Facile synthesis and electrochemical performances of hollow graphene spheres as anode material for lithium-ion batteries

The hollow graphene oxide spheres have been successfully fabricated from graphene oxide nanosheets utilizing a water-in-oil emulsion technique, which were prepared from natural flake graphite by oxidation and ultrasonic treatment. The hollow graphene oxide spheres were reduced to hollow graphene spheres at 500°C for 3 h under an atmosphere of Ar(95%)/H₂(5%). The first reversible specific capacity of the hollow graphene spheres was as high as 903 mAh g^-1 at a current density of 50 mAh g^-1. Even at a high current density of 500 mAh g^-1, the reversible specific capacity remained at 502 mAh g^-1. After 60 cycles, the reversible capacity was still kept at 652 mAh g^-1 at the current density of 50 mAh g^-1. These results indicate that the prepared hollow graphene spheres possess excellent electrochemical performances for lithium storage. The high rate performance of hollow graphene spheres thanks to the hollow structure, thin and porous shells consisting of graphene sheets.

PACS

81.05.ue; 61.48.Gh; 72.80.Vp     

Porous polythiophene as a cathode material for lithium batteries with high capacity and good cycling stability

Polythiophene (PTh) has been synthesized by chemical oxidative polymerization and used as an active cathode material in lithium batteries. The lithium batteries are characterized by cyclic voltammetry (CV), galvanostatic charge/discharge cycling and electrochemical impedance spectroscopic studies (EIS). The lithium battery with the PTh cathode exhibits a discharge voltage of 3.7 V compared to Li⁺/Li and excellent electrochemical performance. PTh can provide large discharge capacities above 50 mA h g⁻¹ and good cycle stability at a high current density 900 mA g⁻¹. After 500 cycles, the discharge capacity is maintained at 50.6 mA h g⁻¹. PTh is a promising candidate for high-voltage power sources with excellent electrochemical performance.     

Hydrothermal synthesis of flower-like Zn2SnO4 composites and their performance as anode materials for lithium-ion batteries

Flower-like Zn₂SnO₄ composites had been prepared through a green hydrothermal synthesis. The structural, morphological and electrochemical properties were investigated by means of XRD, BET, SEM, TEM, and electrochemical measurement. The results show that the as-prepared sample is in high purity phase and of good crystallinity; meanwhile it has a particular 3-D structure and large surface area. Electrochemical measurement suggests that flower-like Zn₂SnO₄ composites exhibit better cycling properties and lower initial irreversible capacities than the solid Zn₂SnO₄ cubes. The first discharge and charge capacities of the material are 1750 mA h g⁻¹ and 880 mA h g⁻¹ respectively. A higher reversible capacity of 501 mA h g⁻¹ was obtained after 50 cycles at a current density of 300 mA g⁻¹. The higher reversible capacity and good stability can be related to the special nanostructural features of the material. Such Zn₂SnO₄ structures synthesized by the simple and cheap method are expected to have potential application in energy storage.     

Preparation of functionalized graphene sheets by a low-temperature thermal exfoliation approach and their electrochemical supercapacitive behaviors

Two kinds of functionalized graphene sheets were produced by thermal exfoliation of graphite oxide. The first kind of functionalized graphene sheets was obtained by thermal exfoliation of graphite oxide at low temperature in air. The second kind was prepared by carbonization of the first kind of functionalized graphene sheets at higher temperature in N₂. Scanning electron microscopy images show that both two kinds of samples possess nanoporous structures. The results of N₂ adsorption-desorption analysis indicate that both of two kinds of samples have high BET surface areas. Moreover, the second kind of functionalized graphene sheets has a relatively higher BET surface area. The results of electrochemical tests is as follows: the specific capacitance values of the first kind of functionalized graphene sheets in aqueous KOH electrolyte are about 230 F g⁻¹; the specific capacitance values of the second kind of functionalized graphene sheets with higher BET surface areas are only about 100 F g⁻¹; however, compared with the first kind of functionalized graphene sheets, the second kind has a higher capacitance retention at large current density because of its good conductive behaviors; furthermore, in non-aqueous EC/DEC electrolyte, the specific capacitance values of the first kind sample and the second kind sample are about 73 F g⁻¹ and 36 F g⁻¹, respectively.     

Synthesis of sawtooth-like Li4Ti5O12 nanosheets as anode materials for Li-ion batteries

Hierarchical layered hydrous lithium titanate and Li₄Ti₅O₁₂ microspheres assembled by nanosheets have been successfully synthesized via a hydrothermal process and subsequent thermal treatment. The electrochemical properties of the two samples have been investigated by galvanostatic methods. The former, with the obvious layered structure and a large surface area, delivers a reversible capacity of 180 mA h g⁻¹ after 200 cycles at 200 mA g⁻¹. As for Li₄Ti₅O₁₂, with the intriguing and unique sawtooth-like morphology, it presents exceptional high rate performance and excellent cycling stability. Up to 132 mA h g⁻¹ is obtained after 200 cycles at 10,000 mA g⁻¹ (57 C), proving itself promising for high-rate applications.     

Electrochemical performance of CoSb3/MWNTs nanocomposite prepared by in situ solvothermal synthesis

In situ solvothermally synthesized composite (SSC) and mechanically blended composite (MBC) of nanosized CoSb₃ and multiwalled carbon nanotubes (MWNTs) were prepared and investigated as potential anode materials for Li-ion batteries. It was found that SSC exhibits an entanglement structure of nanosized CoSb₃ and MWNTs and shows significantly better cycling stability than MBC. The reversible capacity of SSC electrode reaches 312 mA h g⁻¹ at the first cycle and remains above 265 mA h g⁻¹ after 30 cycles.     

High reversible capacity of SnO2/graphene nanocomposite as an anode material for lithium-ion batteries

A gas–liquid interfacial synthesis approach has been developed to prepare SnO₂/graphene nanocomposite. The as-prepared nanocomposite was characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller measurements. Field emission scanning electron microscopy and transmission electron microscopy observation revealed the homogeneous distribution of SnO₂ nanoparticles (2–6 nm in size) on graphene matrix. The electrochemical performances were evaluated by using coin-type cells versus metallic lithium. The SnO₂/graphene nanocomposite prepared by the gas–liquid interface reaction exhibits a high reversible specific capacity of 1304 mAh g⁻¹ at a current density of 100 mA g⁻¹ and excellent rate capability, even at a high current density of 1000 mA g⁻¹, the reversible capacity was still as high as 748 mAh g⁻¹. The electrochemical test results show that the SnO₂/graphene nanocomposite prepared by the gas–liquid interfacial synthesis approach is a promising anode material for lithium-ion batteries.     

Electrochemical properties of La1−xSrxFeO3 (x = 0.2, 0.4) as negative electrode of Ni-MH batteries

La_(1−x)Sr_xFeO₃ (x = 0.2,0.4) powders were prepared by a stearic acid combustion method, and their phase structure and electrochemical properties were investigated systematically. X-ray diffraction (XRD) analysis shows that La_(1−x)Sr_xFeO₃ perovskite-type oxides consist of single-phase orthorhombic structure (x = 0.2) and rhombohedral one (x = 0.4), respectively. The electrochemical test shows that the reaction at La_(1−x)Sr_xFeO₃ oxide electrodes are reversible. The discharge capacities of La_(1−x)Sr_xFeO₃ oxide electrodes increase as the temperature rises. With the increase of the temperature from 298 K to 333 K, their initial discharge capacity mounts up from 324.4 mA h g⁻¹ to 543.0 mA h g⁻¹ (when x = 0.2) and from 147.0 mA h g⁻¹ to 501.5 mA h g⁻¹ (when x = 0.4) at the current density of 31.25 mA g⁻¹, respectively. After 20 charge-discharge cycles, they still remain perovskite-type structure. Being similar to the relationship between the discharge capacity and the temperature, the electrochemical kinetic analysis indicates that the exchange current density and proton diffusion coefficient of La_(1−x)Sr_xFeO₃ oxide electrodes increase with the increase of the temperature. Compared with La_0.8Sr_0.2FeO₃, La_0.6Sr_0.4FeO₃ electrode is a more promising candidate for electrochemical hydrogen storage because of its higher cycle capacity at various temperatures.     

Novel tin-graphite composites as negative electrodes of Li-ion batteries

For the purpose of obtaining an improved performance of the graphite negative electrode of Li-ion batteries, a novel graphite-tin composite has been synthesized by reduction of tin chloride (SnCl₂) with KC₈ in THF medium. This composite contains nano-sized tin particles dispersed on the graphite surface and free tin aggregates. Lithium electrochemical insertion occurs both in graphite and in tin. An experimental reversible specific charge of 489 mA h g⁻¹ is found stable upon cycling. Such a value is lower than the maximum theoretical one of 609 mA h g⁻¹ suggesting that only a part of tin is involved in the lithium insertion/extraction process. This part of active tin responsible for the stable capacity could be that bound to graphite. To the contrary, free tin aggregates could contribute to an extra capacity that decreases upon cycling in relation with the volume changes that occurs during alloying/dealloying.     

Electrochemical properties and hydrogen storage mechanism of perovskite-type oxide LaFeO3 as a negative electrode for Ni/MH batteries

Perovskite-type oxide LaFeO₃ powder was prepared using a stearic acid combustion method. Its phase structure, electrochemical properties and hydrogen storage mechanism as negative electrodes for nickel/metal hydride (Ni/MH) batteries have been investigated systematically. The results of X-ray diffraction (XRD) analysis show that both the calcined powder and the charged/discharged samples after 10 cycles have orthorhombic structures. The discharge capacity, whose maximum value appeared at the first cycle, is 530.3 mA h g⁻¹ at 333 K and increases with an increase in temperature. The discharge capacity decreases distinctly during the first three cycles and then stays steady at about 80 mA h g⁻¹, 160 mA h g⁻¹ and 350 mA h g⁻¹ at 298 K, 313 K and 333 K, respectively. The hydrogen storage mechanism is studied by XRD, X-ray photoelectron spectroscopy (XPS) and mass spectrometry (MS), coupled with pressure-composition-temperature (PCT) methods. Hydrogen atoms may be intercalating into the oxide lattice and forming a homogeneous solid solution during the charging process.     

The characteristics of Ni–Co–Mn–O precursor and Li(Ni1/3Co1/3Mn1/3)O2 cathode powders prepared by spray pyrolysis

Ni–Co–Mn–O precursor powders with spherical shape and dense structure were prepared by spray pyrolysis from a spray solution containing a drying control chemical additive (DCCA) and polymeric precursors. In contrast, the Ni–Co–Mn–O precursor powders obtained from a spray solution without additives had a hollow and porous morphology. Ni–Co–Mn–O precursor powders with a spherical shape and dense structure yielded Li(Ni_1/3Co_1/3Mn_1/3)O₂ cathode powders with a spherical shape and fine size by means of a solid-state reaction with lithium hydroxide. The mean size of the spherical cathode powder was 1.1 μm. The discharge capacity of the Li(Ni_1/3Co_1/3Mn_1/3)O₂ powders with spherical shape and filled morphology was 195 mA h g⁻¹ at a current density of 0.1 C. The discharge capacities of the cathode powders with spherical shape and filled morphology at 55 °C decreased from 183 to 154 mA h g⁻¹ by the 30th cycle at a current density of 0.5 C.     

Si-C-O glass-like compound/exfoliated graphite composites for negative electrode of lithium ion battery

Two low molecular weight silicone compounds, a cyclic type having vinyl groups and a chain-type having Si-H bonds, a catalyst for curing, and a catalyst regulator were mixed. The mixture was impregnated into exfoliated graphite (EG) by sorption, and cured in air at 200 °C. By this process cross-linked silicone coatings were formed on graphite flakes. The composites of Si-C-O glass-like compounds and EG were synthesized by heat treatment of this precursor at 1000-1400 °C for 1 h in argon. The composites formed at 1000-1300 °C were amorphous by XRD and had practically the same chemical composition: Si 44-45, C 27-29, O 25-26, H < 0.5, all in mass%. The ²⁹Si MAS-NMR spectra indicated that the compound formed at 1000 °C was mainly composed of siloxane bonds and amorphous silica, whereas in the compound formed at 1300°C, Si-C bonds and amorphous silica were predominant. The insertion/extraction characteristics of lithium ions for the electrode prepared with composite:poly(vinylidene fluoride) = 90:10 mass% were examined in 1 mol L⁻¹ LiClO₄ solution of ethylene carbonate:diethyl carbonate = 50:50 vol%. High, 650-700 mA h g⁻¹, capacities and steady cycle performance at 50 mA g⁻¹ were achieved with the composites formed at 1250-1300 °C. Capacities of the composites formed at 1200 °C and lower were initially higher but decreased with increasing number of cycles. The composites formed at 1350 °C showed good cycle performance but the capacity was about 500 mA h g⁻¹ due to the formation of β-SiC. Except for the first cycle, the capacity-potential characteristics were similar to those of hard carbons and the coulomb efficiency was 95-100%. For all the composites the capacity was larger than that of graphite (372 mA h g⁻¹) in the range of 50-200 mA g⁻¹. Due to the large insertion capacity of the first cycle, the efficiency was low (60-70%) at first. By short-circuiting the working electrode to the lithium foil counter electrode for a certain period, the irreversible capacity of the first cycle was almost eliminated. It indicates that direct doping of lithium ions into composites is a promising way to increase the efficiency of the first cycle.     

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.     

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.     

Submicron-sized cube-like α-Fe2O3 agglomerates as an anode material for Li-ion batteries

Submicron-sized cube-like α-Fe₂O₃ agglomerates were successfully fabricated via hydrothermal technique. The material showed a high reversible capacity of 900.2 mAh g⁻¹ and excellent capacity retention of 88.9% after 35 cycles at a current density of 40 mA g⁻¹. The initial columbic efficiencies of the as-prepared powder were 82.65 and 80.57% at current densities of 40 and 80 mA g⁻¹, respectively, which is higher than that of other α-Fe₂O₃ electrodes reported so far. We believe that the small crystal size and the high structure stability are responsible for the drastic improvement in initial coulombic efficiency and reversibility.     

Electrochemical studies of LiB compound as anode material for lithium-ion battery

Electrochemical studies of LiB compound were carried out for its application as anode for lithium-ion battery. The compound exhibited a reversible discharge-charge behavior between 0 and 0.75 V versus Li/Li⁺ with a first discharge capacity of 293 mA h g⁻¹. Discharging to 1.0 V, the first discharge capacity of LiB compound was 660 mA h g⁻¹, but a part of this capacity was irreversible. Impedance spectra were measured at several potentials corresponding to different discharge plateaus. The impedance spectra obtained below and above 0.8 V presented significantly different features. The solid electrolyte interphase layer (SEI) was formed below 0.8 V and assumed a good performance of LiB electrode in this potential range. The SEI was found to deteriorate above 0.8 V, which might be associated with the irreversible discharge capacity.     

Activated carbon fiber cloths as electrodes for high performance electric double layer capacitors

Activated carbon fiber cloth (ACFC) electrodes with high double layer capacitance and good rate capability were prepared from polyacrylonitrile (PAN) fabrics by optimizing the carbonization temperature prior to CO₂ activation. The carbonization temperature has a marked effect on both the pore structure and the electrochemical performances of the ACFCs. Moderate carbonization at 600 °C results in higher specific surface area and larger pore size, and hence higher capacitance and better rate capability. The specific capacitance of the ACFCs in 6 mol L⁻¹ KOH aqueous solution can be as high as 208 F g⁻¹. It remains 129 F g⁻¹ as the current density increases to 10 000 mA 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.     

Graphene nanosheets as electrode material for electric double-layer capacitors

Graphene nanosheets (GNSs) with narrow mesopore distribution around 4 nm were mass-produced from natural graphite via the oxidation and rapid heating processes. The effects of oxidant addition on the morphology, structure and electrochemical performance of GNSs as electrode materials for electric double-layer capacitor (EDLC) were systematically investigated. The electrochemical properties of EDLC were influenced by the specific surface area, pore characteristics, layer stacking and oxygen-containing functional group contents of electrode materials. Deeper oxidation makes graphite possess both higher specific surface area and more graphene edges, which are favorable for the enhancement of capacitive performance of EDLC. The electrodes with freestanding graphene nanosheets prepared by coating method exhibited good rate capability and reversibility at high scan rates (to 250 mV s⁻¹) in electrochemical performances. GNS electrode with specific surface area of 524 m² g⁻¹ maintained a stable specific capacitance of 150 F g⁻¹ under specific current of 0.1 A g⁻¹ for 500 cycles of charge/discharge.     

Preparation and characterization of ramsdellite Li2Ti3O7 as an anode material for asymmetric supercapacitors

Ramsdellite Li₂Ti₃O₇ was first synthesized via sol-gel process with good crystallity of an average particle size of 0.175 μm. The product was thoroughly investigated as a lithium intercalation compound, and as an active anode material in asymmetric supercapacitors coupling with activated carbon as cathode. Lithium intercalation reactions were found occurring at 1.32 and 1.62 V versus Li/Li⁺, respectively. A reversible specific capacity of 150 mA h g⁻¹ at 1C was obtained on Li₂Ti₃O₇ electrode in a nonaqueous electrolyte. The charge current was found to strongly influence the anodic discharge capacity in the asymmetric cell. The capacity retention at 10C charge-discharge rate was found to be 75.9% in comparison with that at 1C.