Excellent Performance of Few-Layer Borocarbonitrides as Anode Materials in Lithium-Ion Batteries

Borocarbonitrides (BxCyNz) with a graphene-like structure exhibit a remarkable high lithium cyclability and current rate capability. The electrochemical performance of the BxCyNz materials, synthesized by using a simple solid-state synthesis route based on urea, was strongly dependent on the composition and surface area. Among the three compositions studied, the carbon-rich compound B0.15C0.73N0.12 with the highest surface area showed an exceptional stability (over 100cycles) and rate capability over widely varying current density values (0.05-1Ag(-1)). B0.15C0.73N0.12 has a very high specific capacity of 710mAhg(-1) at 0.05Ag(-1). With the inclusion of a suitable additive in the electrolyte, the specific capacity improved drastically, recording an impressive value of nearly 900mAhg(-1) at 0.05Ag(-1). It is believed that the solid-electrolyte interphase (SEI) layer at the interface of BxCyNz and electrolyte also plays a crucial role in the performance of the BxCyNz .

Variations in Magnetic Properties of Nanostructured Nickel

The magnetic properties of carbon nanotube encapsulated nickel nanowires (C. E. nanowires of diameter similar to 10 nm), and its comparison to other forms of Ni are carried out in this work. The saturation magnetization (M-s) and coercivity (H-c) for C. E. nanowires are 1.0 emu/g and 230 Oe. The temperature dependence of coercivity follows T-0.77 dependence indicating a superparamagnetic behavior. The field-cooled and zero-field-cooled plots indicate that the blocking temperature (T-B) similar to 300 K. These altered magnetic properties of C. E. nanowires are mainly due to the nanoscale confinement effect from carbon nanotube encapsulation. The shape and magnetic environment enhance the total magnetic anisotropy of C. E. nanowires by a factor of four.

Texture evolution during annealing of large-strain deformed nanocrystalline nickel

The recrystallization behaviour of cold-rolled nanocrystalline (nc) nickel has been studied at temperatures between 573 and 1273 K using bulk texture measurements and electron back-scattered diffraction. The texture in nc nickel is different from that of its microcrystalline counterpart, consisting of a strong Goss (G) and rotated Goss (RG) components at 773 K instead of the typical cube component. The texture evolution in nc Ni has been attributed to the prior deformation textures and nucleation advantage of G and RG grains.

A Dinuclear Cadmium(II) Schiff Base Thiocyanato Complex: Crystal Structure and Fluorescence

A new dinuclear cadmium(II) complex, Cd(L)(NCS)](2) (1) has been synthesized using a potentially tetradentate Schiff base ligand HL, 2-((E)-(2-(diethylamino) ethylimino) methyl)-6-methoxyphenol, obtained by the condensation of 2-diethylaminoethylamine and o-vanillin, and characterized by different physicochemical techniques. Crystal structure of the title complex was unambiguously established by single crystal X-ray diffraction which reveals that metal centers are connected by bridging phenolato and chelating methoxy oxygen atoms of the coordinating Schiff bases and embedded in severely distorted octahedral geometries. Fluorescence properties of the ligand and its complex, studied at room temperature indicate that later may serve as strong fluorescent

Calibration Curve with Improved Limit of Detection for Cadmium in Soil: An Approach to Minimize the Matrix Effect in Laser-Induced Breakdown Spectroscopic Analysis

The present article describes a working or combined calibration curve in laser-induced breakdown spectroscopic analysis, which is the cumulative result of the calibration curves obtained from neutral and singly ionized atomic emission spectral lines. This working calibration curve reduces the effect of change in matrix between different zone soils and certified soil samples because it includes both the species' (neutral and singly ionized) concentration of the element of interest. The limit of detection using a working calibration curve is found better as compared to its constituent calibration curves (i.e., individual calibration curves). The quantitative results obtained using the working calibration curve is in better agreement with the result of inductively coupled plasma-atomic emission spectroscopy as compared to the result obtained using its constituent calibration curves.

In-situ Stabilization of Tin Nanoparticles in Porous Carbon Matrix derived from Metal Organic Framework: High Capacity and High Rate Capability Anodes for Lithium-ion Batteries

It is a formidable challenge to arrange tin nanoparticles in a porous matrix for the achievement of high specific capacity and current rate capability anode for lithium-ion batteries. This article discusses a simple and novel synthesis of arranging tin nanoparticles with carbon in a porous configuration for application as anode in lithium-ion batteries. Direct carbonization of synthesized three-dimensional Sn-based MOF: K2Sn2(1,4-bdc)(3)](H2O) (1) (bdc = benzenedicarboxylate) resulted in stabilization of tin nanoparticles in a porous carbon matrix (abbreviated as Sn@C). Sn@C exhibited remarkably high electrochemical lithium stability (tested over 100 charge and discharge cycles) and high specific capacities over a wide range of operating currents (0.2-5 Ag-1). The novel synthesis strategy to obtain Sn@C from a single precursor as discussed herein provides an optimal combination of particle size and dispersion for buffering severe volume changes due to Li-Sn alloying reaction and provides fast pathways for lithium and electron transport.

Texture transition in cold-rolled nickel-40 wt.% cobalt alloy

The micromechanical aspects of rolling texture development in Ni-40 wt.% Co alloy during very large reductions (up to epsilon(t) = 3.9) have been studied. The alloy showed a typical Cu-type texture up to a true strain of epsilon(t) = 3; however, the texture undergoes an abrupt transition to Bs-type on further rolling to epsilon(t) approximate to 4. (The Bs-type texture, here, comprises almost equal fractions of Goss and Bs components.) Microstructural observations, at early stages, show that deformation is accommodated entirely by slip, and very little presence of deformation twinning is observed to explain the texture transition. However, at much higher reduction levels, micrographs show a high fraction of Cu-type shear bands. These bands are predominantly found in Cu-oriented grains and the crystallites inside the shear bands are preferentially oriented towards Goss, which could explain the final texture evolution. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Boron doped defective graphene as a potential anode material for Li-ion batteries

Graphene with large surface area and robust structure has been proposed as a high storage capacity anode material for Li ion batteries. While the inertness of pristine graphene leads to better Li kinetics, poor adsorption leads to Li clustering, significantly affecting the performance of the battery. Here, we show the role of defects and doping in achieving enhanced adsorption without compromising on the high diffusivity of Li. Using first principles density functional theory (DFT) calculations, we carry out a comprehensive study of diffusion kinetics of Li over the plane of the defective structures and calculate the change in the number of Li atoms in the vicinity of defects, with respect to pristine graphene. Our results show that the Li-C interaction, storage capacity and the energy barriers depend sensitively on the type of defects. The un-doped and boron doped mono-vacancy, doped di-vacancy up to two boron, one nitrogen doped di-vacancy, and Stone-Wales defects show low energy barriers that are comparable to pristine graphene. Furthermore, boron doping at mono-vacancy enhances the adsorption of Li. In particular, the two boron doped mono-vacancy graphene shows both a low energy barrier of 0.31 eV and better adsorption, and hence can be considered as a potential candidate for anode material.

Reduced graphene oxide-supported nickel oxide catalyst with improved CO tolerance for formic acid electrooxidation

The superior catalytic activity along with improved CO tolerance for formic acid electro-oxidation has been demonstrated on a NiO-decorated reduced graphene oxide (rGO) catalyst. The cyclic voltammetry response of rGO-NiO/Pt catalyst elucidates improved CO tolerance and follows direct oxidation pathway. It is probably due to the beneficial effect of residual oxygen groups on rGO support which is supported by FT-IR spectrum. A strong interaction of rGO support with NiO nanoparticles facilitates the removal of CO from the catalyst surface. The chronoamperometric response indicates a higher catalytic activity and stability of rGO-NiO/Pt catalyst than the NiO/Pt and unmodified Pt electrode catalyst for a prolonged time of continuous oxidation of formic acid. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Modelling of Effect of Non-Uniform Current Density on the Performance of Soluble Lead Redox Flow Batteries

Soluble lead acid redox flow battery (SLRFB) offers a number of advantages. These advantages can be harnessed after problems associated with buildup of active material on. electrodes (residue) are resolved. A mathematical model is developed to understand residue formation in SLRFB. The model incorporates fluid flow, ion transport, electrode reactions, and non-uniform current distribution on electrode surfaces. A number of limiting cases are studied to conclude that ion transport and electrode reaction on anode simultaneously control battery performance. The model fits the reported cell voltage vs. time profiles very well. During the discharge cycle, the model predicts complete dissolution of deposited material from trailing edge side of the electrodes. With time, the active surface area of electrodes decreases rapidly. The corresponding increase in current density leads to precipitous decrease in cell potential before all the deposited material is dissolved. The successive charge-discharge cycles add to the residue. The model correctly captures the marginal effect of flow rate on cell voltage profiles, and identifies flow rate and flow direction as new variables for controlling residue buildup. Simulations carried out with alternating flow direction and a SLRFB with cylindrical electrodes show improved performance with respect to energy efficiency and residue buildup. (C) 2014 The Electrochemical Society. All rights reserved.

New insights into the development of microstructure and deformation texture in nickel-60 wt.% cobalt alloy

The present study investigates the critical role of deformation twinning and Bs-type shear bands in the evolution of deformation texture in a low stacking fault energy Ni-60Co alloy up to very large rolling strain (epsilon(t) approximate to 4). The alloy develops a strong brass-type rolling texture, and its formation is initiated at the early stages of deformation. Extensive twinning is observed at the intermediate stages of deformation, which causes significant texture reorientation towards alpha-fiber. A pseudo-in-situ electron back-scattered diffraction technique adopted to capture orientation changes within individual grains during the early stages suggests that twinning should be subsequently aided by crystallographic slip to attain alpha-fiber (< 1 1 0 >parallel to ND) orientations. Beyond 40% reduction, deformation is dominated by Bs-type shear bands, and the banding coincides with the evolution of < 1 1 1 >parallel to ND components. The volume fraction of shear bands is significant at higher strains, and crystallites within the bands preferentially show < 1 1 0 >parallel to ND components. The absence of the Cu {1 1 2}< 1 1 1 > component in the initial texture, and subsequently during rolling, indicates that, for the evolution of a brass-type texture, the presence of the Cu component is not a necessary condition. The final rolling texture is a synergistic effect of deformation twinning and shear banding. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

t-Na-2(VO)P2O7: A 3.8 V Pyrophosphate Insertion Material for Sodium-Ion Batteries

Pyrophosphate oxyanionic framework compounds offer a great platform to investigate new battery materials. In our continuing effort to explore pyrophosphate cathodes for sodium-ion batteries, we report, for the first time, the synthesis and use of tetragonal Na-2(VO)P2O7 as a potential sodium-ion insertion material. This material can be easily prepared by using a conventional solid-state route at a relatively low temperature of 400 degrees C. Stabilizing as a tetragonal structure with an open framework, the material offers pathways for Na+ diffusion. The as-synthesized material, with no further cathode optimization, yields a reversible capacity (Q) approaching 80 mAh g(-1) (Q(Theoretical) = 93.4 mAh g(-1)) involving a one electron V5+/V4+ redox potential located at 3.8 V (vs. Na/Na+). Furthermore, the material exhibits decent rate kinetics and reversibility. Combining green synthesis and moderate electrochemical properties, t-Na-2(VO)P2O7 is reported as a new addition to the growing family of pyrophosphate cathodes for sodium-ion batteries.

A Reactive Intermediate, Ni-5(C6H4N3)(6)(CO)(4)], in the Formation of Nonameric Clusters of Nickel, Ni-9(C6H4N3)(12)(CO)(6)] and Ni-9(C6H4N3)(12)(CO)(6)].2(C3H7NO)

Three new molecular compounds, Ni-5(bta)(6)(CO)(4)], I, Ni-9(bta)(12)(CO)(6)], II, Ni-9(bta)(12)(CO)(6)]. 2(C3H7NO), III, (bta = benzotriazole) were prepared employing solvothermal reactions. Of these, I have pentanuclear nickel, whereas II and III have nonanuclear nickel species. The structures are formed by the connectivity between the nickel and benzotriazole giving rise to the 5- and 9-membered nickel clusters. The structures are stabilised by extensive pi aEuro broken vertical bar pi and C-H... pi interactions. Compound II and III are solvotamorphs as they have the same 9-membered nickel clusters and have different solvent molecules. To the best of our knowledge, the compounds I-III represent the first examples of the same transition element existing in two distinct coordination environment in this class of compounds. The studies reveal that compound I is reactive and could be an intermediate in the preparation of II and III. Thermal studies indicate that the compounds are stable upto 350(a similar to)C and at higher temperatures (similar to 800(a similar to)C) the compounds decompose into NiO. Magnetic studies reveal that II is anti-ferromagnetic.

The effect of gamma-gamma ` interface on the tensile and shear strengths of nickel-based superalloys: A first-principles study

First-principles density functional theory has been used to evaluate the shear and cleavage strength in terms of Griffith work and generalized stacking fault energy (GSF) of (001) plane for gamma, gamma' and gamma-gamma' system as a function of distance from the gamma/gamma' interface. Calculation of Griffith work suggests higher cleavage energy for bulk gamma as compared to gamma' while the GSF calculation suggests higher shear strength for bulk gamma' as compared to gamma. It has been found that the shear strength of the cubic plane of the gamma/gamma' interface is marginally lower than those of bulk gamma and gamma' phases. (C) 2014 Elsevier B.V. All rights reserved.