Metal-organic chemical vapor-deposited cobalt oxide films as negative electrodes for thin film Li-ion battery

In this study, thin films of cobalt oxide (Co3O4) have been grown by the metal-organic chemical vapor deposition (MOCVD) technique on stainless steel substrate at two preferred temperatures (450 degrees C and 500 degrees C), using cobalt acetylacetonate dihydrate as precursor. Spherical as well as columnar microstructures of Co3O4 have been observed under controlled growth conditions. Further investigations reveal these films are phase-pure, well crystallized and carbon-free. High-resolution TEM analysis confirms that each columnar structure is a continuous stack of minute crystals. Comparative study between these Co3O4 films grown at 450 degrees C and 500 degrees C has been carried out for their application as negative electrodes in Li-ion batteries. Our method of electrode fabrication leads to a coating of active material directly on current collector without any use of external additives. A high specific capacity of 1168 micro Ah cm(-2) mu m(-1) has been measured reproducibly for the film deposited at 500 degrees C with columnar morphology. Further, high rate capability is observed when cycled at different current densities. The Co3O4 electrode with columnar structure has a specific capacity 38% higher than the electrode with spherical microstructure (grown at 450 degrees C). Impedance measurements on the Co3O4 electrode grown at 500 degrees C also carried out to study the kinetics of the electrode process. (C) 2014 Published by Elsevier B.V.

A novel interferometric technique to estimate thermal diffusivity of `optically transparent solid' using `Isothermal surface velocimetry'

One-dimensional transient heat flow is interpreted as a procession of `macro-scale translatory motion of indexed isothermal surfaces'. A new analytical model is proposed by introducing velocity of isothermal surface in Fourier heat diffusion equation. The velocity dependent function is extracted by revisiting `the concept of thermal layer of heat conduction in solid' and `exact solution' to estimate thermal diffusivity. The experimental approach involves establishment of 1 D unsteady heat flow inside the sample through Step-temperature excitation. A novel self-reference interferometer is utilized to separate a `unique isothermal surface' in time-varying temperature field. The translatory motion of the said isothermal surface is recorded using digital camera to estimate its velocity. From the knowledge of thermo-optic coefficient, temperature of the said isothermal surface is predicted. The performance of proposed method is evaluated for Quartz sample and compared with literature.

Robust, metallic Pd17Se15 and Pd7Se4 phases from a single source precursor and their use as counter electrodes in dye sensitized solar cells

Thin films of conducting palladium selenide phases (Pd17Se15 and Pd7Se4) are prepared using a single source molecular precursor by thermolysis. Varying the mole ratios of palladium and selenium precursors results in palladium organo-selenolate complexes which on thermolysis at different temperatures yield Pd17Se15 and Pd7Se4 phases that are very stable and adherent to the substrate. The organo-selenolate complexes are characterized using small angle XRD, Se-77 NMR and thermogravimetric analysis (TGA). The palladium selenide films are characterized by various techniques such as XRD, XPS, TEM and SEM. Electrical conductivities of the films are determined using the four probe method. The strong adherence of the films to glass substrates coupled with high corrosion resistant behavior towards strong acid and alkaline environments render them to be very effective as electrocatalysts. The catalytic activity towards the I-3(-)/I- redox couple, which is an important reaction in the regeneration of the dye in a dye-sensitized solar cell, is studied. Between the two phases, the Pd17Se15 film shows superior activity as the counter electrode for dye sensitized solar cells with a photocurrent conversion efficiency of 7.45%.

Modeling of Effect of Nucleation Rate and Electrodes' Resistance on Discharge Characteristics of Lead-Acid Batteries

Classical models are not successful in describing discharge characteristics of a lead-acid battery when the current density is varied over a wide range. A model is developed in this work to overcome this lacuna by introducing into the standard models two mechanisms that have not been used earlier. Lead sulfate particles nucleate and grow on active materials of electrodes during discharge, resulting in coverage of active area. Increasing rate of discharge builds supersaturation of lead sulfate rapidly, and causes increased extents of nucleation and coverage. Electrodes behave almost like an insulator due to deposition of lead sulfate when active materials are converted to a critical extent, and this can stop discharge process. Influence of this mechanism is also rate dependent. The new model developed is tested against data on polarization behavior, and capacity drawn as a function of current. The model successfully predicts both polarization curves and Peukert behavior. The model is used to predict charge that can be drawn at a current after partial discharge at a different current. Model suggests that altering nucleation behavior can be useful in enhancing capacity available for discharge. (C) 2015 The Electrochemical Society.

In Situ Crystallographic Probing on Ameliorating Effect of Sulfide Additives and Carbon Grafting in Iron Electrodes

Beneficial effects of carbon grafting into the iron active material for rechargeable alkaline-iron-electrodes with and without Bi2S3 additive is probed by in situ X-ray diffraction in conjunction with Extended X-ray Absorption Fine Structure (EXAFS) and electrochemistry. EXAFS data unravel that the composition of pristine active material (PAM) for iron electrodes comprises 87% of magnetite and 13% of alpha-iron while carbon-grafted active material comprises 60% of magnetite and 40% of alpha-iron. In situ XRD patterns are recorded using a specially designed electrochemical cell. XRD data reflect that magnetite present in PAM iron electrode, without bismuth sulfide additive, is not reduced during charging while PAM iron electrode with bismuth sulfide additive is partially reduced to alpha-Fe/Fe(OH)(2). Interestingly, carbon-grafted-iron electrodes with bismuth sulfide exhibit complete conversion of active material to alpha-Fe/Fe(OH)2. The ameliorating effect of carbon grafting is substantiated by kinetic parameters obtained from steady-state potentiostatic polarization and Tafel plots. The mechanism for iron-electrode charge - discharge reactions are discussed in the light of the potential - pH diagrams for Fe - H2O, S - H2O and FeSads - H2O systems and it is surmised that carbon grafting into iron active material promotes its electrochemical utilization. (C) The Author(s) 2015. Published by ECS. All rights reserved.

Diffractive Optical Analysis for Refractive Index Sensing using Transparent Phase Gratings

We report the implementation of a micro-patterned, glass-based photonic sensing element that is capable of label-free biosensing. The diffractive optical analyzer is based on the differential response of diffracted orders to bulk as well as surface refractive index changes. The differential read-out suppresses signal drifts and enables time-resolved determination of refractive index changes in the sample cell. A remarkable feature of this device is that under appropriate conditions, the measurement sensitivity of the sensor can be enhanced by more than two orders of magnitude due to interference between multiply reflected diffracted orders. A noise-equivalent limit of detection (LoD) of 6 x 10(-7) was achieved with this technique with scope for further improvement.

Real-Time Stress Measurements in Germanium Thin Film Electrodes during Electrochemical Lithiation/Delithiation Cycling

An in situ study of stress evolution and mechanical behavior of germanium as a lithium-ion battery electrode material is presented. Thin films of germanium are cycled in a half-cell configuration with lithium metal foil as counter/reference electrode, with 1M LiPF6 in ethylene carbonate, diethyl carbonate, dimethyl carbonate solution (1:1:1, wt%) as electrolyte. Real-time stress evolution in the germanium thin-film electrodes during electrochemical lithiation/delithiation is measured by monitoring the substrate curvature using the multi-beam optical sensing method. Upon lithiation a-Ge undergoes extensive plastic deformation, with a peak compressive stress reaching as high as -0.76 +/- 0.05 GPa (mean +/- standard deviation). The compressive stress decreases with lithium concentration reaching a value of approximately -0.3 GPa at the end of lithiation. Upon delithiation the stress quickly became tensile and follows a trend that mirrors the behavior on compressive side; the average peak tensile stress of the lithiated Ge samples was approximately 0.83 GPa. The peak tensile stress data along with the SEM analysis was used to estimate a lower bound fracture resistance of lithiated Ge, which is approximately 5.3 J/m(2). It was also observed that the lithiated Ge is rate sensitive, i.e., stress depends on how fast or slow the charging is carried out. (C) The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. All rights reserved.

In Situ NMR Insights into the Electrochemical Reaction of Cu3P Electrodes in Lithium Batteries

This study reports a multinuclei in situ (real-time) NMR spectroscopic characterization of the electrochemical reactions of a negative Cu3P electrode toward lithium. Taking advantage of the different nuclear spin characteristics, we have obtained real-time P-31 and Li-7 NMR data for a comprehensive understanding of the electrochemical mechanism during the discharge and charge processes of a lithium battery. The large NMR chemical shift span of P-31 facilitates the observation of the chemical evolutions of different lithiated and delithiated LixCu3-xP phases, whereas the quadrupolar line features in Li-7 enable identification of asymmetric Li sites. These combined NMR data offer an unambiguous identification of four distinct LixCu3-xP phases, Cu3P, Li0.2Cu2.8P, Li2CuP, and. Li3P, and the characterization of their involvement in the electrochemical reactions. The NMR data led us to propose a delithiation process involving the intercalation of metallic Cu-0 atomic aggregates into the Li2CuP structure to form a Cu-0-Li2-xCu1-xP phase. This process might be responsible for the poor capacity retention in Cu3P lithium batteries when cycled to a low voltage.

Fabrication of Microfluidic-Nanofluidic Channels with Integrated Electrodes

We report on the fabrication of microfluidc-nanofluidic channels on Si incorporated with embedded metallic interconnects. The device aids the study of motion of dispersed particles relative to the fluid under the influence of spatially uniform electric field. Optical lithography in combination with focused ion beam technique was used to fabricate the microfluidic-nanofluidic channels, respectively. Focused ion beam technique was also used for embedding the electrodes in the nanochannel. Gold contact pads were deposited using sputtering. The substrate was finally anodically bonded to a glass substrate.