Synthesis of uniform polycrystalline tin dioxide nanofibers and electrochemical application in lithium-ion batteries

Under optimized synthesis conditions, very large area uniform SnO₂ nanofibers consisting of orderly bonded nanoparticles have been obtained for the first time by thermal pyrolysis and oxidization of electrospun tin(II)2-ethylhexanoate/polyacrylonitrile (PAN) polymer nanofibers in air. The structure and morphology were elaborated by X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The SnO₂ nanofibers delivered a reversible capacity of 446 mAh g⁻¹ after 50 cycles at the 100 mA g⁻¹ rate and excellent rate capability of 477.7 mAh g⁻¹ at 10.0 C. Owing to the improved electrochemical performance, this electrospun SnO₂ nanofiber could be one of the most promising candidate anode materials for the lithium-ion battery.     

Electrochemical properties of heat-treated polymer-derived SiCN anode for lithium ion batteries

Silicon-carbon-nitrogen material (SiCN) is pyrolyzed from polysilylethylenediamine (PSEDA) derivation, followed by a heat-treating process at 1000 °C in Ar atmosphere. This heat-treated SiCN material has an excellent electrochemical performance as an anode for lithium ion batteries. Charge-discharge cycle measurements show that the heat-treated SiCN material exhibits a high first cycle discharge capacity of 829.0 mAh g⁻¹ and stays between 400 and 370 mAh g⁻¹ after 30 cycles. The discharge capacity remains above 300 mAh g⁻¹ at the high current density of 80 and 160 mA g⁻¹. These values are higher than untreated SiCN and commercial graphite anodes, which indicates that the heat-treating process improves the charge-discharge capacity, cycle stability and high-rate ability of SiCN anode. It is seemed that changes of SiCN structure, the formation of loose nano-holes on material surface and the formation of graphitic carbon phase in heat-treating process contribute to the improvement of electrochemical properties for SiCN anode.     

Three-dimensional reticular tin-manganese oxide composite anode materials for lithium ion batteries

Tin-manganese oxide film with three-dimensional (3D) reticular structure has been prepared by electrostatic spray deposition (ESD). X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicate that the film is amorphous. X-ray-photoemission spectroscopy (XPS) demonstrates that the 3D grid is composed of tin-manganese oxide. As an anode electrode for the lithium ion battery, the tin-manganese oxide film has 1188.3 mAh g⁻¹ of initial discharge capacity and very good capacity retention of 656.2 mAh g⁻¹ up to the 30th cycle. Such a composite film can be used as an anode for lithium ion batteries with higher energy densities.     

Modified hydrothermal synthesis of SnOy-SiO2 for lithium-ion battery anodes

A modified hydrothermal method was developed to synthesize tin oxide doped with highly dispersed silicon oxide. The microstructure, morphology and electrochemical performance of the mixtures were analyzed by X-ray diffraction (XRD), infra-red (IR), scanning electron microscopy (SEM) and electrochemical methods. The average size of the particles is about 30 nm. Silicon oxide as matrix should be able to support the anode changes accompanied by the formation of lithium-tin alloys, thus an improvement of the cycleability of the Li-ion battery would be expected. The electrochemical results showed that addition of silicon oxide reduces the irreversible capacity during the first discharge/charge cycle. The material delivers a charge capacity of more than 750 mAh g⁻¹. The capacity loss per-cycle is about 0.9% after cycling 20 times. The electrochemical performance indicates that silicon oxide is an appropriate matrix and these composites are good anode candidates for application in lithium-ion batteries.     

Electrochemical performance of flowerlike CaSnO3 as high capacity anode material for lithium-ion batteries

Nanosized CaSnO₃ is synthesized by a hydrothermal process and characterized by X-ray diffraction (XRD), Raman spectroscopy, and scanning electron microscopy (SEM). The SEM observation shows the sample has a porous flowerlike morphology. The electrochemical results exhibit that the stable and reversible capacity of 547 mAh g⁻¹ is obtained after 50 cycles at 60 mA g⁻¹ (0.1 C) and the corresponding charge capacity is determined to be 316 mAh g⁻¹ at the current density of 2.5 C. Cyclic voltammetry and electrochemical impedance spectroscopy data are analyzed to complement the galvanostatic results. The observed excellent performance is attributed to the porous structure and large surface area of flowerlike CaSnO₃.     

Electrodeposition of iron oxide nanorods on carbon nanofiber scaffolds as an anode material for lithium-ion batteries

Iron oxide film with spaced radial nanorods is formed on the VGCF (vapor-grown carbon nanofiber) scaffolds by means of anodic electrodeposition. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy show that the iron oxide film deposited on the VGCF surface is α-Fe₂O₃ and consists of spaced radial nanorods having 16-21 nm in diameter after annealing at 400 °C. Galvanostatic charge/discharge results indicate that the α-Fe₂O₃/VGCF anode (970 mAh g⁻¹) has higher capacity than bare α-Fe₂O₃ anode (680 mAh g⁻¹) at 10 C current discharge. VGCF scaffolds fabricated by electrophoretic deposition favor the electron conduction, and the spaced radial nanorods on VGCFs facilitate the migration of lithium ion from the electrolyte. Electrochemical reactions between α-Fe₂O₃ and lithium ion are therefore improved significantly by this tailored architecture.     

Enhanced electrochemical properties of LiFePO4/C synthesized with two kinds of carbon sources,PEG-4000 (organic) and Super p (inorganic)

Olivine structured LiFePO₄/C cathode was synthesized via a freeze-drying route and followed by microwave heating with two kinds of carbon sources: PEG-4000 (organic) and Super p (inorganic). XRD patterns indicate that the as-prepared sample has an olivine structure and carbon modification does not affect the structure of the sample. Image of SEM shows a uniform and optimized particles size, which greatly improves the electrochemical properties. TEM result reveals the amorphous carbon around the surface of the particles. At a low rate of 0.1 C, the LiFePO₄/C sample presents a high discharge capacity of 157.8 mAh g⁻¹ which is near the theoretical capacity (170 mAh g⁻¹), and it still attains to 149.1 mAh g⁻¹ after 200 cycles. It also exhibits an excellent rate capacity with high discharge capacities of 143.2 mAh g⁻¹, 137.5 mAh g⁻¹, 123.7 mAh g⁻¹ and 101.6 mAh g⁻¹ at 0.5 C, 1.0 C, 2.0 C and 5.0 C, respectively. EIS results indicate that the charge transfer resistance of LiFePO₄ decreases greatly after carbon coating.     

Electrochemical reaction of the SiMn/C composite for anode in lithium ion batteries

The SiMn-graphite composite powder was prepared by mechanical ball milling and its electrochemical performances were evaluated as the candidate anode materials for lithium ion batteries. It is found that the cyclic performance of the composite materials is improved significantly compared to SiMn alloy and pure silicon. The heat treatment of the electrodes is beneficial for enhancing the cyclic stabilities. The SiMn-20 wt.% graphite composite electrode after annealing at 200 °C has an initial reversible capacity of 463 mAh g⁻¹ and a charge-discharge efficiency of 70%. Moreover, the reversible capacity maintains 426 mAh g⁻¹ after 30 cycles with a coulomb efficiency of over 97%. The phase structure and morphology of the composite were analyzed by X-ray diffraction (XRD) and scanning electron microscopy. The lithiation/delithiation behavior was investigated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry. The composite materials appear to be promising candidates as negative electrodes for lithium rechargeable batteries.     

Electrochemical performances of Al-based composites as anode materials for Li-ion batteries

Al-C, Al-Fe and Al-Fe-C composite materials have been prepared by high-energy ball milling technique. The electrochemical measurements demonstrated that the Al-Fe-C composites have greatly improved electrochemical performances in comparison with Al, Al-C and Al-Fe anode. For example, Al₇₁Fe₉C₂₀ can deliver the reversible capacity of 436 mAh g⁻¹ at first cycle and 255 mAh g⁻¹ at 15th cycle. This improved electrochemical performance could be attributed to the alloying formation of Al with Fe and the buffering effect by the graphite matrix. This suggests that the Al-Fe-C composite has a potential possibility to be developed as an anode material for lithium-ion batteries.     

Mesoporous polyaniline or polypyrrole/anatase TiO2 nanocomposite as anode materials for lithium-ion batteries

A functional composite as anode materials for lithium-ion batteries, which contains highly dispersed TiO₂ nanocrystals in polyaniline matrix and well-defined mesopores, is fabricated by employing a novel one-step approach. The as-prepared mesoporous polyaniline/anatase TiO₂ nanocomposite has a high specific surface area of 224 m² g⁻¹ and a predominant pore size of 3.6 nm. The electrochemical performance of the as-prepared composite as anode material is investigated by cyclic voltammograms and galvanostatic method. The results demonstrate that the polyaniline/anatase nanocomposite provides larger initial discharge capacity of 233 mAh g⁻¹ and good cycle stability at the high current density of 2000 mA g⁻¹. After 70th cycles, the discharge capacity is maintained at 140 mAh g⁻¹. The excellent electrochemical performance of the polyaniline/TiO₂ nanocomposite is mainly attributed to its special structure. Furthermore, it is accessible to extend the novel strategy to other polymer/TiO₂ composites, and the mesoporous polypyrrole/anatase TiO₂ is also successfully fabricated.     

The preparation of nano-sulfur/MWCNTs and its electrochemical performance

In this work, a novel nano-sulfur/MWCNTs composite with modified multi-wall carbon nano-tubes (MWCNTs) as sulfur-fixed matrix for Li/S battery is reported. Based on different solubility of sulfur in different solvents, nano-sulfur/MWCNTs composite was prepared by solvents exchange method. The composite was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The modified MWCNTs are considered that not only acts as a conducting material, but also a matrix for sulfur. The electrochemical performance of the nano-sulfur/MWCNTs composite was tested. The results indicated that nano-sulfur/MWCNTs composite had the specific capacity of 1380 mAh g⁻¹, 1326 mAh g⁻¹ and 1210 mAh g⁻¹ in the initial cycle at 100 mA g⁻¹, 200 mA g⁻¹ and 300 mAh g⁻¹ discharge rates respectively, and remained a reversible capacity of 1020 mAh g⁻¹, 870 mAh g⁻¹ and 810 mAh g⁻¹ after 30 cycles. The electrochemical performances confirm that the modified MWCNTs as sulfur-fixed matrix show better ability than any other carbon in cathode of Li/S batteries that had been reported.     

1-Alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids as highly safe electrolyte for Li/LiFePO4 battery

Several 1-alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids (alkyl-DMimTFSI) were prepared by changing carbon chain lengths and configuration of the alkyl group, and their electrochemical properties and compatibility with Li/LiFePO₄ battery electrodes were investigated in detail. Experiments indicated the type of ionic liquid has a wide electrochemical window (−0.16 to 5.2 V vs. Li⁺/Li) and are theoretically feasible as an electrolyte for batteries with metallic lithium as anode. Addition of vinylene carbonate (VC) improves the compatibility of alkyl-DMimTFSI-based electrolytes towards lithium anode and LiFePO₄ cathode, and enhanced the formation of solid electrolyte interface to protect lithium anodes from corrosion. The electrochemical properties of the ionic liquids obviously depend on carbon chain length and configuration of the alkyl, including ionic conductivity, viscosity, and charge/discharge capacity etc. Among five alkyl-DMimTFSI-LiTFSI-VC electrolytes, Li/LiFePO₄ battery with the electrolyte-based on amyl-DMimTFSI shows best charge/discharge capacity and reversibility due to relatively high conductivity and low viscosity, its initial discharge capacity is about 152.6 mAh g⁻¹, which the value is near to theoretical specific capacity (170 mAh g⁻¹). Although the battery with electrolyte-based isooctyl-DMimTFSI has lowest initial discharge capacity (8.1 mAh g⁻¹) due to relatively poor conductivity and high viscosity, the value will be dramatically added to 129.6 mAh g⁻¹ when 10% propylene carbonate was introduced into the ternary electrolyte as diluent. These results clearly indicates this type of ionic liquids have fine application prospect for lithium batteries as highly safety electrolytes in the future.     

A new high-performance cathode material for rechargeable lithium-ion batteries: Polypyrrole/vanadium oxide nanotubes

Polypyrrole/vanadium oxide nanotubes (PPy/VOx-NTs) as a new high-performance cathode material for rechargeable lithium-ion batteries are synthesized by a combination of hydrothermal treatment and cationic exchange technique. The morphologies and structures of the as-prepared samples are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, thermogravimetry and differential scanning calorimeter (TG-DSC) and X-ray powder diffraction (XRD). The results indicate that the organic templates are mainly substituted by the conducting polymer polypyrrole without destroying the previous nanotube structure. Their electrochemical properties are evaluated via galvanostatic charge/discharge cycling, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). It is found that PPy/VOx-NTs exhibit high discharge capacity and excellent cycling performance at different current densities compared to vanadium oxide nanotubes (VOx-NTs). After 20 cycles, the reversible capacity of PPy/VOx-NTs (159.5 mAh g⁻¹) at the current density of 80 mA g⁻¹ is about four times of magnitude higher than that of VOx-NTs (37.5 mAh g⁻¹). The improved electrochemical performance could be attributed to the enhanced electronic conductivity and the improved structural flexibility resulted from the incorporation of the conducting polymer polypyrrole.     

Nano/micro-hybrid NiS cathodes for lithium ion batteries

The present study highlights a low temperature process by which 1D stacked 3D microstructures of nickel sulfide comprised of nanospikes have been synthesized and assembled as cathodes for lithium chalcogenide batteries. These micro/nano-clusters were synthesized hydrothermally under different conditions. These clusters exhibited a surface area of 15 m² g⁻¹. The present study also provides the first reports on the electrochemical performance of these NiS microclusters as cathode materials in lithium fluoro-Tris-sulfonimide electrolyte for lithium ion batteries. A detailed study has been performed to elucidate how surface morphology and redox reaction behaviors underlying these electrodes impact the cyclic behavior and specific capacity. This electrode−electrolyte combination showed minimal dissolution of the electrode in the electrolyte which was confirmed by inductively coupled plasma atomic emission spectroscopy. From the electrochemical analysis performed an intrinsic correlation between the capacity, self-discharge property and the surface morphology has been deduced and explained on the basis of relative contributions from the redox reactions of nickel sulfide in lithium fluoro-Tris-sulfonimide electrolyte. A working model of lithium battery in a coin cell form is also shown exhibiting a specific capacity of 550 mAh g⁻¹.     

Enhanced cycling performance of Fe3O4-graphene nanocomposite as an anode material for lithium-ion batteries

Fe₃O₄-graphene nanocomposite was prepared by a gas/liquid interface reaction. The structure and morphology of the Fe₃O₄-graphene nanocomposite were characterized by X-ray diffraction, scanning electron microscopy and high-resolution transmission electron microscopy. The electrochemical performances were evaluated in coin-type cells. Electrochemical tests show that the Fe₃O₄-22.7 wt.% graphene nanocomposite exhibits much higher capacity retention with a large reversible specific capacity of 1048 mAh g⁻¹ (99% of the initial reversible specific capacity) at the 90th cycle in comparison with that of the bare Fe₃O₄ nanoparticles (only 226 mAh g⁻¹ at the 34th cycle). The enhanced cycling performance can be attributed to the facts that the graphene sheets distributed between the Fe₃O₄ nanoparticles can prevent the aggregation of the Fe₃O₄ nanoparticles, and the Fe₃O₄-graphene nanocomposite can provide buffering spaces against the volume changes of Fe₃O₄ nanoparticles during electrochemical cycling.     

Nonaqueous and template-free synthesis of Sb doped SnO2 microspheres and their application to lithium-ion battery anode

Antimony doped SnO₂ (ATO) microspheres composed of ATO nanoparticles were prepared by using a hydrothermal process in a nonaqueous and template-free solution from the inorganic precursors (SnCl₄ and Sb(OC₂H₅)₃). The physical properties of the as-synthesized samples were investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption-desorption isotherms, and X-ray photoelectron spectrum (XPS). The resulting particles were highly crystalline ATO microspheres in the diameter range of 3-10 μm and with many pores. The as-prepared samples were used as negative materials for lithium-ion battery, whose charge-discharge properties, cyclic voltammetry, and cycle performance were examined. The results showed that a high initial discharge capacity of 1981 mAh g⁻¹ and a charge capacity of 957 mAh g⁻¹ in a potential range of 0.005-3.0 V was achieved, which suggests that tin oxide-based materials work as high capacity anodes for lithium-ion rechargeable batteries. The cycle performance is improved because the conducting ATO nanoparticles can also perform as a better matrix for lithium-ion battery anode.     

A novel micro-spherical CoSn2/Sn alloy composite as high capacity anode materials for Li-ion rechargeable batteries

Micro-scaled spherical CoSn₂/Sn alloy powders synthesized from oxides of Sn and Co via carbothermal reduction at 800 °C were examined for use as anode materials in Li-ion battery. The phase composition and particle morphology of the CoSn₂/Sn alloy composite powders were investigated by XRD, SEM and TEM. The prepared CoSn₂/Sn alloy composite electrode exhibits a low initial irreversible capacity of ca. 140 mAh g⁻¹, a high specific capacity of ca. 600 mAh g⁻¹ at constant current density of 50 mA g⁻¹, and a good rate capability. The stable discharge capacities of 500-515 mAh g⁻¹ and the columbic efficiencies of 95.8-98.1% were obtained at current density of 500 mA g⁻¹. The relatively large particle size of CoSn₂/Sn alloy composite powder is apparently favorable for the lowering of initial capacity loss of electrode, while the loose particle structural characteristic and the Co addition in Sn matrix should be responsible for the improvement of cycling stability of CoSn₂/Sn electrode.     

Preparation and electrochemical characterization of TiO2 nanowires as an electrode material for lithium-ion batteries

Anatase TiO₂ nanowires containing minor TiO₂(B) phase were prepared by a hydrothermal chemical reaction followed by the post-heat treatment at 400 °C. The phase structure and morphology were analyzed by X-ray diffraction, Raman scattering, transmission electron microscope, and field-emission scanning electron microscopy. The electrochemical properties were investigated by employing constant current discharge-charge test, cyclic voltammetry, and electrochemical impedance techniques. These nanowires exhibited high rate capacity of 280 mAh g⁻¹ even after 40 cycles, and the coulombic efficiency was approximately 98%, indicating excellent cycling stability and reversibility. The electrochemical impedance spectra showed a stable kinetic process of the electrode reaction. These results indicated that the TiO₂ nanowires have promising application for high energy density lithium-ion batteries.     

Cobalt-boron amorphous alloy prepared in water/cetyl-trimethyl-ammonium bromide/n-hexanol microemulsion as anode for alkaline secondary batteries

Amorphous cobalt-boron (Co-B) with uniform nanoparticles was prepared for the first time via reduction of cobalt acetate by potassium borohydride in the water/cetyl-trimethyl-ammonium bromide/n-hexanol microemulsion system. The sample was characterized by X-ray diffraction, transmission electron microscopy, nitrogen adsorption-desorption, X-ray photoelectron spectroscopy, inductively coupled plasma, cyclic voltammetry, differential scanning calorimetry, temperature-programmed desorption, scanning electron microscopy, charge-discharge test and electrochemical impedance spectra. The results demonstrate that electrochemical activity of the as-synthesized Co-B was higher than that of the regular Co-B prepared in aqueous solution. It indicates that the homogeneous distribution and large specific surface area helped the electrochemical hydrogen storage of the as-synthesized Co-B. Furthermore, the as-synthesized Co-B even had 347 mAh g⁻¹ after 50 cycles, while the regular Co-B prepared in aqueous solution only had 254 mAh g⁻¹ after 30 cycles at a current of 100 mA g⁻¹. The better cycling performance can be ascribed to its smaller interfacial impedance between electrode and electrolyte.     

Nickel oxide/hydroxide nanoplatelets synthesized by chemical precipitation for electrochemical capacitors

Nickel hydroxide powder prepared by directly chemical precipitation method at room temperature has a nanoplatelet-like morphology and could be converted into nickel oxide at annealing temperature higher than 300 °C, confirmed by the thermal gravimetric analysis and X-ray diffraction. Annealing temperature influences significantly both the electrical conductivity and the specific surface area of nickel oxide/hydroxide powder, and consequently determines the capacitor behavior. Electrochemical capacitive behavior of the synthesized nickel hydroxide/oxide film is investigated by cyclic voltammetry and electrochemical impedance spectroscope methods. After 300 °C annealing, the highest specific capacitance of 108 F g⁻¹ is obtained at scan rate of 10 mV s⁻¹. When annealing temperature is lower than 300 °C, the electrical conductivity of nickel hydroxide dominates primarily the capacitive behavior. When annealing temperature is higher than 300 °C, both electrical conductivity and specific surface area of the nickel oxide dominate the capacitive behavior.