Influence of Oxide Particle Network Morphology on Ion Solvation and Transport in ``Soggy Sand''Electrolytes

The role of oxide surface chemical composition and solvent on ion solvation and ion transport of ``soggy sand'' electrolytes are discussed here. A ``soggy sand'' electrolyte system comprising dispersions of hydrophilic/hydrophobic functionalized aerosil silica in lithium perchlorate methoxy polyethylene glycol solution was employed for the study. Static and dynamic rheology measurements show formation of an attractive particle network in the case of the composite with unmodified aerosil silica (i.e., with surface silanol groups) as well as composites with hydrophobic alkane groups. While particle network in the composite with hydrophilic aerosil silica (unmodified) were due to hydrogen bonding, hydrophobic aerosil silica particles were held together via van der Waals forces. The network strength in the latter case (i.e., for hydrophobic composites) were weaker compared with the composite with unmodified aerosil silica. Both unmodified silica as well as hydrophobic silica composites displayed solid-like mechanical strength. No enhancement in ionic conductivity compared to the liquid electrolyte was observed in the case of the unmodified silica. This was attributed to the existence of a very strong particle network, which led to the ``expulsion'' of all conducting entities from the interfacial region between adjacent particles. The ionic conductivity for composites with hydrophobic aerosil particles displayed ionic conductivity dependent on the size of the hydrophobic chemical moiety. No spanning attractive particle network was observed for aerosil particles with surfaces modified with stronger hydrophilic groups (than silanol). The composite resembled a sol, and no percolation in ionic conductivity was observed.

Metal-ion-ligand interactions in thermotropic liquid crystals

The interactions of lithium perchlorate with ligands such as dimethyl sulphoxide, acetonitrile, pyridine and the Schiff base liquid crystals are investigated. The experiments open a new field for the study of metal-ion-ligand interactions in thermotropic liquid crystals.

HNbWO6 and HTaWO6: Novel layered oxides related to the rutile structure. Synthesis and investigation of ion-exchange and intercalation behaviour

New protonated layered oxides, HMWO6·1.5H2O (M=Nb or Ta), have been synthesized by topotactic exchange of lithium in trirutile LiMWO6 with protons by treatment with dilute HNO3. The tetragonal cell constants are a=4.71 (2) and c=25.70 (8)Å for HNbWO6·1.5H2O and a=4.70 (2) and c=25.75 (9) Å for HTaWO6·1.5H2O. Partially hydrated compounds, HMWO6·0.5H2O and anhydrous compounds, HMWO6 retain the layered structure. The structure of these oxides consists of MWO6 sheets built up of M/W-oxygen octahedra with rutile type corner- and edge-sharing. Interlayer protons in HMWO6 are exchanged with Li+, Na+, K+ and Tl+. HMWO6 exhibit Brønsted acidity intercalating n-alkylamines and pyridine.

Soft matter electrolytes based on polymethylmetacrylate dispersions in lithium bis(trifluoromethanesulfonyl)imide/1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids

Ion transport in a polymer-ionic liquid (IL) soft matter composite electrolyte is discussed here in detail in the context of polymer-ionic liquid interaction and glass transition temperature The dispersion of polymethylmetacrylate (PMMA) in 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF6) and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) resulted in transparent composite electrolytes with a jelly-like consistency The composite ionic conductivity measured over the range -30 C to 60 C was always lower than that of the neat BMITFSI/BMIPF6 and LiTFSI-BMITFSI/LiTFSI-BMIPF6 electrolytes but still very high (>1 mS/cm at 25 degrees C up to 50 wt% PMMA) While addition of LiTFSI to IL does not influence the glass T-g and T-m melting temperature significantly dispersion of PMMA (especially at higher contents) resulted in increase in T-g and disappearance of T-m In general the profile of temperature-dependent ionic conductivity could be fitted to Vogel-Tamman-Fulcher (VTF) suggesting a solvent assisted ion transport However for higher PMMA concentration sharp demarcation of temperature regimes between thermally activated and solvent assisted ion transport were observed with the glass transition temperature acting as the reference point for transformation from one form of transport mechanism to the other Because of the beneficial physico-chemical properties and interesting ion transport mechanism we envisage the present soft matter electrolytes to be promising for application in electrochromic devices (C) 2010 Elsevier Ltd All rights reserved

Dielectric Relaxation Spectroscopy for Evaluation of the Influence of Solvent Dynamics on Ion Transport in Succinonitrile-Salt Plastic Crystalline Electrolytes

Influence of succinonitrile (SN) dynamics on ion transport in SN-lithium perchlorate (LiClO4) electrolytes is discussed here via dielectric relaxation spectroscopy. Dielectric relaxation spectroscopy (similar to 2 x 10(-3) Hz to 3 MHz) of SN and SN-LiClO4 was studied as a function of salt content (up to 7 mol % or 1 M) and temperature (-20 to +60 degrees C). Analyses of real and imaginary parts of permittivity convincingly reveal the influence Of trans gauche isomerism and solvent-salt association (solvation) effects on ion transport. The relaxation processes are highly dependent on the salt concentration and temperature. While pristine SN display only intrinsic dynamics (i.e., trans-gauche isomerism) which enhances with an increase in temperature, SN-LiClO4 electrolytes especially at high salt concentrations (similar to 0.04-1 M) show salt-induced relaxation processes. In the concentrated electrolytes, the intrinsic dynamics was observed to be a function of salt content, becoming faster with an increase in salt concentration. Deconvolution of the imaginary part of the permittivity spectra using Havriliak-Negami (HN) function show a relaxation process corresponding to the above phenomena. The permittivity data analyzed using HN and Kohlrausch-Williams-Watta (KWW) functions show non-Debye relaxation processes and enhancement in the trans phase (enhanced solvent dynamics) as a function of salt concentration and temperature.

Brillouin Scattering Investigation of Solvation Dynamics in Succinonitrile-Lithium Salt Plastic Crystalline Electrolytes

Temperature dependent Brillouin scattering studies have been performed to ascertain the influence of solvent dynamics on ion-transport in succinonitrile-lithium salt plastic crystalline electrolytes. Though very rarely employed, we observe that Brillouin spectroscopy is an invaluable tool for investigation of solvent dynamics. Analysis of various acoustic (long wavelength) phonon modes observed in the Brillouin scattering spectra reveal the influence of trans-gauche isomerism and as well as ion-association effects on ion transport. Although pristine SN and dilute SN-LiClO(4) samples show only the bulk longitudinal-acoustic (LA) mode, concentrated SN-LiClO(4) (similar to 0.3-1 M) electrolytes display both the bulk LA mode as well as salt induced brillouin modes at ambient temperature. The appearance of more than one brillouin mode is attributed to the scattering of light from regions with different compressibilities (''compactness''). Correspondingly, these modes show a large decrease in the full width at half-maximum (abbreviated as nu(f)) as the temperature decreases. Anomalous temperature dependent behavior of nu(f) with addition of salt could be attributed to the presence of disorder or strong coupling with a neighbor. The shape of the spectrum was evaluated using a Lorentzian and Fano line shape function depending on the nature and behavior of the Brillouin modes.

Gray track formation in KTiOPO4 by swift ion irradiation

Potassium titanyl phosphate single crystals were irradiated with 48 MeV lithium ions at fluences varying from 5×1012 to 1016 ions/cm2. The defects created in the crystal have been characterized using x-ray rocking curve measurements, optical transmittance, and photoluminescence spectroscopy. From x-ray rocking curve studies, the full width at half maximum for the irradiated samples was observed to increase, indicating lattice strain caused by the energetic ions. Optical transparency of these samples was found to decrease upon irradiation. The irradiated samples exhibited a broadband luminescence in the 700–900 nm region, for fluences above 5×1013 ions/cm2. The results indicate that ion-beam-induced optical effects in KTiOPO4 single crystals are very similar to the ones obtained for crystals with “gray tracks,” which are attributed to the electronic transitions in the Ti3+ levels.

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.

Polymer template-assisted microemulsion synthesis of large surface area, porous Li2MnO3 and its characterization as a positive electrode material of Li-ion cells

Lithium-rich manganese oxide (Li2MnO3) is prepared by reverse microemulsion method employing Pluronic acid (P123) as a soft template and studied as a positive electrode material. The as-prepared sample possesses good crystalline structure with a broadly distributed mesoporosity but low surface area. As expected, cyclic voltammetry and charge-discharge data indicate poor electrochemical activity. However, the sample gains surface area with narrowly distributed mesoporosity and also electrochemical activity after treating in 4 M H2SO4. A discharge capacity of about 160 mAh g(-1) is obtained. When the acid-treated sample is heated at 300 A degrees C, the resulting porous sample with a large surface area and dual porosity provides a discharge capacity of 240 mAh g(-1). The rate capability study suggests that the sample provides about 150 mAh g(-1) at a specific discharge current of 1.25 A g(-1). Although the cycling stability is poor, the high rate capability is attributed to porous nature of the material.

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.

Helix-sheet interconversion in a synthetic pore lining peptide derived from a designed ion channel

We have designed a four-helix protein that is expected to tetramerize in the membrane to form an ion channel with a structurally well defined pore. A synthetic peptide corresponding to the channel lining helix facilitates ion transport across liposomal membranes and largely helical in membranes. Detailed circular dichroism studies of the peptide in methanol, water and methanal-water mixtures reveal that it is helical in methanol, beta-structured in 97.5% water and a combination of these two structures at intermediate compositions of methanol and water. A fluorescence resonance energy transfer study of the peptide shows that the peptide is monomeric in methanol but undergoes extensive anti-parallel aggregation in aqueous solution.

Synthesis and vesicle formation from hybrid bolaphile/amphiphile ion-pairs. Evidence of membrane property modulation by molecular design

Four new hybrid (bolaphile/amphiphile) ion-pairs were synthesized. Electron microscopy indicated that each of these forms bilayer membranes upon dispersion in aqueous media. Membrane properties have also been examined by differential scanning calorimetry, microcalorimetry, temperature-dependent fluorescence anisotropy measurements, and UV-vis spectroscopy. The T-m values for the vesicular 1, 2, 3, 4, and 5 were 38, 12, 85, 31.3, and 41.6 degrees C, respectively. Interestingly the T-m values for 1 and 3 were found to depend on their concentration. The entrapment of small solute and the release capability have also been examined to demonstrate that these bilayers form enclosed vesicles. X-ray diffraction of the cast films has been performed to understand the nature and the thickness of these membrane organizations. The membrane widths ranged from 33 to 47 Angstrom. Finally, the above observations have been analyzed in light of the results obtained from molecular modeling studies. Thus we have demonstrated that membrane properties can be modulated by simple structural changes at the amphiphile level. It was shown that by judicious incorporation of central, isomeric, disubstituted aromatic units as structural anchors into different bolaphiles, one can modulate the properties of the resulting vesicles.

Void Geometry Driven Spin Crossover in Zeolite-Encapsulated Cobalt Tris(bipyridyl) Complex Ion

The cobalt(II) tris(bipyridyl) complex ion encapsulated in zeolite-Y supercages exhibits a thermally driven interconversion between a low-spin and a high-spin state-a phenomenon not observed for this ion either in solid state or in solution. From a comparative study of the magnetism and optical spectroscopy of the encapsulated and unencapsulated complex ion, supported by molecular modeling, such spin behavior is shown to be intramolecular in origin. In the unencapsulated or free state, the [Co(bipy)(3)](2+) ion exhibits a marked trigonal prismatic distortion, but on encapsulation, the topology of the supercage forces it to adopt a near-octahedral geometry. An analysis using the angular overlap ligand field model with spectroscopically derived parameters shows that the geometry does indeed give rise to a low-spin ground state, and suggests a possible scenario for the spin state interconversion.

Effect of ion nitriding on the microstructure and properties of Maraging steel (250 Grade)

In the present investigation, ion nitriding of Maraging steel (250 grade) has been carried out at three different temperatures i.e., at 435 degrees C, 450 degrees C and 465 degrees C for 10 h duration in order to achieve good wear resistance along with high strength required for the slat track component of aircraft. The microstructure of the base material and the nitrided layer was examined by optical and scanning electron microscope, and various phases present were determined by X-ray diffraction. Various properties, such as, hardness, case depth, tensile, impact, fatigue properties and corrosion resistance were investigated for both un-nitrided and ion-nitrided materials. It is observed that the microstructure of the core material remains unaltered and Fe4N is formed in the hardened surface layer after ion nitriding at all the three temperatures employed. Surface hardness increases substantially after ion nitriding. Surface hardness remains almost the same but case depth increases with the increase in ion nitriding temperature due to greater diffusivity at higher temperatures. Tensile strength, fatigue strength and corrosion resistance are improved but ductility and energy absorbed in impact test decrease on ion nitriding. These results are explained on the basis of microstructural observations. The properties obtained after ion nitriding at 450 degrees C for 10 h are found to be optimum when compared to the other two ion nitriding temperatures.

Enhancement of nonvolatile polarization and pyroelectric sensitivity in lithium tantalate (LT)/poly(vinylidene fluoride) (PVDF) nanocomposite

We report the ferroelectric and pyroelectric properties of the composite films of lithium tantalate (LT) nanoparticle in poly(vinylidene fluoride) PVDF matrix at different volume fractions of LT (f(LT) = 0.047, 0.09 and 0.17). For an applied electric field of 150 kV cm(-1) the nonvolatile polarization of the composite was observed to increase from 0.014 mu C cm(-2) at f(LT) = 0 to 2.06 mu C cm(-2) at f(LT) = 0.17. For f(LT) = 0.17, the composite films exhibit a saturated ferroelectric hysteresis loop with a remanent polarization (2P(r) = 4.13 mu C cm(-2)). Compared with pure poled PVDF the composite films also showed a factor of about five enhancement in the pyroelectric coefficient at f(LT) = 0.17. When used in energy detection mode the pyroelectric voltage sensitivity of the composite films was found to increase from 3.93 to 18.5 VJ(-1) with an increase in f(LT) from 0.0 to 0.17.