Nanostructured electrode materials for electrochemical energy storage and conversion

Manipulation of matter at the nanoscale is a way forward to move beyond our current choices in electrochemical energy storage and conversion technologies with promise of higher efficiency, environmental benignity, and cost-effectiveness. Electrochemical processes being basically surface phenomena, tailored multifunctional nanoarchitecturing can lead to improvements in terms of electronic and ionic conductivities, diffusion and mass transport, and electron transfer and electrocatalysis. The nanoscale is also a domain in which queer properties surface: those associated with conversion electrodes, ceramic particles enhancing the conductivity of polymer electrolytes, and transition metal oxide powders catalyzing fuel cell reactions, to cite a few. Although this review attempts to present a bird's eye view of the vast literature that has accumulated in this rather infant field, it also lists a few representative studies that establish the beneficial effects of going `nano'. Investigations on nanostructuring and use of nanoparticles and nanoarchitectures related to lithium-ion batteries (active materials and electrolytes), supercapacitors (electrical double-layer capacitors, supercapacitors based on pseudo-capacitance, and hybrid supercapacitors), and fuel cells (electrocatalysts, membranes and hydrogen storage materials) are highlighted. (C) 2012 John Wiley & Sons, Ltd.

Sensitivity of polarization fluctuations to the nature of protein-water interactions: Study of biological water in four different protein-water systems

Since the time of Kirkwood, observed deviations in magnitude of the dielectric constant of aqueous protein solution from that of neat water (similar to 80) and slower decay of polarization have been subjects of enormous interest, controversy, and debate. Most of the common proteins have large permanent dipole moments (often more than 100 D) that can influence structure and dynamics of even distant water molecules, thereby affecting collective polarization fluctuation of the solution, which in turn can significantly alter solution's dielectric constant. Therefore, distance dependence of polarization fluctuation can provide important insight into the nature of biological water. We explore these aspects by studying aqueous solutions of four different proteins of different characteristics and varying sizes, chicken villin headpiece subdomain (HP-36), immunoglobulin binding domain protein G (GB1), hen-egg white lysozyme (LYS), and Myoglobin (MYO). We simulate fairly large systems consisting of single protein molecule and 20000-30000 water molecules (varied according to the protein size), providing a concentration in the range of similar to 2-3 mM. We find that the calculated dielectric constant of the system shows a noticeable increment in all the cases compared to that of neat water. Total dipole moment auto time correlation function of water < dM(W) (0)delta M-W (t) > is found to be sensitive to the nature of the protein. Surprisingly, dipole moment of the protein and total dipole moment of the water molecules are found to be only weakly coupled. Shellwise decomposition of water molecules around protein reveals higher density of first layer compared to the succeeding ones. We also calculate heuristic effective dielectric constant of successive layers and find that the layer adjacent to protein has much lower value (similar to 50). However, progressive layers exhibit successive increment of dielectric constant, finally reaching a value close to that of bulk 4-5 layers away. We also calculate shellwise orientational correlation function and tetrahedral order parameter to understand the local dynamics and structural re-arrangement of water. Theoretical analysis providing simple method for calculation of shellwise local dielectric constant and implication of these findings are elaborately discussed in the present work. (C) 2014 AIP Publishing LLC.

Antioxidant activity and electrochemical elucidation of the enigmatic redox behavior of curcumin and its structurally modified analogues

Here, we report studies on the antioxidant activity and redox behavior of curcumin and its structurally modified synthetic analogues. We have synthesized a number of analogues of curcumin which abrogate its keto-enol tautomerism or substitute the methylene group at the centre of its heptadione moiety implicated in the hydride transfer and studied their redox property. From cyclic voltammetric studies, it is demonstrated that H-atom transfer from CH2 group at the center of the heptadione link also plays an important role in the antioxidant properties of curcumin along with that of its phenolic -OH group. In addition, we also show that the conversion of 1, 3-dicarbonyl moiety of curcumin to an isosteric heterocycle as in pyrazole curcumin, which decreases its rotational freedom, leads to an improvement of its redox properties as well as its antioxidant activity. (C) 2014 Elsevier Ltd. All rights reserved.

Analogous stress and electric field driven structural transformation and decrease in polarization coherence on poling around the morphotropic phase boundary in BiScO3-PbTiO3

The nature of the stress and electric field driven structural and microstructural transformations in the morphotropic phase boundary (MPB) compositions of the high Curie point piezoelectric system BiScO3-PbTiO3 has been examined by ex situ based techniques. Using a powder poling technique, which is based on the concept of exploiting the irreversible structural change that occurs after the application of a strong electric field and stress independently, it was possible to ascertain that both moderate stress and electric field induce identical structural transformation-a fraction of the monoclinic phase transforms irreversibly to the tetragonal phase. Moreover, analysis of the dielectric response before and after poling revealed a counterintuitive phenomenon of poling induced decrease in the spatial coherence of polarization for compositions around the MPB and not so for compositions far away from the MPB range. Exploiting the greater sensitivity of this technique, we demonstrate that the criticality associated with the interferroelectric transition spans a wider composition range than what is conventionally reported in the literature based on bulk x-ray/neutron powder diffraction techniques.

Structural, magnetic and electrochemical investigation of novel binary Na2-x(Fe1-yMny)P2O7 (0 <= y <= 1) pyrophosphate compounds for rechargeable sodium-ion batteries

Pyrophosphate cathodes have been recently reported as a competent family of insertion compounds for sodium-ion batteries. In the current study, we have investigated the binary Na2 - x(Fe1 - yMny)P2O7 (0 <= y <= 1) pyrophosphate family, synthesized by the classical solid-state method. They form a continuous solid solution maintaining triclinic P-1 (#2) symmetry. The local structural coordination differs mainly by different degrees of Na site occupancy and preferential occupation of the Fe2 site by Mn. The structural and magnetic properties of these mixed-metal pyrophosphate phases have been studied. In each case, complete Fe3+/Fe2+ redox activity has been obtained centered at 3 V vs. Na. The Fe3+/Fe2+ redox process involves multiple steps between 2.5 and 3 V owing to Na-cation ordering during electrochemical cycling, which merge to form a broad single Fe3+/Fe2+ redox peak upon progressive Mn-doping. (C) 2014 Elsevier B.V. All rights reserved.

Polarization switching and high piezoelectric response in Sn-modified BaTiO3

BaTiO3 is shown to exhibit anomalous piezoelectric response, comparable to that of lead-zirconate titanate, by dilute Sn modification (1-4 mol%). Using a newly discovered powder poling technique it is shown that the mechanism associated with this anomalous strain response involves electric-field-induced switching of polarization vector from 001] towards 101] pseudocubic direction. This switchability is significantly enhanced by tuning the tetragonal-orthorhombic first-order criticality near to room temperature.

Synthesis, crystal structure and spectroscopic and electrochemical properties of bridged trisbenzoato copper-zinc heterobinuclear complex of 2,2 `-bipyridine

The synthesis of the heterobinuclear copper-zinc complex CuZn(bz)(3)(bpy)(2)]ClO4 (bz = benzoate) from benzoic acid and bipyridine is described. Single crystal X-ray diffraction studies of the heterobinuclear complex reveals the geometry of the benzoato bridged Cu(II)-Zn(II) centre. The copper or zinc atom is pentacoordinate, with two oxygen atoms from bridging benzoato groups and two nitrogen atoms from one bipyridine forming an approximate plane and a bridging oxygen atom from a monodentate benzoate group. The Cu-Zn distance is 3.345 angstrom. The complex is normal paramagnetic having mu(eff) value equal to 1.75 BM, ruling out the possibility of Cu-Cu interaction in the structural unit. The ESR spectrum of the complex in CH3CN at RT exhibit an isotropic four line spectrum centred at g = 2.142 and hyperfine coupling constants A(av) = 63 x 10(-4) cm(-1), characteristic of a mononuclear square-pyramidal copper(II) complexes. At LNT, the complex shows an isotropic spectrum with g(parallel to) = 2.254 and g(perpendicular to) =2.071 and A(parallel to) = 160 x 10(-4) cm(-1). The Hamiltonian parameters are characteristic of distorted square pyramidal geometry. Cyclic voltammetric studies of the complex have indicated quasi-reversible behaviour in acetonitrile solution. (C) 2014 Elsevier B.V. All rights reserved.

Structural investigation of resorcinol based symmetrical banana mesogens by XRD, NMR and polarization measurements

Synthesis and structural characterization of two novel symmetrical banana mesogens built from resorcinol with seven phenyl rings linked by ester and imine with a terminal dodecyl/dodecyloxy chain has been carried out. Density functional theory (DFT) has been employed for obtaining the geometry optimized structures, the dipole moments and C-13 NMR chemical shifts. The HOPM and DSC studies revealed enantiotropic B-2 and B-7 phases for the dodecyl and dodecyloxy homologs respectively. The powder X-ray studies of both the mesogens indicate the presence of layer ordering. The polarization measurements reveal an anti-ferroelectric switching for the B-2 phase of the dodecyl homolog whose structure has been identified as SmCSPA. The B-7 phase of the dodecyloxy homolog was found to be non-switchable. High resolution C-13 NMR study of the dodecyl homolog in its mesophase has been carried out. C-13-H-1 dipolar couplings obtained from the 2-dimensional separated local field spectroscopy experiment were used to obtain the orientational order parameters of the different segments of the mesogen. Very large C-13-H-1 dipolar couplings observed for the carbons of the central phenyl ring (9.7-12.3 kHz) in comparison to the dipolar couplings of those of the side arm phenyl rings (less than 3 kHz) are a direct consequence of the ordering in the banana phase and the shape of the molecule. From the ratio of the local order parameter values, the bent-angle of the mesogen could be determined in a straight forward manner to be 120.5 degrees.

Effect of radio frequency power and thickness on the electrochemical properties of Li2-x MnO3-y thin films

In the present work, Li2-x MnO3-y (LMO) thin films have been deposited by radio frequency (RF) reactive magnetron sputtering using acid-treated Li2MnO3 powder target. Systematic investigations have been carried out to study the effect of RF power on the physicochemical properties of LMO thin films deposited on platinized silicon substrates. X-ray diffraction, electron microscopy, surface chemical analysis and electrochemical studies were carried out for the LMO films after post deposition annealing treatment at 500 A degrees C for 1 h in air ambience. Galvanostatic charge discharge studies carried out using the LMO thin film electrodes, delivered a highest discharge capacity of 139 mu Ah mu m(-1) cm(-2) in the potential window 2.0-3.5 V vs. Li/Li+ at 100 W RF power and lowest discharge capacity of 80 mu Ah mu m(-1) cm(-2) at 75 W RF power. Thereafter, the physicochemical properties of LMO films deposited using optimized RF power 100 W on stainless steel substrates has been studied in the thickness range of 70 to 300 nm as a case study. From the galvanostatic charge discharge experiments, a stable discharge capacity of 68 mu Ah mu m(-1) cm(-2) was achieved in the potential window 2.0-4.2 V vs. Li/Li+ tested up to 30 cycles. As the thickness increased, the specific discharge capacity started reducing with higher magnitude of capacity fading.

Preferential polarization and its reversal in polycrystalline BiFeO3/La0.5Sr0.5CoO3 heterostructures

Polycrystalline BiFeO3 thin films were grown on La0.5Sr0.5CoO3 buffered Pt (200)/TiO2/SiO2/Si substrates under different oxygen partial pressures (10, 25, 50 and 100 mTorr) by puked laser ablation. Piezo-response Force Microscopy and Piezo-Force Spectroscopy have shown that all the films are ferroelectric in nature with locally switchable domains. It has also revealed a preferential downward domain orientation in as-grown films grown under lower oxygen partial pressure (10 and 25 mTorr) with a reversal of preferential domain orientation as the oxygen partial pressure is increased to 100 mTorr during laser ablation. Such phenomena are atypical of multi-grained polycrystalline ferroelectric films and have been discussed On the basis of detect formation with changing growth conditions. For the 50 mTorr grown film, asymmetric domain stability and retention during write-read studies has been observed which is attributed to grain-size-related defect concentration, affecting pinning centres that inhibit domain wall motion. (C) 2015 Elsevier Ltd. All rights reserved.

Electrochemical exfoliation of graphite to produce graphene using tetrasodium pyrophosphate

An electrochemical exfoliation based synthetic methodology to produce graphene is provided. An eco-friendly and non-toxic tetrasodium pyrophosphate solution in which the pyrophosphate anion acts as an intercalating ion was used as the electroactive media. Five different ion intercalation potentials were used. Characterization by microscopy, X-ray diffraction, Raman spectroscopy and UV-Visible spectroscopic techniques confirmed that all the potentials produced nano to micrometer sized graphene sheets. No trace of graphene oxide was detected. It was observed that (i) an increase in the intercalation potential increased the graphene yield and (ii) the defect density of graphene did not change significantly with a change in the intercalation potential.

A Comparative Study on Electrochemical Behaviour of Co3O4 and Co3O4-MWCNTs for Supercapacitors

Co3O4 and Co3O4/MWCNTs were prepared by hydrothermal process under autogenous pressure in Teflon lined autoclave and calcined at 250 degrees C. Both samples were characterized by PXRD, FT-IR, SEM-EDS, TEM & FT-Raman to evaluate their surface and bulk properties. The PXRD pattern of the materials indicated the formation of cubic phase of Co3O4. FT-IR results showed the presence of metal oxygen bond in the samples. The SEM and TEM images of the Co3O4 / MWCNTs indicated spherical and cubic aggregates of metal oxide particles (10-30 nm) decorated both on the surface and inside the tubes of carbon nanotubes. The characteristic Ig and Id (graphitic and defects) Raman bands indicated the retention of tubular structure of MWCNTs even after the deposition of Co3O4. The calcined Co3O4-MWCNTs composites and Co3O4 exhibited specific capacitance of 284 & 205 F/g at a sweep rate of 2mVs(-1) in 6M KOH by cyclic voltammetry. The psuedocapacitance performances of calcined Co3O4-MWCNTs were found to be better than Co3O4. Chronopotentiometric studies made for the materials at a current density of 500mA/g indicated 100% columbic efficiency at 2000th cycle for Co3O4/ MWCNTs which is a better electrode material than Co3O4.

Sulfate Chemistry for High-Voltage Insertion Materials: Synthetic, Structural and Electrochemical Insights

Rechargeable batteries based on Li and Na ions have been growing leaps and bounds since their inception in the 1970s. They enjoy significant attention from both the fundamental science point of view and practical applications ranging from portable electronics to hybrid vehicles and grid storage. The steady demand for building better batteries calls for discovery, optimisation and implementation of novel positive insertion (cathode) materials. In this quest, chemists have tried to unravel many future cathode materials by taking into consideration their eco-friendly synthesis, material/process economy, high energy density, safety, easy handling and sustainability. Interestingly, sulfate-based cathodes offer a good combination of sustainable syntheses and high energy density owing to their high-voltage operation, stemming from electronegative SO42- units. This review delivers a sneak peak at the recent advances in the discovery and development of sulfate-containing cathode materials by focusing on their synthesis, crystal structure and electrochemical performance. Several family of cathodes are independently discussed. They are 1) fluorosulfates AMSO(4)F], 2) bihydrated fluorosulfates AMSO(4)F2H(2)O], 3) hydroxysulfate AMSO(4)OH], 4) bisulfates A(2)M(SO4)(2)], 5) hydrated bisulfates A(2)M(SO4)(2)nH(2)O], 6) oxysulfates Fe-2(SO4)(2)O] and 7) polysulfates A(2)M(2)(SO4)(3)]. A comparative study of these sulfate-based cathodes has been provided to offer an outlook on the future development of high-voltage polyanionic cathode materials for next-generation batteries.

Electrochemical exfoliation of graphite for producing graphene using saccharin

A green electrochemical exfoliation route to produce graphene from graphite electrode has been provided. Saccharin which is a non-toxic and biocompatible artificial sweetener was used as an intercalating agent in aqueous media. Graphene samples were produced using five different exfoliation potentials. Microscopic and spectroscopic analysis confirmed the presence of few layer graphene sheets in as-exfoliated product. Important observations made were: (a) graphene layers from nano-to-micro meter sizes were produced; (b) number of graphene layers decreased with increase in the intercalation potential, (c) yield of graphene increased with increase in the exfoliation potential and (d) defect density in the exfoliated graphene layer was sensitive to the exfoliation potential in a way that with increase in the exfoliation potential the defect density initially increased and then eventually decreased.

Synergistic effect of colchicine and iodide ions on the corrosion of mild steel in 0.5 M H2SO4

The inhibition behavior of colchicine (CC) on the corrosion of mild steel in 0.5 M H2SO4 was evaluated by electrochemical methods such as potentiodynamic polarization and electrochemical impedance spectroscopic measurements. The inhibition efficiency increases with increasing concentration of CC. The potentiodynamic polarization results reveal that CC act as a mixed-type inhibitor by retarding both cathodic and anodic corrosion reactions. Additionally, the synergism was carried out between CC and KI to improve the corrosion inhibition behavior of CC on mild steel. The adsorption of both CC alone and the combined inhibitor (CC + KI) on mild steel surface follows Langmuir adsorption isotherm. The synergism parameter (S (theta) ) was calculated to recognize the existence of synergism between CC and iodide ions. Lastly, an adsorption mechanism of CC molecules with iodide ions is discussed.