na-ion batteries.

The calf thymus DNA (ctDNA) damage induced by water-soluble CdSe quantum dots (QDs) was investigated using nucleic acid molecular "light switches" as probe. It was found that little ctDNA was damaged by CdSe QDs without UV irradiation. However, under UV irradiation, ctDNA was nicked by CdSe QDs very clearly. The mechanism of ctDNA damage was also discussed. The results strongly suggested that the ctDNA damage caused by CdSe QDs was not due to photo-induced liberation of Cd(2+), but due to the production of free radicals and reactive oxygen species.

A competitive immunoassay for clenbuterol (CLB) based on capillary electrophoresis with chemiluminescence (CL) detection was established. The method was based on the competitive reaction of horseradish peroxidase (HRP)-labeled CLB (CLB-HRP) and free CLB with anti-CLB antiserum. The factors affecting the electrophoresis and CL detection were systematically investigated with HRP as a model sample. Under the optimal conditions, the tracer CLB-HRP and the immunoassay complex were separated, and the linear range and the detection limit (S/N=3) for CLB were 5.0-40nmoll(-1) and 1.2nmoll(-1), respectively. The proposed method has been applied satisfactorily in the analysis of urine sample.

A mediatorless microbial fuel cell based on the direct biocatalysis of Escherichia coli shows significantly enhanced performance by using bacteria electrochemically-evolved in fuel cell environments through a natural selection process and a carbon/PTFE composite anode with an optimized PTFE content.

Based on the quenching of the fluorescence of CdSe quantum dots (QDs) by spironolactone, a simple, rapid and specific method for spironolactone determination was proposed. In the optimum conditions, spironolactone concentration versus quantum dot fluorescence gave a linear response with an excellent 0.997 correlation coefficient, between 2.5 and 700 mg/mL (6.0-1680 micromol/L) and the limit of detection (S/N=3) was 0.2 microg/mL (0.48 micromol/L). The contents of spironolactone in pharmaceutical tablets were determined by the proposed method and the results agreed with the claimed values. The possible mechanism for the reaction was also discussed.

The electrooxidation behavior of BH4(-) on electrocatalytic Pt, hydrolytically active Ni, and noncatalytic Au electrodes were comparatively reexamined and a more generalized reaction mechanism was proposed to explain the very different anodic properties of BH4(-) on the different metal electrodes. In this mechanism, the anodic reaction behavior of BH4(-) are determined by a pair of conjugated reactions: electrochemical oxidation and chemical hydrolysis of BH4(-), the relative rates of which depend on the anodic materials, applied potentials, and chemical states of the anodic surfaces. At Pt surface, the electron number of BH4(-) oxidation increases with the increased potential polarization, while the actual electron number of BH4(-) oxidation on Ni electrode is 4 at most due to the poor electrocatalytic activity of the oxidized Ni surface and the strong catalytic activity of metallic Ni for chemical recombination of the adsorbed H intermediate. On the hydrolytic-inactive Au surface, the anodic reaction of BH4(-) can proceed predominately through direct electrochemical oxidation, delivering a near 8e discharge capacity.

A nanocrystalline Li[Li(0.12)Ni(0.32)Mn(0.56)]O(2) powder was synthesized via the pyrolysis of polyacrylate salt precursors prepared by in situ polymerization of the metal salts and acrylate acid. The pyrolysis mechanism of the polymeric precursor is discussed by use of thermal analysis. Layered crystalline structure of the resulting compound was characterized by powder X-ray diffraction and high-resolution transmission electron (TEM) micrographs. The results revealed that the Li[Li(0.12)Ni(0.32)Mn(0.56)]O(2) as prepared has nanosized morphology and good crystallinity even if calcined at 900 degrees C, and the electrodes made from these nanoparticles exhibited high-rate characteristics and can deliver stable discharge capacity (163 mA.h/g) with excellent capacity retention at appropriate charge-discharge voltage interval. Since this preparation method is simple and particularly suitable for preparation of mixed metal oxides, it can be used for industrial production of highly homogeneous metal oxide cathode materials of the lithium-ion batteries.

In our experiment, it was observed that isoniazid could enhance the chemiluminescence (CL) emission of tris-(1,10-phenanthroline)ruthenium(II) (Ru(phen)3(2+))-cerium(IV) (Ce(IV)) system and this enhancement effect was dependent on the concentration of isoniazid, based on which, a novel CL system was established for the detection of isoniazid. Under the optimum experimental conditions, the dynamic range and detection limit are 7.0 x 10(-2) to 6.5 microg ml(-1) and 2.5 x 10(-2) microg ml(-1), respectively. The R.S.D. is 3.4% (n = 11). The proposed method has been applied to detect the content of isoniazid in the injection solution with satisfactory results. The possible mechanism of the CL reaction was studied.

In our experiments, it was observed that adding bromide to Pb2+ solution of N,N'-dimethylformamide (DMF), the highly emissive cluster Pb4Br11(3-) can be formed and the fluorescence intensity of the formed cluster is proportional to the concentration of Pb2+, based on which, a novel, simple approach that uses the emission from itself as the sensor for determination of Pb2+ is proposed. Under the optimum conditions, the linear range and detection limit is 1.0 x 10(-7) to 1.0 x 10(-5) mol l(-1) (correlation coefficient r = 0.9997) and 7.6 x 10(-9) mol l(-1), respectively. Foreign substrates effects were also investigated. The proposed method has been successfully applied to the determination of lead in the synthetic samples. The mechanism of the reaction is also studied.

Base on the enhancement of Rayleigh light scattering signals of molecular "light switches" by DNA under acidic condition, a sensitive and convenient method for DNA determination was proposed. The experiments indicated that, under optimum conditions, good linear relationships were obtained between the Rayleigh light scattering intensity and the concentration of nucleic acids. The detect limits of calf thymus DNA (ctDNA) were 13.0 ng ml(-1), 4.2 ng ml(-1), 51.5 ng ml(-1) and 3.0 ng ml(-1) with four "light switches", respectively. Plasmid DNA extracted from Bacillus subtilis were determined by the proposed method with satisfactory results, and the recovery rates of calf thymus DNA were in the range of 94.6-110.7%.

A chemiluminescence (CL) method for the determination of barbituric acid (BA) was proposed, which is based on the enhancement of BA to the CL intensity of Tris-(1,10-phenanthroline)ruthenium(II) (Ru(phen)(3)(2+))-cerium(IV) (Ce(IV)) system. The concentration of BA is proportional to the CL intensity in the range of 5.0 x 10(-3)-2.0 microg ml(-1). The detection limit is 6.9 x 10(-4) microg ml(-1). The relative standard deviation (R.S.D.) of determining 11 samples containing 0.20 microg ml(-1) BA is 3.2%. This CL method has been successfully applied to the determination of BA in the synthetic samples. The mechanism of CL reaction was studied.