Controllable one-step synthesis of magnetite/carbon nanotubes composite and its electrochemical properties

Magnetite nanocrystals are deposited on carbon nanotubes by a reflux method in diethylene glycol. The morphological characterization proves that magnetite nanocrystals are decorated on the external surfaces of carbon nanotubes. The crystal size of magnetite nanocrystals can be readily tuned by adjusting the content of sodium acetate, but the content of sodium acetate has little effect on the amount of magnetite. The magnetite/carbon nanotubes composites exhibit an initial capacity as high as 840 mAh g⁻¹ and an excellent cycling performance for lithium storage. The reversible capacity, as high as 390 mAh g⁻¹, can be maintained after 75 charge/discharge cycles. The research has potential implications for the application of magnetite/carbon nanotubes composites as anode materials of lithium ion batteries.     

Binder-free combination of amorphous TiO<Subscript>2</Subscript> nanotube arrays with highly conductive Cu bridges for lithium ion battery anode

Binder-free combination of highly conductive Cu bridges with amorphous TiO₂ nanotube arrays for lithium ion battery anode were designed and achieved via one-step facile electrodeposition. The obtained composite Cu/TiO₂ nanotubes electrode was studied in terms of XRD, SEM, EDX, galvanostatic charge/discharge, cycle stability, rate performance, and AC impedance. As expected, the composite electrode delivered higher discharge capacity, rate performance, and cycle stability than the bare one, possibly due to improved electrical conductivity and the synergy effect between conductive Cu bridges and amorphous TiO₂ nanotube arrays.     

Enhanced rate performance of polypyrrole-coated sulfur/MWCNT cathode material: a kinetic study by electrochemical impedance spectroscopy

Lithium-sulfur batteries have a poor cyclability and inferior rate capability due to the shuttle effect of lithium polysulfides. To solve these problems, a sulfur-coated MWCNT composite (S/MWCNT) was coated with conductive polypyrrole (PPy) to trap the polysulfides and facilitate charge and lithium ion transport. From the contact angle measurement, it is found that the PPy coating improves the wettability of the S/MWCNT composite. Compared with the bare S/MWCNT composite, the PPy-coated S/MWCNT composite cathode exhibited improved cycle stability and high-rate performance. A reversible discharge capacity of 671 mAh g^?1 was maintained after 50 cycles at 3 C for the PPy-coated composite. The effect of PPy coating on kinetic property was investigated by electrochemical impedance spectroscopy (EIS). The electrolyte resistance, surface film resistance, charge transfer resistance, lithium ion diffusion coefficient, and exchange current density were evaluated from the EIS measurements. The EIS results reveal that the PPy coating increases both Li ion diffusion into the cathode and exchange current density. The as-prepared PPy-coated S/MWCNT composite can be considered to be a promising candidate for high capacity and high-rate performance cathode material.     

Carbon-coated hollow CoO microporous nanospheres synthesized by CoF<Subscript>2</Subscript> as the intermediates as anode materials for lithium-ion batteries

Uniformly carbon-coated hollow CoO microporous nanospheres have been successfully synthesized by the facile hydrothermal method using CoF₂ as the intermediates and glucose as the carbon source. The whole synthesis process can avoid using the toxic surfactant additives and tedious post-processing. The glucose-derived carbon not only suppresses the aggregation of CoO nanoparticles, but also plays an important role on the stabilization of hollow CoO microporous nanosphere structure. The specific structure can largely improve the electronic conductivity and accommodate the volume change of CoO electrode in the electrochemical processes. When used as anode materials of lithium ion batteries, the hollow CoO/C microporous composites exhibit exceptionally high-rate performances, high-specific capacity, and improved cycle performances. This study may provide a new approach for the synthesis of carbon-coated hollow microporous architecture electrode for high-performance batteries.     

Enhancement of the electrochemical performance of silicon/carbon composite material for lithium ion batteries

The silicon/carbon (Si/C) composite material was prepared, and the electrochemical performance was investigated as a promising anode material for lithium ion batteries. The results show that the binder in the electrode acts as an important role for improving the reversible capacity of the Si/C materials during cycling. The Si/C electrode with CMC/SBR binder possesses a better cycle performance than that with PVDF binder. The Si/C composite material shows an initial reversible capacity of more than 700 mAh∙g⁻¹ and remains a reversible capacity of 597 mAh g⁻¹ after 40 cycles.     

Structural transformation of graphite by arc-discharge

The formation of novel structures by the passage of an electric current through graphite is described. These structures apparently consist of hollow three-dimensional graphitic shells bounded by curved and faceted planes, typically made up of two graphene layers. The curved structures were frequently decorated with nano-scale carbon particles, or short nanotubes. In some cases, nanotubes were found to be seamlessly connected to the thin shells, indicating that the formation of the shells and the nanotubes is intimately connected. Small nanotubes or nanoparticles were also sometimes found encapsulated inside the hollow structures, while fullerene-like particles were often seen attached to the outside surfaces. With their high surface areas and structural perfection, the new carbon structures may have applications as anodes of lithium ion batteries or as components of composite materials.     

One-step synthesis of Fe3O4@C/reduced-graphite oxide nanocomposites for high-performance lithium ion batteries

In this paper, we propose a facile one-step strategy to prepare Fe₃O₄@amorphous carbon/reduced graphite oxide nanocomposites (FCRGs) under hydrothermal conditions. A transmission electron microscopy image has shown that the as-formed Fe₃O₄ nanoparticles coated with a layer of amorphous carbon are wrapped by reduced graphite oxide (r-GO) sheets. The diameter of Fe₃O₄ nanoparticles is less than 50 nm. N₂ adsorption/desorption isotherms indicate that the specific surface area of FCRG is 31.6 m²/g with porous structure. FCRG exhibits improved cycling stability and rate performances as a potential anode material for high-performance lithium ion batteries.     

Facile Synthesis of Porous MnO Microspheres for High‐Performance Lithium‐Ion Batteries

Manganese oxide is a highly promising anode material of lithium‐ion batteries (LIBs) for its low insertion voltage and high reversible capacity. Porous MnO microspheres are prepared by a facile method in this work. As an anode material of LIB, it can deliver a high reversible capacity up to 1234.2 mA h g^?1 after 300 cycles at 0.2 C, and a capacity of 690.0 mA h g^?1 in the 500th cycle at 2 C. The capacity increase with cycling can be attributed to the growth of reversible polymer/gel‐like film, and the better cycling stability and the superior rate performance can be attributed to the featured structure of the microspheres composed of nanoparticles with a short transport path for lithium ions, a large specific surface, and material/electrolyte contact area. The results suggest that the porous MnO microspheres can function as a promising anode material for high‐performance LIBs.     

Hollow Silica Spheres Embedded in a Porous Carbon Matrix and Its Superior Performance as the Anode for Lithium‐Ion Batteries

Silica (SiO₂) is regarded as one of the most promising anode materials for lithium‐ion batteries due to the high theoretical specific capacity and extremely low cost. However, the low intrinsic electrical conductivity and the big volume change during charge/discharge cycles result in a poor electrochemical performance. Here, hollow silica spheres embedded in porous carbon (HSS–C) composites are synthesized and investigated as an anode material for lithium‐ion batteries. The HSS–C composites demonstrate a high specific capacity of about 910 mA h g^?1 at a rate of 200 mA g^?1 after 150 cycles and exhibit good rate capability. The porous carbon with a large surface area and void space filled both inside and outside of the hollow silica spheres acts as an excellent conductive layer to enhance the overall conductivity of the electrode, shortens the diffusion path length for the transport of lithium ions, and also buffers the volume change accompanied with lithium‐ion insertion/extraction processes.     

Effect of SO<Subscript>2</Subscript> and CO<Subscript>2</Subscript> additives on the cycle performances of commercial lithium-ion batteries

The effects of SO₂ and CO₂ additives in electrolytes on the cycle properties of liquid-state Al-plastic film lithium-ion batteries were first investigated. The experimental electrolytes were added with different amounts of SO₂ and CO₂. The baseline electrolyte was 1 mol L⁻¹ LiPF₆ in ethylene carbonate/dimethylcarbonate/ethyl-methyl carbonate (1:1:1, by volume), and graphite was used as anode. The main analysis tools were cycling test, rate capability, internal resistance test, low-temperature performance, and thermal stability. The results showed that both of the additives could promote to form an excellent solid electrolyte interface film on the surface of graphite anode, leading to excellent cycle performances, the capacity retentions of CO₂ and S5 were 94% and 97% after 400 cycles, respectively. Besides, the results also exhibited that the electrochemical performances of internal resistance, rate capability, low-temperature performance, and thermal stability were not changed significantly by the use of SO₂ and CO₂ as electrolyte additives.     

One-pot facile synthesis of CuS/graphene composite as anode materials for lithium ion batteries

CuS/graphene composite has been synthesized by the one-pot hydrothermal method using thiourea as the sulfur source and reducing agent. The formation of CuS nanoparticles and the reduction of graphene oxide occur simultaneously during the hydrothermal process, which enables a uniform dispersion of CuS nanoparticles on the graphene nanosheets. The electrochemical performance of CuS/graphene composite was studied as anode materials for lithium ion batteries. The obtained CuS/graphene composite exhibits a relative high reversible capacity and good cycling stability. The good electrochemical performance of CuS/graphene composite can be attributed to graphene, which improves the electronic conductivity of composite and enhances the interfacial stability of electrode and electrolyte.     

纳米碳管的电化学贮锂性能

用透射电镜、高分辨透射电镜、X射线衍射和拉曼光谱表征了用催化热解法制备的纳米碳管的结构,研究了纳米碳管的电化学嵌脱锂性能。以纳米级铁粉为催化剂热解乙炔气得到的纳米碳管石墨化程度较低,结构中存在褶皱的石墨层、乱层石墨和微孔等缺陷,具有国交高的贮锂容量,初始容量为640mAh/g,但循环稳定性较差。而以纳米级氧化铁粉为催化剂热解乙烯得到的纳米碳管结构比较规则,循环稳定性较好,但贮锂容量较低,初始容量为282mAh/g。讨论了纳米碳管的结构对其温度特性和不同电流密度下的充放电容易的影响。     

Electrochemical performance of Sn-Sb-Cu film anodes prepared by layer-by-layer electrodeposition

A novel layer-by-layer electrodeposition and heat-treatment approach was attempted to obtain Sn-Sb-Cu film anode for lithium ion batteries. The preparation of Sn-Sb-Cu anodes started with galvanostatic electrochemically depositing antimony and tin sequentially on the substrate of copper foil collector. Sn-Sb and Cu-Sb alloys were formed when heated. The SEM analysis showed that the crystalline grains become bigger and the surface of the Sn-Sb-Cu anode becomes more denser after annealing. The energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) analysis showed the antimony, tin and copper were alloyed to form SnSb and Cu₂Sb after heat treatment. The X-ray photoelectron spectroscopy (XPS) analysis showed the surface of the Sn-Sb-Cu electrode was covered by a thin oxide layer. Electrochemical measurements showed that the annealed Sn-Sb-Cu anode has high reversible capacity and good capacity retention. It exhibited a reversible capacity of about 962 mAh/g in the initial cycle, which still remained 715 mAh/g after 30 cycles.     

Electrochemical characteristics of sulfur composite cathode for reversible lithium storage

The electrochemical characteristics of the sulfur composite cathode for reversible lithium storage were investigated. The sulfur composites showed novel electrochemical characteristics as well as high specific capacity and good cycleability. The sulfur composite presented the average discharge voltage of 1.9 V, which was just the half of conventional LiCoO₂ cathode materials, indicating that the double cells in series presented the same working voltage as conventional LiCoO₂ cells and meaning that the sulfur composite cells will have good interchangeability with conventional LiCoO₂ cells. The overcharge test showed that the sulfur composite cell cannot be charged over 5.0 V, indicating that the sulfur composite cell presented the intrinsic safety for overcharge. Overcharge can cause serious problems for the conventional Li ion cells. The overcharge test also showed that the sulfur composite cell was destroyed when the cell was charged over 4.0 V, resulting in that the cell cannot normally be discharged again. It is found, however, that the sulfur composite cell can be discharged again at very low current density of a 0.002-C rate after the cell was overcharged. Being much safer than lithium metal anode, the graphite anode was used to fabricate sulfur composite/graphite lithium ion cells with a prelithiated sulfur composite cathode, which was produced by electrochemical lithiation. The charge/discharge and cycling characteristics of the sulfur composite/graphite cell was investigated. The result showed that the sulfur composite/graphite cells can be normally cycled and showed the different voltages from that of the cell with the lithium metal anode. This paves the effective way to fabricate safer sulfur composite/graphite lithium ion cells.     

A Facile Method for Synthesis of Porous NiCo2O4 Nanorods as a High‐Performance Anode Material for Li‐Ion Batteries

Porous electrode materials with large specific surface area, relatively short diffusion path, and higher electrical conductivity, which display both better rate capabilities and good cycle lives, have huge benefits for practical applications in lithium‐ion batteries. Here, uniform porous NiCo₂O₄ nanorods (PNNs) with pore‐size distribution in the range of 10–30 nm and lengths of up to several micrometers are synthesized through a convenient oxalate co‐precipitation method followed by a calcining process. The PNN electrode exhibits high reversible capacity and outstanding cycling stability (after 150 cycles still maintain about 650 mA h g^?1 at a current density of 100 mA g^?1), as well as high Coulombic efficiency (>98%). Moreover, the PNNs also exhibit an excellent rate performance, and deliver a stable reversible specific capacity of 450 mA h g^?1 even at 2000 mA g^?1. These results demonstrate that the PNNs are promising anode materials for high‐performance Li‐ion batteries.     

Chemically shortened multi-walled carbon nanotubes used as anode materials for lithium-ion batteries

An easy chemically cutting process, modified Hummers' method, was proposed to treat multi-walled carbon nanotubes, successfully cutting pristine long, entangled carbon nanotubes into hydrosoluble pieces, mostly less than 200 nm. This short, chemically oxidized carbon nanotube was then applied as an anode material for lithium-ion batteries. The as-prepared material possessed higher reversible capacity and coulombic efficiency. The intrinsic factors were explored by X-ray photoelectron spectroscopy and cyclic voltammetry.     

High‐Capacity Anode Materials for Lithium‐Ion Batteries: Choice of Elements and Structures for Active Particles

Growing market demand for portable energy storage has triggered significant research on high‐capacity lithium‐ion (Li‐ion) battery anodes. Various elements have been utilized in innovative structures to enable these anodes, which can potentially increase the energy density and decrease the cost of Li‐ion batteries. In this review, electrode and material parameters are considered in anode fabrication. The periodic table is then used to explore how the choice of anode material affects rate performance, cycle stability, Li‐ion insertion/extraction potentials, voltage hysteresis, volumetric and specific capacities, and other critical parameters. Silicon (Si), germanium (Ge), and tin (Sn) anodes receive more attention in literature and in this review, but other elements, such as antimony (Sb), lead (Pb), magnesium (Mg), aluminum (Al), gallium (Ga), phosphorus (P), arsenic (As), bismuth (Bi), and zinc (Zn) are also discussed. Among conversion anodes focus is placed on oxides, nitrides, phosphides, and hydrides. Nanostructured carbon (C) receives separate consideration. Issues in high‐ capacity research, such as volume change, insufficient coulombic efficiency, and solid electrolyte interphase (SEI) layer stability are elucidated. Finally, advanced carbon composites utilizing carbon nanotubes (CNT), graphene, and size preserving external shells are discussed, including high mass loading (thick) electrodes and electrodes capable of providing load‐bearing properties.     

Surface modification of natural vein graphite for the anode application in Li-ion rechargeable batteries

Natural vein graphite with high purity and crystallinity is seldom used as anode material in lithium-ion rechargeable batteries (LIB) due to impurities and inherent surface structure. This study focuses on improving the surface properties of purified natural vein graphite surface by employing mild chemical oxidation. Needle-platy graphite sample with initial average carbon percentage of 99.83% was improved to 99.98% after treatment with 5 vol.% HCl. Surface modification of purified graphite was done by chemical oxidation with (NH₄)₂S₂O₈ and HNO₃. Fourier-transform infrared spectra of graphite after chemical indicating surface oxidation of graphite surface. X-ray diffraction and scanning electron microscopic studies show the improvement of graphite structure without modification of crystalline structure. Electrochemical performance of lithium-ion cell assembled with developed anode material shows noticeable improvement of the reversible capacity and coulombic efficiency in the first cycle and cycling behavior after surface modification.     

Effect of nickel coating on electrochemical performance of graphite anodes for lithium ion batteries

Among the different materials often studied and proposed as negative electrodes for lithium-ion batteries, graphite anodes are the most used in commercial batteries. For this study, synthetic graphite was tested. During the first discharge 0.2 Li ions were consumed for the formation of the SEI film and the capacity reaches about 387 mAh/g. But at the end of the first charge only 72% of the initial charge was recovered (the reversible capacity is about 279 mAh/g). In order to improve this performance we have deposited metallic nickel on graphite with the intention to obtain a homogeneous thin layer able to modify the nature of the SEI film, to allow the diffusion of lithium ions through the protective layer, and also to increase the performance of graphite electrodes. The results show a decrease of the irreversible capacity loss (16% instead of 28% for pure graphite electrodes) as well as better cycleability for a nickel-deposited graphite electrode with only 11% weight ratio of nickel. On the other hand, an increase of the nickel content decreases this performance.     

Electrochemical performance of modified artificial graphite as anode material for lithium ion batteries

Artificial graphite anode material was modified by coating an amorphous carbon layer on the particle surface via a sol-gel and pyrolysis route. The electrochemical measurements demonstrate that appropriate carbon coating can increase the specific capacity and the initial coulombic efficiency of the graphite material, while excessive carbon coating leads to the decrease in specific capacity. Thick coating layer is obviously unfavorable for the lithium ion diffusion due to the increased diffusion distance, but the decreased specific surface area caused by carbon coating is beneficial to the decrease of initial irreversible capacity loss. The sample coated with 5 wt.% glucose exhibits a stable specific capacity of 340 mAhg^?1. Carbon coating can remarkably enhance the rate capability of the graphite anode material, which is mainly attributed to the increased diffusion coefficient of lithium ion.