Synthesis and electrochemical properties of graphene-SnS2 nanocomposites for lithium-ion batteries

Graphene-SnS₂ nanocomposites were prepared via a solvothermal method with different loading of SnS₂. The nanostructure and morphology of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The XRD patterns revealed that hexagonal SnS₂ was obtained. SEM and TEM results indicated that SnS₂ particles distributed homogeneously on graphene sheets. The electrochemical properties of the samples as active anode materials for lithium-ion batteries were examined by constant current charge–discharge cycling. The composite with weight ratio between graphene and SnS₂ of 1:4 had the highest rate capability among all the samples and its reversible capacity after 50 cycles was 351 mAh/g, which was much higher than that of the pure SnS₂ (23 mAh/g). With graphene as conductive matrix, homogeneous distribution of SnS₂ nanoparticles can be ensured and volume changes of the nanoparticles during the charge and discharge processes can be accomodated effectively, which results in good electrochemical performance of the composites.     

SnS2 Nanoplatelet@Graphene Nanocomposites as High‐Capacity Anode Materials for Sodium‐Ion Batteries

Na‐ion batteries have been attracting intensive investigations as a possible alternative to Li‐ion batteries. Herein, we report the synthesis of SnS₂ nanoplatelet@graphene nanocomposites by using a morphology‐controlled hydrothermal method. The as‐prepared SnS₂/graphene nanocomposites present a unique two‐dimensional platelet‐on‐sheet nanoarchitecture, which has been identified by scanning and transmission electron microscopy. When applied as the anode material for Na‐ion batteries, the SnS₂/graphene nanosheets achieved a high reversible specific sodium‐ion storage capacity of 725 mA h g^?1, stable cyclability, and an enhanced high‐rate capability. The improved electrochemical performance for reversible sodium‐ion storage could be ascribed to the synergistic effects of the SnS₂ nanoplatelet/graphene nanosheets as an integrated hybrid nanoarchitecture, in which the graphene nanosheets provide electronic conductivity and cushion for the active SnS₂ nanoplatelets during Na‐ion insertion and extraction processes.     

Electrodeposition of high-pressure-stable bcc phase bismuth flowerlike micro/nanocomposite architectures at room temperature without surfactant

Three-dimensional (3D) bismuth flowerlike micro/nanocomposite architectures were successfully prepared on Cu substrates by electrochemical self-assembly in aqueous solution at room temperature. The morphology, crystal structure, and composition were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDS). Results show that the synthesized 3D architectures are built with dozens of two-dimensional (2D) single crystal nanoscaled petals, which are high-pressure-stable bcc phase Bi. The thickness of the 2D petals is about 60 nm. The effects of the concentration of Bi³⁺ ions and the electric potential gradient on the evolution of the Bi flowerlike micro/nanocomposite architectures are discussed.     

Facile synthesis of CoWO<Subscript>4</Subscript>/RGO composites as superior anode materials for lithium-ion batteries

In this paper, a facile method has been developed to synthesize supported CoWO₄ on the reduced graphene oxide (RGO) as high-performance anode material for Li-ion batteries. The composites with cuboid-like CoWO₄ nanoparticles were prepared by directly adding graphene oxide into the precursor solution followed by a hydrothermal treatment. Different analytical methods like high-resolution TEM, XRD, TGA, and XPS characterizations were employed to illustrate structural information of the as-prepared CoWO₄ and CoWO₄/RGO composites. In addition, the Li-ion battery performance using the composites as anode materials was also discussed based on the detailed galvanostatic charge-discharge cycling tests. The result shows that the specific capacity of the as-prepared CoWO₄/RGO composites can reach 533.3 mAh g^?1 after 50 cycles at a current density of 100 mA g^?1. During the whole cyclic process, the coulombic efficiency was maintained higher than 90%. Therefore, CoWO₄, as an environment-friendly and cost-effective anode material, has promising potential for Li-ion batteries.     

Large-scale synthesis of single-crystal hexagonal tungsten trioxide nanowires and electrochemical lithium intercalation into the nanocrystals

Single-crystal nanowires of hexagonal tungsten trioxide in a large scale have been successfully prepared by a simple hydrothermal method without any templates and catalysts. Uniform h-WO₃ nanowires with diameter of 25-50 nm and length of up to several micrometers are obtained. It is found that the morphology and crystal form of the final products are strongly dependent on the amount of the sulfate and pH value of the reaction system. The electrochemical performances of the as-prepared h-WO₃ nanowires as anodic materials of Li-ion batteries have also been investigated. It deliveres a discharge capacity of 218 mAh g⁻¹ for the first cycle. In addition, the cycle ability of the nanocrystals is superior to that of bulk materials, which implies the morphology and particle size have the influence on the electrochemical performances.     

Kirkendall-effect-based growth of dendrite-shaped CuO hollow micro/nanostructures for lithium-ion battery anodes

Three-dimensional (3D) dendrite-shaped CuO hollow micro/nanostructures have been prepared via a Kirkendall-effect-based approach for the first time and have been demonstrated as a high-performance anode material for lithium-ion batteries. The as-prepared hollow structures were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and electrochemical properties. A CuO hollow structure composed of nanocubes outside and a dense film inside was selected as a typical example of the optimized design; it exhibited significantly improved cyclability at a current rate of 0.5 C, with the average Coulombic efficiency of ∼97.0% and 57.9% retention of the discharge capacity of the second cycle after 50 cycles. The correlation between the structure features of the hollow CuO and their electrochemical behavior was discussed in detail. Smaller size of primary structure and larger internal space of electrode materials are crucial to better electrochemical performance. This work represents that Kirkendall effect is a promising method to fabricate excellent hollow electrode materials for Li-ion batteries.     

Three-Dimensional Carbon Framework Anchored Polyoxometalate as a High-Performance Anode for Lithium-Ion Batteries

Recently, it has become very important to develop cost-effective anode materials for the large-scale use of lithium-ion batteries (LIBs). Polyoxometalates (POMs) have been considered as one of the most promising alternatives for LIB electrodes owing to their reversible multi-electron-transfer capacity. Herein, Keggin-type [PMo₁₂O₄₀]³⁻ (donated as PMo₁₂) clusters are anchored onto a 3D microporous carbon framework derived from ZIF-8 through electrostatic interactions. The PMo₁₂ clusters can be immobilized steadily and uniformly on the carbon framework, which provides enhanced electrical conductivity and high stability. Compared with PMo₁₂ itself, the as-prepared novel 3D Carbon-PMo₁₂ composite displays a significantly improved Li-ion storage performance as an LIB anode, with excellent reversible specific capacity and rate capacity, as well as high cycling performance (discharge capacity of 985 mA h g⁻¹ after 200 cycles), which are superior to other POM-based anode materials reported so far. The high performance of the Carbon-PMo₁₂ composite can be attributed to the 3D conductive network with fast electron transport, high ratio of pseudocapacitive contribution, and evenly distributed PMo₁₂ clusters with reversible 24-electron transfer capacity. This work offers a facile way to explore novel LIB anodes consisting of electroactive molecule clusters.     

Hydrides compounds for electrochemical applications

Hydrides have been used since a long time for solid-state hydrogen storage and electrochemical nickel-metal hydride batteries. Besides these applications, growing attention has been devoted to their development as anode materials, as well as solid electrolytes for Li-ion and other ion batteries. Herein, we review and summarize the recent advances of hydrides as negative electrodes for Ni-MH and A-ion batteries (A = Li, Na), and as electrolyte for all solid-state batteries (ASSB). Metallic hydrides such as intergrowth compounds are highlighted as the best compromise up to now for Ni-MH. Regarding anodes of Li-ion batteries, MgH₂, especially its combination with TiH₂, provides very promising results. Complex hydrides such as Li-borohydride and related closo-borates and monovalent carborate boron clusters appear to be very attractive as solid electrolytes for Li-based ASSB, whereas closo-hydroborate sodium salts and closo-carboborates are investigated for Na- and Mg-ASSB. Finally, further research directions are foreseen for hydrides in electrochemical applications.     

Tin oxide-titanium oxide/graphene composited as anode materials for lithium-ion batteries

A tin oxide-titanium oxide/graphene (SnO₂-TiO₂/G) ternary nanocomposite as high-performance anode for Li-ion batteries was prepared via a simple reflux method. The graphite oxide (GO) was reduced to graphene nanosheet, and the SnO₂-TiO₂ nanocomposites were evenly distributed on the graphene matrix in the SnO₂-TiO₂/G nanocomposite. The as-prepared SnO₂-TiO₂/G nanocomposites were employed as anode materials for lithium-ion batteries, showing an outstanding performance with high reversible capacity and long cycle life. The composite delivered a superior initial discharge capacity of 1,594.6 mAh g^?1 and a reversible specific capacity of 1,500.3 mAh g^?1 at a current density of 100 mA g^?1. After 100 cycles, the reversible discharge capacity was still maintained at 1,177.4 mAh g^?1 at a current density of 100 mA g^?1 with a high retained rate of reversible capacity of 73.8 %. The addition of small amount of TiO₂ nanoparticles improved the cycling stability and specific capacity of SnO₂-TiO₂/G nanocomposite, obviously. The results demonstrate that the SnO₂-TiO₂/G nanocomposite is a promising alternative anode material for practical Li-ion batteries.     

Facile simultaneous polymerization enabled in-situ confinement of size-tailored GeO2 nanocrystals in continuous S-Doped carbons for lithium storage

GeO₂ is a promising anode material for lithium ion batteries due to its high theoretical capacity (1126 mAh g^?1 for reversibly storing 4.4 Li⁺), and moderately low operating voltage (<1.5 V). Nevertheless, the fabrication of truly durable GeO₂ anode with satisfactory rate capability and cycling stability remains a big challenge because of its inherent low conductivity, and the large volume expansion upon charge-discharge that causes severe capacity fading. In this study, an innovative nanostructure with size-adjustable GeO₂ nanoparticles (16–26 nm) embedded in continuous S-doped carbon (GeO₂/S-doped carbon, GSC) has been successfully fabricated via a facile in-situ simultaneous polymerization method followed by heat treatment. The electrochemical results indicate that the as-prepared GSC composites show high reversible capacity (672.9 mAh g^?1 at 50 mA g^?1), superior rate capability (332.9 mAh g^?1 at 1000 mA g^?1), and long-term cycle life (179 mAh g^?1 after 500 cycles at 1000 mA g^?1) as anode materials for lithium ion batteries. The excellent electrochemical performance of GSC nanocomposites could be ascribed to the homogeneous and continuous S-doped carbon matrix, which provides shortened ion diffusion pathway, increased electrical conductivity, enhanced structural stability, and introduced surface/interface property.     

SnS2–graphene nanocomposites as anodes of lithium-ion batteries

SnS₂–graphene nanocomposites are synthesized by a hydrothermal method, and their application as anodes of lithium-ion batteries has been investigated. SnS₂ nanosheets are uniformly coating on the surface of graphene. SnS₂–graphene nanocomposites exhibit high cyclability and capacity. The reversible capacity is 766 mAh/g at 0.2C rate and maintains at 570 mAh/g after 30 cycles. Such a high performance can be attributed to high electron and Li-ion conductivity, large surface area, good mechanical flexibility of graphene nanosheets and the synergetic effect between graphene and SnS₂ nanostructures. The present results indicate that SnS₂–graphene nanocomposites have potential applications in lithium-ion battery anodes.     

Nanostructured Sn/TiO2/C composite as a high-performance anode for Li-ion batteries

A nanostructured Sn/TiO₂/C composite was prepared from SnO, Ti, and carbon powders using a mechanochemical reduction method and evaluated as an anode material in rechargeable Li-ion batteries. The Sn/TiO₂/C nanocomposite was composed of uniformly dispersed nanocrystalline Sn and rutile TiO₂ in amorphous carbon matrix. In addition, electrochemical Li insertion/extraction in rutile TiO₂ was examined by ex situ XRD and extended X-ray absorption fine structure. The Sn/TiO₂/C nanocomposite exhibited excellent electrochemical performance, which highlights its potential as a new alternative anode material in Li-ion batteries.     

Hydrothermal Realization of a Hierarchical,Flowerlike MnWO4@MWCNTs Nanocomposite with Enhanced Reversible Li Storage as a New Anode Material

A phase‐pure MnWO₄‐based nanocomposite, MnWO₄@MWCNTs (MWCNTs=multiwalled carbon nanotubes), was successfully synthesized through a simple hydrothermal reaction at 180 °C by adjusting the pH of the precursor medium. The resulting nanocomposite maintains the original flowerlike morphology of MnWO₄ with hierarchical structures composed of numerous single‐crystalline nanorods that drive growth preferentially along the [001] direction. The growth mechanism for the flowerlike formations is also discussed. In addition, the Li electroactivity of pure MnWO₄ and MnWO₄@MWCNTs electrodes was investigated. As an anode for Li‐ion batteries, the MnWO₄@MWCNTs nanocomposite showed enhanced electrochemical performance in reversible Li storage relative to that shown by bare MnWO₄ electrodes, including a high capacity of 425 mAh g^?1 and superior rate performance. This performance can be attributed to the synergistic effect of the nanocomposite combined with the MWCNTs, which provide efficient electron transport in their role as a conductor.     

Electrochemical Behavior of Polypyrrole‐modified SnS2 for Use as Anode Material in Lithium‐Ion Batteries

SnS₂/polypyrrole (PPy) composites were successfully synthesized by PPy modification of SnS₂ via a simple and effective solvothermal and chemical method. The microstructure, morphology, electrical conductivity, PPy content, and electrochemical properties of these materials were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), four‐point probe technique, thermogavimetry (TG), and constant‐current charge/discharge tests, respectively. The results demonstrate that PPy is tightly coated on the 3D flower‐like SnS₂ and that the conductivity of SnS₂ /PPy composites can be greatly improved by the PPy modification. The electrochemical results indicate that PPy is not involved in the electrode reaction, but it can dramatically improve the reversible capacity and cyclic performance. The recharge capacity retention after 30 cycles remained at 523 mAh/g, which is significantly higher than that of SnS₂ without modification by PPy. The better cycling performance compared to SnS₂ nanoparticles should be due to the 3D nano‐flower‐like SnS₂ particles and the modification of SnS₂ by PPy.     

Low-temperature growth of vertically aligned In2O3 nanoblades with improved lithium storage properties

Vertically aligned Indium oxide (In₂O₃) nanoblades are successfully obtained through plasma enhanced chemical vapor deposition (PECVD) approach. By using plasma, the reaction between InCl₃ and O₂ was able to take place, yielding vertically aligned blade like nanostructure. The novel In₂O₃ nanostructures exhibit improved electrochemical properties when used as anode materials for lithium-ion batteries. The In₂O₃ electrode reveals reversible capacity of 580 mAh g^?1 after 100 cycles, much higher than that of the In₂O₃ thin films. The result suggests that proper structural modification of In₂O₃ thin film may contribute to the improvement of electrochemical properties. The In₂O₃ electrodes with large reversible capacity and stable cycling performance may provide new insight of anode materials applied in thin film lithium-ion batteries.     

Constructing oxygen-deficient V2O3@C nanospheres for high performance potassium ion batteries

Potassium ion batteries (PIBs) have been regarded as promising alternatives to lithium ion batteries (LIBs) on account of their abundant resource and low cost in large scale energy storage applications. However, it still remains great challenges to explore suitable electrode materials that can reversibly accommodate large size of potassium ions. Here, we construct oxygen-deficient V₂O₃ nanoparticles encapsulated in amorphous carbon shell (O_d-V₂O₃@C) as anode materials for PIBs by subtly combining the strategies of morphology and deficiency engineering. The MOF derived nanostructure along with uniform carbon coating layer can not only enables fast K⁺ migration and charge transfer kinetics, but also accommodate volume change and maintain structural stability. Besides, the introduction of oxygen deficiency intrinsically tunes the electronic structure of materials according to DFT calculation, and thus lead to improved electrochemical performance. When utilized as anode for PIBs, O_d-V₂O₃@C electrode exhibits superior rate capability (reversible capacities of 262.8, 227.8, 201.5, 179.8, 156.9 mAh/g at 100, 200, 500, 1000 and 2000 mA/g, respectively), and ultralong cycle life (127.4 mAh/g after 1000 cycles at 2 A/g). This study demonstrates a feasible way to realize high performance PIBs through morphology and deficiency engineering.     

锂离子电池锡薄膜负极制备及电化学性能研究

应用真空蒸发法在泡沫铜基底上制备锡薄膜负极.XRD、SEM分析表征薄膜的物相结构及其微观形貌,并测试了材料的电化学性能.结果表明,泡沫铜基底的三维结构增强了活性物质与基底的结合力.在同一基底温度下,锡颗粒随蒸发时间延长逐渐增大,电池电化学性能降低;而在同一时间内,升高基底温度,颗粒无明显变化,电池循环寿命有了很大提高.样品A″电池(基底温度:200℃,蒸发时间:0.5 h)经100次充放电循环后比容量仍达407.3 mAh·g-1.     

Designed Tetranuclear Iron-oxo Clusters with Redox Activity for High-Performance Lithium Storage

Polyoxometalates (POMs) are considered as promising catalysts with unique redox activity at the molecular level for energy storage. However, eco-friendly iron-oxo clusters with special metal coordination structures have rarely been reported for Li-ion storage. Herein, three novel redox-active tetranuclear iron-oxo clusters have been synthesized using the solvothermal method with different ratios of Fe³⁺ and SO₄²⁻. Further, they can serve as anode materials for Li-ion batteries. Among them, cluster H₆[Fe₄O₂(H₂O)₂(SO₄)₇]⋅H₂O, the stable structure extended by SO₄²⁻ with a unique 1D pore, displays a specific discharge capacity of 1784 mAh g⁻¹ at 0.2 C and good cycle performance (at 0.2 C and 4 C). This is the first instance of inorganic iron-oxo clusters being used for Li-ion storage. Our findings present a new molecular model system with a well-defined structure and offer new design concepts for the practical application of studying the multi-electron redox activity of iron-oxo clusters.     

Flowerlike Vanadium Sesquioxide: Solvothermal Preparation and Electrochemical Properties

A novel 3D hierarchical flowerlike vanadium sesquioxide (V₂O₃) nano/microarchitecture consisting of numerous nanoflakes is prepared via a solvothermal approach followed by an appropriate heating treatment. The as‐obtained nanostructured V₂O₃ flower is characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) analysis, and transmission electron microscopy (TEM) (or/and high‐resolution TEM, HRTEM), and it is found that the V₂O₃ flower is constructed by single‐crystalline nanoflakes. Furthermore, it is demonstrated that the surface of the flowerlike V₂O₃ material is composed of nanostructured pores, which derive from the adsorption/desorption of nitrogen, and that the pore‐size distribution depends on the unique three‐dimensional interconnection between nanoflakes and on their intrinsic properties. The electrochemical behavior of the V₂O₃ flower for lithium‐ion insertion/extraction in non‐aqueous solution as well as the faradaic capacitance for pesudocapacitors in a neutral aqueous solution are also investigated. A reversible discharge capacity as high as 325 mA h g^?1 is obtained at a current density of 0.02 A g^?1 from a LiClO₄/EC:DEC electrolyte solution (i.e. LiClO₄ in ethyl carbonate and diethyl carbonate). When used as the cathode material of pesudocapacitors in Li₂SO₄, the flowerlike oxide displayed a very high initial capacitance of 218 F g^?1 at a current density of 0.05 A g^?1. We believe that the good performance of the flowerlike V₂O₃ electrode is most probably due to its unique 3D hierarchical nano/microarchitecture, which shows that the electrochemical properties of a cathodic material do not only depend on the oxidation state of that material but also—to a large extent—on its crystalline structure and morphology. The aforementioned properties suggest that the present V₂O₃ flower materials may have a great potential to be employed as electrode materials in rechargeable lithium batteries and pesudocapacitors.     

Breaking Mass Transport Limitations by Iodized Polyacrylonitrile Anodes for Extremely Fast-Charging Lithium-Ion Batteries

The fast-charging capability of rechargeable batteries is greatly limited by the sluggish ion transport kinetics in anode materials. Here we develop an iodized polyacrylonitrile (I-PAN) anode that can boost the bulk/interphase lithium (Li)-ion diffusion kinetics and accelerate Li-ion desolvation process to realize high-performance fast-charging Li-ion batteries. The iodine immobilized in I-PAN framework expands ion transport channels, compresses the electric double layer, and changes the inner Helmholtz plane to form LiF/LiI-rich solid electrolyte interphase layer. The dissolved iodine ions in the electrolyte self-induced by the interfacial nucleophilic substitution of PF₆⁻ not only promote the Li-ion desolvation process, but also reuse the plated/dead Li formed on the anode under fast-charging conditions. Consequently, the I-PAN anode exhibits a high capacity of 228.5 mAh g⁻¹ (39 % of capacity at 0.5 A g⁻¹ delivered in 18 seconds) and negligible capacity decay for 10000 cycles at 20 A g⁻¹. The I-PAN||LiNi_0.8Co_0.1Mn_0.1O₂ full cell shows excellent fast-charging performance with attractive capacities and negligible capacity decay for 1000 cycles at extremely high rates of 5 C and 10 C (1 C=180 mA g⁻¹). We also demonstrate high-performance fast-charging sodium-ion batteries using I-PAN anodes.