Synthesis and Characterization of Vanadium Nitride/Carbon Nanocomposites.

The present work focuses on the synthesis of a vanadium nitride (VN)/carbon nanocomposite material via the thermal decomposition of vanadyl phthalocyanine (VOPC). The morphology and chemical structure of the synthesized compounds were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), Fourier transformed infrared spectroscopy (FTIR), X-ray diffraction (XRD), and X-ray photoemission spectroscopy (XPS). The successful syntheses of the VOPC and non-metalated phthalocyanine (H2PC) precursors were confirmed using FTIR and XRD. The VN particles present a needle-like morphology in the VN synthesized by the sol-gel method. The morphology of the VN/C composite material exhibited small clusters of VN particles. The XRD analysis of the thermally decomposed VOPC indicated a mixture of amorphous carbon and VN nanoparticles (VN(TD)) with a cubic structure in the space group FM-3M consistent with that of VN. The XPS results confirmed the presence of V(III)-N bonds in the resultant material, indicating the formation of a VN/C nanocomposite. The VN/C nanocomposite synthesized through thermal decomposition exhibited a high carbon content and a cluster-like distribution of VN particles. The VN/C nanocomposite was used as an anode material in LIBs, which delivered a specific capacity of 307 mAh g-1 after 100 cycles and an excellent Coulombic efficiency of 99.8 at the 100th cycle.

Synthesis and Characterization of Titanium Nitride-Carbon Composites and Their Use in Lithium-Ion Batteries.

This work focuses on the synthesis of titanium nitride-carbon (TiN-carbon) composites by the thermal decomposition of a titanyl phthalocyanine (TiN(TD)) precursor into TiN. The synthesis of TiN was also performed using the sol-gel method (TiN(SG)) of an alkoxide/urea. The structure and morphology of the TiN-carbon and its precursors were characterized by XRD, FTIR, SEM, TEM, EDS, and XPS. The FTIR results confirmed the presence of the titanium phthalocyanine (TiOPC) complex, while the XRD data corroborated the decomposition of TiOPC into TiN. The resultant TiN exhibited a cubic structure with the FM3-M lattice, aligning with the crystal system of the synthesized TiN via the alkoxide route. The XPS results indicated that the particles synthesized from the thermal decomposition of TiOPC resulted in the formation of TiN-carbon composites. The TiN particles were present as clusters of small spherical particles within the carbon matrix, displaying a porous sponge-like morphology. The proposed thermal decomposition method resulted in the formation of metal nitride composites with high carbon content, which were used as anodes for Li-ion half cells. The TiN-carbon composite anode showed a good specific capacity after 100 cycles at a current density of 100 mAg-1.

The Use of Succinonitrile as an Electrolyte Additive for Composite-Fiber Membranes in Lithium-Ion Batteries.

In the present work, the effect of temperature and additives on the ionic conductivity of mixed organic/ionic liquid electrolytes (MOILEs) was investigated by conducting galvanostatic charge/discharge and ionic conductivity experiments. The mixed electrolyte is based on the ionic liquid (IL) (EMI/TFSI/LiTFSI) and organic solvents EC/DMC (1:1 v/v). The effect of electrolyte type on the electrochemical performance of a LiCoO2 cathode and a SnO2/C composite anode in lithium anode (or cathode) half-cells was also investigated. The results demonstrated that the addition of 5 wt.% succinonitrile (SN) resulted in enhanced ionic conductivity of a 60% EMI-TFSI 40% EC/DMC MOILE from ~14 mS·cm-1 to ~26 mS·cm-1 at room temperature. Additionally, at a temperature of 100 °C, an increase in ionic conductivity from ~38 to ~69 mS·cm-1 was observed for the MOILE with 5 wt% SN. The improvement in the ionic conductivity is attributed to the high polarity of SN and its ability to dissolve various types of salts such as LiTFSI. The galvanostatic charge/discharge results showed that the LiCoO2 cathode with the MOILE (without SN) exhibited a 39% specific capacity loss at the 50th cycle while the LiCoO2 cathode in the MOILE with 5 wt.% SN showed a decrease in specific capacity of only 14%. The addition of 5 wt.% SN to the MOILE with a SnO2/C composite-fiber anode resulted in improved cycling performance and rate capability of the SnO2/C composite-membrane anode in lithium anode half-cells. Based on the results reported in this work, a new avenue and promising outcome for the future use of MOILEs with SN in lithium-ion batteries (LIBs) can be opened.

Investigation into the thermodynamics and kinetics of the binding of Cu2+ and Pb2+ to TiS2 nanoparticles synthesized using a solvothermal process.

In the present study, titanium (IV) sulfide (TiS2) was synthesized and investigated for the removal of Cu2+ and Pb2+ ions from aqueous solutions. TiS2 nanoparticles synthesized through a solvothermal synthesis were characterized using x-ray diffraction (XRD) and scanning electron microscopy (SEM). The average particle size for the TiS2 material was determined to be 8.03 ± 0.98 nm from the diffraction pattern. Studies were performed to examine the effects of pH, temperature, time, and interfering ions on the binding of Cu2+ and Pb2+ to the TiS2. As well isotherm studies were performed to determine the binding capacity of TiS2 for both Cu2+ and Pb2+ ions. The pH profile studies showed optimal binding occurred at pH 2 for the sorption of both Cu2+ and Pb2+ to the TiS2. The isotherm studies showed the adsorption capacities at temperatures of 4, 22, and 45°C for Cu2+ were 243, 222, and 153 mg/g, respectively. An opposite trend in the adsorption was observed for Pb2+ binding to the TiS2. The observed binding capacities for Pb2+ were 32, 166, and 357 mg/g, at temperatures of 4, 22, and 45°C, respectively. The thermodynamic parameters for binding showed a non-spontaneous process for the sorption of Cu2+ whereas a spontaneous binding process was observed for the sorption of Pb2+. Additionally, the binding of Cu2+ on TiS2 in the presence of interfering ions (Na+, K+, Mg2+, and/or Ca2+) was observed to decrease at high concentrations; however, the binding of Pb2+ was unaffected by the presence of the same cations.

Centrifugal Spinning: An Alternative for Large Scale Production of Silicon-Carbon Composite Nanofibers for Lithium Ion Battery Anodes.

Composites made of silicon nanostructures in carbon matrixes are promising materials for anodes in Li ion batteries given the synergistic storage capacity of silicon combined with the chemical stability and electrical conductivity of carbonaceous materials. This work presents the development of Si/C composite fine fiber mats produced by carbonization of poly(vinyl alcohol) (PVA)/Si composites. PVA has a high carbon content (ca. 54.5%) and, being water-soluble, it promotes the development of environmentally friendly materials. Si nanoparticles were dispersed in PVA solutions and transformed into fine fibers using a centrifugal spinning technique given its potential for large scale production. The Si/PVA fibers mats were then subjected to dehydration by exposing them to sulfuric acid vapor. The dehydration improved the thermal and chemical stability of the PVA matrix, allowing further carbonization at 800 °C. The resulting Si/C composite fibers produced binder-free anodes for lithium ion batteries that delivered specific discharge and charge capacities of 952 mA h g-1 and 862 mA g-1, respectively, with a Columbic efficiency of 99% after 50 cycles.

α-Fe2O3 nanoparticle-loaded carbon nanofibers as stable and high-capacity anodes for rechargeable lithium-ion batteries.

α-Fe(2)O(3) nanoparticle-loaded carbon nanofiber composites were fabricated via electrospinning FeCl(3)·6H(2)O salt-polyacrylonitrile precursors in N,N-dimethylformamide solvent and the subsequent carbonization in inert gas. Scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and elemental analysis were used to study the morphology and composition of α-Fe(2)O(3)-carbon nanofiber composites. It was indicated that α-Fe(2)O(3) nanoparticles with an average size of about 20 nm have a homogeneous dispersion along the carbon nanofiber surface. The resultant α-Fe(2)O(3)-carbon nanofiber composites were used directly as the anode material in rechargeable lithium half cells, and their electrochemical performance was evaluated. The results indicated that these α-Fe(2)O(3)-carbon nanofiber composites have high reversible capacity, good capacity retention, and acceptable rate capability when used as anode materials for rechargeable lithium-ion batteries.

Sulfonated polystyrene fiber network-induced hybrid proton exchange membranes.

A novel type of hybrid membrane was fabricated by incorporating sulfonated polystyrene (S-PS) electrospun fibers into Nafion for the application in proton exchange membrane fuel cells. With the introduction of S-PS fiber mats, a large amount of sulfonic acid groups in Nafion aggregated onto the interfaces between S-PS fibers and the ionomer matrix, forming continuous pathways for facile proton transport. The resultant hybrid membranes had higher proton conductivities than that of recast Nafion, and the conductivities were controlled by selectively adjusting the fiber diameters. Consequently, hybrid membranes fabricated by ionomers, such as Nafion, incorporated with ionic-conducting nanofibers established a promising strategy for the rational design of high-performance proton exchange membranes.

Structural, mechanical and osmotic properties of injectable hyaluronan-based composite hydrogels.

The osmotic and scattering properties of hyaluronan-based composite hydrogels composed of stiff biopolymer chains (carboxymethylated thiolated hyaluronan (CMHA-S)) crosslinked by a flexible polymer (polyethylene glycol diacrylate (PEGDA)) are investigated and analyzed in terms of the scaling theory. The total pre-gel polymer weight concentration is varied between 0.5 wt.% and 3.2 wt.%, while the mole ratio between the reactive PEG chain ends and the thiolated HA moieties is changed between 0.15 and 1.0. The shear modulus G of the fully swollen gels exhibits a stronger dependence on pre-gel concentration than on the crosslink density. Osmotic deswelling measurements reveal that the osmotic mixing pressure depends on the weight ratio CMHA-S/PEGDA, and is practically unaffected by the pre-gel concentration. Small-angle neutron scattering observations indicate that the thermodynamic properties of these composite gels are governed by total polymer concentration, i.e., specific interactions between the two polymeric components do not play a significant role.

Rheological properties of cross-linked hyaluronan-gelatin hydrogels for tissue engineering.

Hydrogels that mimic the natural extracellular matrix (ECM) are used in three-dimensional cell culture, cell therapy, and tissue engineering. A semi-synthetic ECM based on cross-linked hyaluronana offers experimental control of both composition and gel stiffness. The mechanical properties of the ECM in part determine the ultimate cell phenotype. We now describe a rheological study of synthetic ECM hydrogels with storage shear moduli that span three orders of magnitude, from 11 to 3 500 Pa, a range important for engineering of soft tissues. The concentration of the chemically modified HA and the cross-linking density were the main determinants of gel stiffness. Increase in the ratio of thiol-modified gelatin reduced gel stiffness by diluting the effective concentration of the HA component.