The effect of particle size on performance of cathode materials of Li-ion batteries

Beginning with the ‘frog-leg experiment’ by Galvani (1786), followed by the demonstrations of Volta pile by Volta (1792) and lead-acid accumulator by Plante´ (1859), several battery chemistries have been developed and realized commercially. The development of lithium-ion rechargeable battery in the early 1990s is a breakthrough in the science and technology of batteries. Owing to its high energy density and high operating voltage, the Li-ion battery has become the battery of choice for various portable applications such as note-book computers, cellular telephones, camcorders, etc. Huge efforts are underway in succeeding the development of large size batteries for electric vehicle applications. The origin of lithium-ion battery lies in the discovery that Li+-ions can reversibly be intercalated into/de-intercalated from the Van der Walls gap between graphene sheets of carbon materials at a potential close to the Li/Li+ electrode. By employing carbon as the negative electrode material in rechargeable lithium-ion batteries, the problems associated with metallic lithium in rechargeable lithium batteries have been mitigated. Complimentary investigations on intercalation compounds based on transition metals have resulted in establishing LiCoO2 as the promising cathode material. By employing carbon and LiCoO2, respectively, as the negative and positive electrodes in a non-aqueous lithium-salt electrolyte,a Li-ion cell with a voltage value of about 3.5 V has resulted.Subsequent to commercialization of Li-ion batteries, a number of research activities concerning various aspects of the battery components began in several laboratories across the globe. Regarding the positive electrode materials, research priorities have been to develop different kinds of active materials concerning various aspects such as safety, high capacity, low cost, high stability with long cycle-life, environmental compatibility,understanding relationships between crystallographic and electrochemical properties. The present review discusses the published literature on different positive electrode materials of Li-ion batteries, with a focus on the effect of particle size on electrochemical performance.

Protein Model Discrimination Using Mutational Sensitivity Derived from Deep Sequencing

A major bottleneck in protein structure prediction is the selection of correct models from a pool of decoys. Relative activities of similar to 1,200 individual single-site mutants in a saturation library of the bacterial toxin CcdB were estimated by determining their relative populations using deep sequencing. This phenotypic information was used to define an empirical score for each residue (Rank Score), which correlated with the residue depth, and identify active-site residues. Using these correlations, similar to 98% of correct models of CcdB (RMSD <= 4 angstrom) were identified from a large set of decoys. The model-discrimination methodology was further validated on eleven different monomeric proteins using simulated RankScore values. The methodology is also a rapid, accurate way to obtain relative activities of each mutant in a large pool and derive sequence-structure-function relationships without protein isolation or characterization. It can be applied to any system in which mutational effects can be monitored by a phenotypic readout.

Low temperature synthesis of layered NaxCoO2 and KxCoO2 from NaOH/KOH fluxes and their ion exchange properties

We report a low temperature synthesis of layered Na0×20CoO2 and K0×44CoO2 phases from NaOH and KOH fluxes at 400°C. These layered oxides are employed to prepare hexagonal HCoO2, LixCoO2 and Delafossite AgCoO2 phases by ion exchange method. The resulting oxides were characterised by powder X-ray diffraction, X-ray photoelectron spectroscopy, SEM and EDX analysis. Final compositions of all these oxides are obtained from chemical analysis of elements present. Na0×20CoO2 oxide exhibits insulating to metal like behaviour, whereas AgCoO2 is semiconducting.

External-cavity semiconductor laser sensor

The spectral characteristics of a diode laser are significantly affected due to interference caused between the laser diode output and the optical feedback in the external-cavity. This optical feedback effect is of practical use for linewidth reduction, tuning or for sensing applications. A sensor based on this effect is attractive due to its simplicity, low cost and compactness. This optical sensor has been used so far, in different configuration such as for sensing displacement induced by different parameters. In this paper we report a compact optical sensor consisting of a semiconductor laser coupled to an external cavity. Theoretical analysis of the self- mixing interference for optical sensing applications is given for moderate optical feedback case. A comparison is made with our experimental observations. Experimental results are in good agreement with the simulated power modulation based on self-mixing interference theory. Displacements as small as 10-4 nm have been measured using this sensor. The developed sensor showed a fringe sensitivity of one fringe per 400nm displacement for reflector distance of around 10cms. The sensor has also been tested for magnetic field and temperature induced displacement measurements.

Enhanced photoluminescence of Gd2O3:Eu3+ nanophosphors with alkali (M = Li+, Na+, K+) metal ion co-doping

Gd1.95Eu0.4M0.01O3 (M = Li+ Na+ K+) nanophosphors have been synthesized by a low temperature solution combustion (LSC) method. Powder X-ray diffraction pattern (PXRD), scanning electron microscopy (SEM), UV-vis and photoluminescence (PL) measurements were carried out to characterize their structural and luminescent properties. The excitation and emission spectra indicated that the phosphor could be well excited by UV light (243 nm) and emit red light about 612 nm. The effect of alkali co-dopant on PL properties has been examined. The results showed that incorporation of Li+, Na+ and K+ in to Gd2O3:Eu3+ phosphor would lead to a remarkable increase of photoluminescence. The PL intensity of Gd2O3:Eu3+ phosphor was improved evidently by co-doping with Li+ ions whose radius is less than that of Gd3+ and hardly with Na+, K+ whose radius is larger than that of Gd3+. The effect of co-dopants on enhanced luminescence was mainly regarded as the result of a suitable local distortion of crystal field surrounding the Eu3+ activator. These results will play an important role in seeking some more effective co-dopants. (C) 2011 Published by Elsevier B.V.

Nanoindentation response of an ion irradiated Zr-based bulk metallic glass

Nanoindentation experiments were conducted on a Ni+ ion-irradiated Zr-based bulk metallic glass (BMG). The irradiation was carried out using 2.5, 5, 10 and 15 MeV ions and a flux of similar to 10(16) ions/cm(2). Post mortem imaging of the indents reveals a transition in the deformation mechanism of the irradiated regions from heterogeneous shear banding to homogeneous flow. Additionally, the load-displacement curves exhibit a transition from serrated to continuous flow with increasing severity of irradiation damage. The stress-strain response obtained from micro-pillar compression experiments complements the indentation response exhibiting a decrease in the flow stress and an `apparent' strain hardening at the lowest irradiation damage investigated, which is not observed in the as-cast alloy. (C) 2011 Elsevier B.V. All rights reserved.

Ion Transport in Liquid Salt Solutions with Oxide Dispersions:``Soggy Sand'' Electrolytes

``Soggy sand'' electrolyte, which essentially consists of oxide dispersions in nonaqueous liquid salt solutions, comprises an important class of soft matter electrolytes. The ion transport mechanism of soggy sand electrolyte is complex. The configuration of particles in the liquid solution has been observed to depend in a nontrivial manner on various parameters related to the oxide (concentration, size, surface chemistry) and solvent (dielectric constant, viscosity) as well as time. The state of the particles in solution not only affects ionic conductivity but also effectively the mechanical and electrochemical properties of the solid liquid composite. Apart from comprehensive understanding of the underlying phenomena that govern ion transport, which will benefit design of better electrolytes, the problem has far-reaching implications in diverse fields such as catalysis, colloid chemistry, and biotechnology.

Reactive biased target ion beam deposited W-DLC nanocomposite thin films - Microstructure and its mechanical properties

Tungsten incorporated diamond like carbon (W-DLC) nanocomposite thin films with variable fractions of tungsten were deposited by using reactive biased target ion beam deposition technique. The influence of tungsten incorporation on the microstructure, surface topography, mechanical and tribological properties of the DLC were studied using X-ray photoelectron spectroscopy (XPS), Raman spectroscopy. Atomic force microscope (AFM), transmission electron microscopy (TEM), nano-indentation and nano-scratch tests. The amount of W in films gets increases with increasing target bias voltage and most of the incorporated W reacts with carbon to form WC nanoclusters. Using TEM and FFT pattern, it was found that spherical shaped WC nanoclusters were uniformly dispersed in the DLC matrix and attains hexagonal (W2C) crystalline structure at higher W concentration. On the other hand, the incorporation of tungsten led to increase the formation of C-sp(2) hybridized bonding in DLC network and which is reflected in the hardness and elastic modulus of W-DLC films. Moreover, W-DLC films show very low friction coefficient and increased adhesion to the substrate than the DLC film, which could be closely related to its unique nanostructure of the W incorporated thin films. (C) 2011 Elsevier B.V. All rights reserved.

Swift heavy ion induced structural, iono and photoluminescence properties of beta-CaSiO3:Dy3+ nanophosphor

CaSiO3:Dy3+ (1-5 mol%) nanophosphors have been prepared by a low temperature solution combustion method. The structural and luminescence (ionoluminescence; IL and photoluminescence; PL) studies have been carried out for pristine and ion irradiated samples. The XRD patterns of pristine sample show a prominent peak at (320) for the monoclinic structure of beta-CaSiO3. Upon ion irradiation, the intensity of the prominent peak is decreased at the fluence of 7.81 x 10(12) ions cm(-2) and at higher fluence of 15.62 x 10(12) ions cm(-2), the prominent peak completely vanishes. The decrease in peak intensity might be due to the stress induced point defects. On-line IL and in situ PL studies have been carried out on pelletized samples bombarded with 100 MeV Si7+ ions with fluences in the range (7.81-15.62) x 10(12) ions cm(-2). The characteristic emission peaks at 481,574, 664 and 754 nm recorded in both IL and PL are attributed to the luminescence centers activated by Dy3+ ions. It is found that IL and PL emissions intensity decreases with increase in Si7+ ion fluence. The decrease in intensity can be due to the destruction of Si-O-Si and O-Si-O type species present on the surface of the sample. FTIR studies also confirm the Si-O-Si and O-Si-O type species observed to be sensitive for swift heavy ion (SHI) irradiated samples. (C) 2012 Elsevier B.V. All rights reserved.

Lead ion sensor with electrodes modified by imidazole-functionalized polyaniline

Glassy carbon electrodes (GCE) and carbon paste electrodes (CPE) were modified with imidazole functionalized polyaniline with the aim to develop a sensor for lead (II) in both acidic and basic aqueous solution. The electrodes were characterized by cyclic voltammetry and differential pulse adsorptive stripping voltammetry. The limit of detections obtained with glassy carbon electrode and carbon paste electrode are 20 ng mL(-1) and 2 ng mL(-1) of lead ion, respectively. An interference study was carried out with Cd(II), As(III), Hg(II) and Co(II) ions. Cd(II) ions interfere significantly (peak overlap) and As(III) has a depressing effect on the lead signal. The influence of pH was investigated indicating that bare and modified GCE and CPE show optimum response at pH 4.0 +/- 0.05.

Nitrates-melt synthesized LiNi0.8Co0.2O2 and its performance as cathode in Li-ion cells

Layered LiNi0.8Co0.2O2 crystallizing in R (3) over barm space group is synthesized by decomposing the constituent metal-nitrate precursors. Oxidizing nature of metal nitrates stabilizes nickel in +3 oxidation state, enabling a high degree of cation ordering in the layered LiNi0.8Co0.2O2. The powder sample characterized by XRD Rietveld refinement reveals <2% Li-Ni site exchange in the layers. Scanning electron microscopic studies on the as-synthesized LiNi0.8Co0.2O2 sample reflect well defined particles of cubic morphology with particle size ranging between 200 and 250 nm. Cyclic voltammograms suggest that LiNi0.8Co0.2O2 undergoes phase transformation on first charge with resultant phase being completely reversible in subsequent cycles. The first-charge-cycle phase transition is further supported by impedance spectroscopy that shows substantial reduction in resistance during initial de-intercalation. Galvanostatic charge-discharge cycles reflect a first-discharge capacity of 184 mAh g(-1) which is stabilized at 170 mAh g(-1) over 50 cycles.

Flux tube model signals for baryon correlations in heavy ion collisions

The flux tube model offers a pictorial description of what happens during the deconfinement phase transition in QCD. The three-point vertices of a flux tube network lead to formation of baryons upon hadronization. Therefore, correlations in the baryon number distribution at the last scattering surface are related to the preceding pattern of the flux tube vertices in the quark-gluon plasma, and provide a signature of the nearby deconfinement phase transition. I discuss the nature of the expected signal, and how to extract it from the experimental data for heavy ion collisions at RHIC and LHC.

Layer-by-Layer Self-Assembled Metal-Ion- (Ag-, Co-, Ni-, and Pd-) Doped TiO2 Nanoparticles: Synthesis, Characterisation, and Visible Light Degradation of Rhodamine B

Metal-ion- (Ag, Co, Ni and Pd) doped titania nanocatalysts were successfully deposited on glass slides by layer-by-layer (LbL) self-assembly technique using a poly(styrene sulfonate sodium salt) (PSS) and poly(allylamine hydrochloride) (PAH) polyelectrolyte system. Solid diffuse reflectance (SDR) studies showed a linear increase in absorbance at 416 nm with increase in the number of m-TiO2 thin films. The LbL assembled thin films were tested for their photocatalytic activity through the degradation of Rhodamine B under visible-light illumination. From the scanning electron microscope (SEM), the thin films had a porous morphology and the atomic force microscope (AFM) studies showed ``rough'' surfaces. The porous and rough surface morphology resulted in high surface areas hence the high photocatalytic degradation (up to 97% over a 6.5 h irradiation period) using visible-light observed. Increasing the number of multilayers deposited on the glass slides resulted in increased film thickness and an increased rate of photodegradation due to increase in the availability of more nanocatalysts (more sites for photodegradation). The LbL assembled thin films had strong adhesion properties which made them highly stable thus displaying the same efficiencies after five (5) reusability cycles.

One step synthesis of monoclinic VO2 (B) bundles of nanorods: Cathode for Li ion battery

One of the metastable phases of vanadium dioxide, VO2(B) bundles of nanorods and microspheres have been synthesized through a simple hydrothermal method by dispersing V2O5 in aqueous quinol. The obtained products were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and electrochemical discharge-charge test for lithium battery. It was found that the morphologies of the obtained VO2(B) can be tuned by manipulating the relative amount of quinol. The electrochemical test found that the bundles of nanorods exhibit an initial discharge capacity of 171 mAh g(-1) and its almost stabilized capacity was reached to 108 mAh g(-1) after 47 cycles at a current density of 0.1 mA g(-1). The formation mechanism of the VO2(B) bundles of nanorods and microspheres was also discussed. (C) 2012 Elsevier Inc. All rights reserved.