Two Methods for Intercalation of Surfactants into Graphite Oxide.

The intercalation properties of graphite oxide are important; however, the specific processes and mechanisms associated with intercalation have rarely been elucidated. In this paper, two types of surfactants, polyvinylpyrrolidone and tetradecyltrimethylammonium bromide, were used to thoroughly explore the intercalation properties of graphite oxide. The polyvinylpyrrolidone and tetradecyltrimethylammonium bromide-intercalated graphite oxide composites were synthesized under different conditions and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray energy dispersive spectroscopy, and transmission electron microscopy. It was found that polyvinylpyrrolidone could be directly intercalated into the graphite oxide layers and tetradecyltrimethylammonium bromide could not effectively react with the waterdispersed graphite oxide. With a low quantity of polyvinylpyrrolidone, only a part of the graphite oxide was intercalated, and the interlayer spacing of the polyvinylpyrrolidone-intercalated composites increased as the polyvinylpyrrolidone: graphite oxide mass ratio increased. When the graphite oxide was dispersed in a 0.05 N NaOH solution, the tetradecyltrimethylammonium bromide rapidly reacted with the graphite oxide, while the mixture of polyvinylpyrrolidone and graphite oxide could not be effectively separated. The intercalated spacing of the tetradecyltrimethylammonium bromideintercalated graphite oxide increased with the tetradecyltrimethylammonium bromide: graphite oxide mass ratio, but its crystalline structure was not as ordered as the polyvinylpyrrolidone-intercalated graphite oxide prepared in the water solution. The infrared spectra of the two surfactant-intercalated graphite oxide samples revealed that the polyvinylpyrrolidone is bonded to the graphite oxide via hydrogen bonding, while the tetradecyltrimethylammonium bromide is bonded via ionic bonding. The mechanism analysis indicated that the polyvinylpyrrolidone could directly enter the graphite oxide layers in the water solution because of the driving force of hydrogen bonding. However, processes such as graphite oxide exfoliation, reactions between the graphite oxide and tetradecyltrimethylammonium bromide, and reaggregation of the graphite oxide sheets are necessary for the formation of tetradecyltrimethylammonium bromide-intercalated graphite oxide.

Layered Li2MnO3·3LiNi(0.5-x)Mn(0.5-x)Co(2x)O2 microspheres with Mn-rich cores as high performance cathode materials for lithium ion batteries.

Layered Li2MnO3·3LiNi0.5-xMn0.5-xCo2xO2 (x = 0, 0.05, 0.1, 0.165) microspheres with Mn-rich core were successfully synthesized by a simple two-step precipitation calcination method and intensively evaluated as cathode materials for lithium ion batteries. The X-ray powder diffractometry (XRD) results indicate that the growth of Li2MnO3-like regions is impeded due to the presence of cobalt (Co) in the material. The field-emission scanning electron microscopy (FESEM) data reveal the core-shell-like structure with a Mn-rich core in the as-prepared particles. The charge-discharge testing reveals that the capacity is markedly improved by adding Co. The activation of the cathode after Co doping becomes easier and can be accomplished completely when charged to 4.6 V at the C/40 rate in the initial cycle. Superior electrochemical performances are obtained for samples with x = 0.05 and 0.1. The corresponding initial discharge capacities are separately 281 and 285 mA h g(-1) at C/40 between 2 and 4.6 V at room temperature. After 250 cycles at C/2, the respective capacity retentions are 71.2% and 70.4%, which are better compared to the normal Li-excess Li2MnO3·3LiNi0.4Mn0.4Co0.2O2 sample with a uniform distribution of Mn element in the particles. The initial discharge capacities of both samples are approximately 250 mA h g(-1) at a rate of C/2 between 2 and 4.6 V at 55 °C after activation. Furthermore, the samples are investigated by electrochemical impedance spectroscopy (EIS) at room and elevated temperature, revealing that the key factor affecting electrochemical performance is the charge transfer resistance in the particles.

Solvothermal synthesis of monodisperse LiFePO4 micro hollow spheres as high performance cathode material for lithium ion batteries.

A microspherical, hollow LiFePO4 (LFP) cathode material with polycrystal structure was simply synthesized by a solvothermal method using spherical Li3PO4 as the self-sacrificed template and FeCl2·4H2O as the Fe(2+) source. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the LFP micro hollow spheres have a quite uniform size of ~1 µm consisting of aggregated nanoparticles. The influences of solvent and Fe(2+) source on the phase and morphology of the final product were chiefly investigated, and a direct ion exchange reaction between spherical Li3PO4 templates and Fe(2+) ions was firstly proposed on the basis of the X-ray powder diffraction (XRD) transformation of the products. The LFP nanoparticles in the micro hollow spheres could finely coat a uniform carbon layer ~3.5 nm by a glucose solution impregnating-drying-sintering process. The electrochemical measurements show that the carbon coated LFP materials could exhibit high charge-discharge capacities of 158, 144, 125, 101, and even 72 mAh g(-1) at 0.1, 1, 5, 20, and 50 C, respectively. It could also maintain 80% of the initial discharge capacity after cycling for 2000 times at 20 C.

Hierarchical assembly of Ti(IV)/Sn(II) co-doped SnO2 nanosheets along sacrificial titanate nanowires: synthesis, characterization and electrochemical properties.

Hierarchical assembly of Ti(IV)/Sn(II)-doped SnO2 nanosheets along titanate nanowires serving as both sacrificial templates and a Ti(IV) source is demonstrated, using SnCl2 as a tin precursor and Sn(II) dopants and NaF as the morphology controlling agent. Excess fluoride inhibits the hydrolysis of SnCl2, promoting heterogeneous nucleation of Sn(II)-doped SnO2 on the titanate nanowires due to the insufficient oxidization of Sn(II) to Sn(IV). Simultaneously, titanate nanowires are dissolved forming Ti(4+) species under the etching effect of in situ generated HF resulting in spontaneous Ti(4+) ion doping of SnO2 nanosheets formed under hydrothermal conditions. Compositional analysis indicates that Ti(4+) ions are incorporated by substitution of Sn sites at a high level (16-18 at.%), with uniform distribution and no phase separation. Mössbauer spectroscopy quantified the relative content of Sn(II) and Sn(IV) in both Sn(II)-doped and Ti(IV)/Sn(II) co-doped SnO2 samples. Electrochemical properties were investigated as an anode material in lithium ion batteries, demonstrating that Ti-doped SnO2 nanosheets show improved cycle performance, which is attributed to the alleviation of inherent volume expansion of the SnO2-based anode materials by substituting part of Sn sites with Ti dopants.

Large-scale fabrication of graphene-wrapped FeF3 nanocrystals as cathode materials for lithium ion batteries.

Graphene-wrapped FeF3 nanocrystals (FeF3/G) have been successfully fabricated for the first time by a vapour-solid method, which can be generalized to synthesize other metal fluorides. The as-synthesized FeF3/G delivers a charge capacity of 155, 113, and 73 mA h g(-1) at 104, 502, and 1040 mA g(-1) in turn, displaying superior rate capability to bare FeF3. Moreover, it exhibits stable cyclability over 100 cycles with a charge capacity of 185.6 and 119.8 mA h g(-1) at 20.8 and 208 mA g(-1), respectively, which could be ascribed to the buffering effect and lowered resistance from the graphene. This versatile vapour-solid method and the improved cyclability provide a promising avenue for the application of metal fluorides as cathode materials.

Fabrication of LiF/Fe/Graphene nanocomposites as cathode material for lithium-ion batteries.

Homogeneous LiF/Fe/Graphene nanocomposites as cathode material for lithium ion batteries have been synthesized for the first time by a facile two-step strategy, which not only avoids the use of highly corrosive reagents and expensive precursors but also fully takes advantage of the excellent electronic conductivity of graphene. The capacity remains higher than 150 mA h g(-1) after 180 cylces, indicating high reversible capacity and stable cyclability. The ex situ XRD and HRTEM investigations on the cycled LiF/Fe/G nanocomposites confirm the formation of FeF(x) and the coexistence of LiF and FeF(x) at the charged state. Therefore, the heterostructure nanocomposites of LiF/Fe/Graphene with nano-LiF and ultrafine Fe homogeneously anchored on graphene sheets could open up a novel avenue for the application of iron fluorides as high-performance cathode materials for lithium-ion batteries.