Effect of SO<Subscript>2</Subscript> and CO<Subscript>2</Subscript> additives on the cycle performances of commercial lithium-ion batteries

The effects of SO₂ and CO₂ additives in electrolytes on the cycle properties of liquid-state Al-plastic film lithium-ion batteries were first investigated. The experimental electrolytes were added with different amounts of SO₂ and CO₂. The baseline electrolyte was 1 mol L⁻¹ LiPF₆ in ethylene carbonate/dimethylcarbonate/ethyl-methyl carbonate (1:1:1, by volume), and graphite was used as anode. The main analysis tools were cycling test, rate capability, internal resistance test, low-temperature performance, and thermal stability. The results showed that both of the additives could promote to form an excellent solid electrolyte interface film on the surface of graphite anode, leading to excellent cycle performances, the capacity retentions of CO₂ and S5 were 94% and 97% after 400 cycles, respectively. Besides, the results also exhibited that the electrochemical performances of internal resistance, rate capability, low-temperature performance, and thermal stability were not changed significantly by the use of SO₂ and CO₂ as electrolyte additives.     

Semiconducting SnO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> (S-T) composites for detection of SO<Subscript>2</Subscript> gas

SnO₂-TiO₂ (S-T) composites with different molar ratios were prepared by mechanical mixing followed by sintering at 700 °C for 4 h in air. The structural and microstructural properties of the composites were investigated using powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM). S-T composites were investigated by introducing SO₂ to test their chemical stability using PXRD and SEM coupled with energy dispersive X-ray (EDX) analysis. The sensing performance was measured at different temperatures using various SO₂ concentrations (10–100 ppm). A composite comprising 25 mol% of SnO₂ and 75 mol% TiO₂ (S25-T75) exhibited the highest sensitivity comparing to other S-T composites studied under the presently investigated conditions. t ₉₀ (90 % of response time) was found to be ～5 min for thick pellet (~2 mm in thickness). SO₂ sensing mechanism has been explained through the band structure model.     

Electrical properties of Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>-based composite systems

Composite electrolytes are well-known multiphase systems and exhibit maxima in the conductivity at certain second-phase concentration. An attempt has been made to investigate a number of sodium sulfate (Na₂SO₄)-based composite systems. The dispersoids that have been used are MgO, Al₂O₃, and SiO₂. The samples have been characterized using impedance spectroscopy, X-ray diffraction, and differential scanning calorimetry. The maximum conductivity has been observed for MgO dispersed system, and the percolation threshold has been observed at 30-mol% dispersoid, MgO concentration. Interestingly, two maxima have been observed in case of the Na₂SO₄–SiO₂ and Na₂SO₄–Al₂O₃ composite systems. In the Na₂SO₄–SiO₂ system, the first maximum occurs at lower concentration, i.e., in the range between 10 and 20 mol%, whereas the second occurs at the 40-mol% dispersoid concentration. For the Na₂SO₄–Al₂O₃ system, although slightly indistinguishable, two peaks in the conductivity vs composition plot have been observed around 12- and 30-mol% Al₂O₃ concentrations.     

Calculation of the growth kinetics and dispersity of K<Subscript>2</Subscript>SO<Subscript>4</Subscript> crystals in drops of an evaporating solution

Experimental data on the evaporation kinetics of saturated K₂SO₄ solution drops and the nucleation kinetics of the first crystals are used to develop a simple procedure for the calculation of the solution concentration and the number, size, and dispersity of growing crystals. The calculation results agree well with the experimental data on the growth kinetics of K₂SO₄ crystals and their dispersity after complete evaporation of water. The dispersity of crystals is shown to linearly depend on the reciprocal time of evaporation of drops having different initial heights.     

Effect of uniaxial pressure on the infrared spectra of (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>SO<Subscript>4</Subscript> crystals

The infrared reflectance spectra of a mechanically free or uniaxial-pressure-confined (NH₄)₂SO₄ crystal were studied for the first time in the spectral range 800–1700 cm^?1 in three crystallographic directions. Using the Kramers-Kronig relations, the dispersion and pressure dependences of the following quantities are obtained: the index of refraction n, the real (?₁) and imaginary (?₂) parts of the permittivity, the frequencies of longitudinal (ω_LO) and transverse (ω_TO) optical vibrations, the damping constant γ, and the oscillator strength f of the mechanically free or clamped (NH₄)₂SO₄ crystal. A considerable change in the main reflection bands with pressure was observed, which is due to the effect of uniaxial pressure on the NH₄ and SO₄ tetrahedral frames.     

Cold SO<Subscript>2</Subscript> molecules by Stark deceleration

We produce SO₂ molecules with a centre of mass velocity near zero using a Stark decelerator. Since the initial kinetic energy of the supersonic SO₂ molecular beam is high, and the removed kinetic energy per stage is small, 326 deceleration stages are necessary to bring SO₂ to a complete standstill, significantly more than in other experiments. We show that in such a decelerator possible loss due to coupling between the motional degrees of freedom must be considered. Experimental results are compared with 3D Monte-Carlo simulations and the quantum state selectivity of the Stark decelerator is demonstrated.     

First-principles calculations of SO<Subscript>2</Subscript> sensing with Si nanowires

High chemical reactivity and large surface-to-volume ratio have recently led to growinginterest in the employment of silicon nanowires (SiNWs) in sensing applications forchemical species detection. The working principle of SiNWs sensors resides in thepossibility to induce modifications in their electronic properties via molecularinteraction. A detailed analysis of the interaction of Si with molecular compounds is thenrequired to design and optimize NW-based sensors. Here we study the mechanisms ofadsorption on SiNWs of SO₂, an air pollutant with pernicious effects on humans.First-principles density-functional calculations are performed to calculate the electronicstructure of a SO₂molecule adsorbed at a silicon surface in case of undoped substrate and in presence ofsubstitutional subsurface and deep boron impurities. Comparing the results with the caseof NO₂ adsorption –a similar molecule that, nonetheless has a very different interaction with a Si surface –,we show the specific traits of SO₂ interaction: formation of localized states in theband-gap and absence of reactivation of pre-existing and passivated sub-surfaceimpurities. A connection between the modifications in the system electronic structure andthe strength of the molecular interaction is discussed.     

Effect of molecular weight of PMMA on the conductivity and viscosity behavior of polymer gel electrolytes containing NH<Subscript>4</Subscript>CF<Subscript>3</Subscript>SO<Subscript>3</Subscript>

The addition of polymethyl methacrylate (PMMA) having different molecular weights to electrolytes containing ammonium trifluoromethanesulfonate (NH₄CF₃SO₃) in diethyl carbonate (DEC) has been found to result in conductivity enhancement and to yield gel electrolytes with conductivity higher than the corresponding liquid electrolytes. The increase in conductivity has been found to be due to the dissociation of undissociated NH₄CF₃SO₃ and ion aggregates present in the electrolytes, and this has been supported by Fourier transform infrared spectroscopy results, which suggests active interaction of PMMA and NH₄CF₃SO₃ in these gel electrolytes. The increase in conductivity also depends upon the molecular weight of the polymer used and is relatively more for PMMA having lower molecular weight. The increase in viscosity with PMMA addition also depends upon the molecular weight of the polymer and is closely related to the conductivity behavior of these electrolytes. Polymer gel electrolytes have been found to be thermally stable up to a temperature of 125 °C.     

Morphology-controlled PANI nanowire electrode by using deposition scan rate in H<Subscript>2</Subscript>SO<Subscript>4</Subscript>/PVA polymer electrolyte for electrochemical capacitor

Polyaniline (PANI) nanowire electrode was successfully prepared using electrodeposition method. The morphology, thickness, and electrochemical performance of PANI electrode can be controlled by varying the deposition scan rates. Lower deposition scan rate results in compact and aggregates of PANI nanowire morphology. The uniform nanowire of PANI was obtained at the applied scan rate of 100 mV s^?1, and it was used as symmetric electrode coupled with H₂SO₄/polyvinyl alcohol (PVA) gel electrolyte. The different concentrations of H₂SO₄ acid in polymer electrolyte have influenced the electrochemical performance as well. The optimum specific capacitance and energy density of P100 PANI electrode in 3 M H₂SO₄/PVA gel polymer electrolyte was 377 F g^?1 and 95.4 Wh kg^?1 at the scan rate of 1 mV s^?1. The good stability of the electrode in this system is applicable to many wearable electronics applications.     

The synthesis of (Y<Subscript>1-x</Subscript>Gd<Subscript>x</Subscript>)<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu phosphor particles by flame spray pyrolysis with LiCl flux

(Y_1-xGd_x)₂O₃:Eu phosphor particles with dense morphology were prepared by flame spray pyrolysis and the effect of LiCl flux on the crystallinity, morphology, and photoluminescence characteristics of the particles was investigated. All as-prepared particles had monoclinic phase regardless of flux and had different luminescence characteristics from those of commercial Y₂O₃:Eu particles of cubic phase. The addition of LiCl flux reduced the post-treatment temperature by 300 °C for phase transformation from the monoclinic phase to the cubic phase. The post-treatment temperature of (Y_0.75Gd_0.25)₂O₃:Eu particles for phase transformation decreased from 1100 °C to 700 °C when LiCl flux was used. The morphology of the particles was also influenced by the Y/Gd ratio and the LiCl flux. The as-prepared particles had spherical shape and non-aggregation characteristics regardless of Y/Gd ratio and flux. The sphericity of the as-prepared particles prepared without flux was maintained after post-treatment for phase transformation in all Y/Gd ratios. However, LiCl addition promoted the aggregation between product particles. The prepared particles had high photoluminescence intensities comparable to that of the commercial product. PACS 64.70.Kb; 78.55.-m; 81.20.Rg; 75.50.Tt     

The Effect of Uniaxial Pressures on the Infrared Spectra of LiNH<Subscript>4</Subscript>SO<Subscript>4</Subscript> Crystals

The infrared reflection spectra of mechanically free and uniaxially compressed LiNH₄SO₄ crystals are studied for the first time in the spectral range of 800–1700 сm^–1 along three crystallophysical directions. The Kramers–Kronig dispersion relations are used to determine the dispersion and baric dependences of refractive index n and the real ε₁ and imaginary ε₂ parts of the dielectric constant and to calculate the frequencies of longitudinal ω_LO and transverse ω_ТO vibrations, decay constant γ, and oscillator strength f of mechanically free and compressed LiNH₄SO₄ crystals. The considerable changes observed in the main reflection bands are explained by the effect of uniaxial pressures on the NH₄ and SO₄ tetrahedra.     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanofiller on the electrical,thermal and structural properties of PEO:PPG based nanocomposite polymer electrolyte

A new series of nanocomposite polymer electrolyte (NCPE) system comprising of polyethylene oxide (PEO) and polypropylene glycol (PPG) as blended polymer host, zinc trifluoromethanesulfonate [Zn(CF₃SO₃)₂] as dopant salt and nanocrystalline alumina [Al₂O₃] as filler was prepared by solution casting technique. The present system consisting of five different compositions of 87.5 wt% (PEO:PPG)–12.5 wt% Zn(CF₃SO₃)₂ + x wt% Al₂O₃ [where x = 1, 3, 5, 7 and 9, respectively] has been thoroughly characterized by various analytical techniques such as electrical impedance spectroscopy, X-ray diffraction (XRD) studies, differential scanning calorimetry (DSC), scanning electron microscopic (SEM) analysis and linear sweep voltammetry (LSV). The maximum room temperature ionic conductivity exhibited by the NCPE was found to be 2.1 × 10^?4 S cm^?1 for 3 wt% loading of Al₂O₃ which is an order higher than that of the optimized filler-free zinc salt doped polymer electrolyte system at 298 K. The evidence of a decrease in the degree of crystallinity responsible for the enhanced conductivity was revealed by the XRD data and further confirmed by DSC and SEM results. Moreover, the electrochemical stability window of the highly conducting electrolyte matrix has been experimentally determined by linear sweep voltammetry and found to be 3.6 V which is fairly adequate for the construction of zinc primary batteries as well as zinc-based rechargeable batteries at ambient conditions.     

Preparation of RE<Subscript>2</Subscript>O<Subscript>2</Subscript>SO<Subscript>4</Subscript> (RE=La,Pr-Lu) microspheres from rare-earth-based infinite coordination polymers

Rare-earth-based infinite coordination polymer (RE-ICP) spheres with diameters ranging from 50 nm to 2 μm have been prepared using meso-2,3-dimercaptosuccinic acid (DMSA) as ligand under hydrothermal conditions. RE₂O₂SO₄ microspheres with similar morphology were obtained by calcining the corresponding RE-ICP spheres. However, as for Ce-ICP and Sc-ICP, CeO₂ and Sc₂O₃ were obtained. The products were characterized using X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, infrared spectroscopy, laser Raman spectrometry, and energy-dispersive X-ray spectrum. Elemental analysis and inductive coupled plasma atomic emission spectrometer were adopted to study the composition of the Eu-ICP. To explore their potential applications, several samples of the products were selected and their properties were investigated. The Eu-ICP and Eu₂O₂SO₄ microspheres give strong red emissions when excited with a 394-nm ultraviolet light. Furthermore, the Eu-ICP displays a high selectivity for Fe(III). The obtained CeO₂ has a strong absorption in the UV region and the Gd₂O₂SO₄ microspheres show paramagnetic behavior.

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Graphical abstract A series of RE₂O₂SO₄ microspheres were prepared using a coordination polymer precursor method.

     

Nonempirical calculation of linear and nonlinear polarizability of TeO<Subscript>2</Subscript>-based molecular clusters and piezoelectric properties of crystalline tellurium oxide

Polarization characteristics of the paratellurite TeO₂ crystal were studied in the model of the molecular cluster represented by the (TeO₂)₃ molecular chain. Nonempirical calculations of linear and nonlinear polarizability reveal a steep growth of the second hyperpolarizability when passing on from the single TeO₂ molecule to the molecular chain (TeO₂)₃, which may be related to intermolecular contacts. Linear polarizability of isostructural molecules SO₂, SeO₂, and TeO₂ have an equal order of magnitude, while the second hyperpolarizability of TeO₂ is somewhat higher than that of SeO₂ and exceeds the SO₂ polarizability by an order of magnitude.     

Oxidation of hydrogen sulfide and corrosion of stainless steel in gas mixtures containing H<Subscript>2</Subscript>S,O<Subscript>2</Subscript>, H<Subscript>2</Subscript>O,and CO<Subscript>2</Subscript>

The composition of volatile and solid products of oxidation of hydrogen sulfide and stainless steel in gas mixtures containing H₂S, O₂, H₂O, and CO₂ has been determined using mass spectrometry, x-ray diffraction analysis, and scanning electron microscopy. It has been shown that holding an H₂S–O₂ mixture at 301 K results in prevailing formation of elemental sulfur and iron sulfides in the form of porous hygroscopic crust on the reactor wall surface. Formation of gas-phase sulfur causes self-acceleration of the oxidation of hydrogen sulfide; the resulting water triggers corrosion of the reactor wall. Heating of the resulting sulfur-sulfide crust in O₂ medium is accompanied by formation of SO₂ and heat release at T > 508 K. After heating of the H₂S–CO₂ mixture to 615 K, H₂ and COS were found in the volatile reactants; no noticeable corrosion of the reactor wall has been detected. It has been established that addition of O₂ to the H₂S–CO₂ mixture and its heating to 673 K leads to formation of ferrous sulfates. The mechanisms of the observed processes are discussed.     

V<Subscript>2</Subscript>O<Subscript>5</Subscript>-SiO<Subscript>2</Subscript> hybrid as anode material for aqueous rechargeable lithium batteries

V₂O₅-SiO₂ hybrid material was fabricated by heat-treating a mixture of H₂SiO₃ and V₂O₅. SEM, TEM, XRD, and N₂ isotherm analyses were performed to characterize the morphology and structure details of the as-prepared V₂O₅-SiO₂. The possibility of using the as-prepared V₂O₅-SiO₂ as anode material for aqueous lithium-ion batteries was investigated. Potentiostatic and galvanostatic results indicated that the intercalation/de-intercalation of Li⁺ in this material in aqueous electrolyte was quasi-reversible. It was also found that a discharge capacity of up to 199.1 mAh g^?1 was obtained at a current density of 50 mA g^?1 in aqueous solution of 1 M Li₂SO₄, a value which is much higher than the available reported capacities of vanadium (+5) oxides in aqueous electrolytes.     

A Water-Soluble Fluorescent Probe for SO<Subscript>2</Subscript> Derivatives in Aqueous Solution and Serum Based on Phenanthroimidazole Dye

A water-soluble fluorescent SO₂ derivatives probe PI-SO ₂ based on a phenanthroimidazole dye, and a sensitive SO₂ recognition site, aldehyde was constructed. The probe PI-SO ₂ exhibits desirable properties such as high sensitivity, high selectivity and good water-solubility. Significantly, we have demonstrated that the probe PI-SO ₂ is suitable for rapidly fluorescence detecting of SO₂ derivatives in aqueous solution and serum. The application of the novel probe PI-SO ₂ proved that it was not only a useful tool for the detection of SO₂ derivatives in vitro, but also a potential assay for investigating the effects of SO₂ derivatives, and demonstrating its value in practical applicationin of complex biological samples.     

First-principle study of the electronic structure and magnetism in RuSr<Subscript>2</Subscript>GdCu<Subscript>2</Subscript>O<Subscript>8</Subscript> under pressure

We have performed a first-principle calculation of the structural, electronic and high pressure properties of RuSr₂GdCu₂O₈, a ferromagnetic superconductor, by employing a full-potential linearized augmented plane-wave method within the density-functional theory. The effect of pressure was achieved by varying the volume of the unit cell with constant a:b:c ratio. The experimentally observed anti-phase rotation of RuO₆ octahedra has been attributed to the residual forces on O_Ru which results in shear strain in the RuO₂ layer. Partial charge analysis shows that applying pressure up to 6 GPa leads to hole creation in the CuO₂ sheets which causes increase in the superconducting transition temperature. We have estimated the Curie temperature T _M of this compound in the mean-field approximation using Heisenberg model with first-nearest neighbor exchange interactions determined from DFT calculations for parallel and anti-parallel spin configurations of Ru moment in RuO₂ planes. The effect of pressure causes the magnetic moment of Ru atoms to decrease due to the increase of hybridization between the adjacent Ru atoms. The calculated exchange splitting in Cu d _{x 2 - y 2} states increases slightly with pressure but it is still very small that it does not affect superconductivity, and the hole doping mechanism is dominant.     

Photodesorption from ultra-thin metal films – a comparison of SO<Subscript>2</Subscript> and NO<Subscript>2</Subscript> on Ag/Si(100)

The photochemistry of SO₂ on thin epitaxial Ag films (5–60 nm) deposited on Si(100) has been studied using laser light with the wavelengths of 266, 355, and 532 nm. SO₂ desorbs with cross sections of 1.7×10^-19,1.7×10^-20 and 2.9×10^-21 cm², respectively. The average translation energy, 〈E_trans/2k〉, is 440 K for 266 and 355 nm light, and 270 K for 532 nm light. Cross sections for a 60 nm thick Ag film are practically identical to the ones for Ag(111) as the substrate. An increase by a factor of ∼3.5 is observed when the film thickness is reduced to 5 nm for 266 and 355 nm light. No significant change is observed for 532 nm excitation. The film thickness has no significant influence on the translational energy of the photodesorbed molecules. The data are discussed in connection with the change of absorptivity of the metal film–semiconductor system. A model is put forward which takes into account the light absorption in the Si substrate and the reduced relaxation of excited electrons in Si. Modelling indicates that electrons excited in the Si substrate with energies and parallel momenta not allowed in Ag contribute to the surface chemistry after crossing the gap in the projected band structure of Ag(111). PACS 82.45.MP; 73.63.-b; 82.50.Bc     

Dispersity and growth kinetics of K<Subscript>2</Subscript>SO<Subscript>4</Subscript> crystals in drops of an evaporating solution

Growth of K₂SO₄ crystals is studied in solution drops that have different initial heights and evaporate in different times. The dependences of the crystal size on the crystal growth time are obtained. The following three crystal growth modes are detected: rapid crystal growth in a supersaturated solution, a stop in the growth as a result of complete removal of supersaturation, and slow growth at a quasi-equilibrium solution concentration. The dispersities of the crystals that are retained at the bottom of the drop after complete evaporation of the solvent are calculated. A linear relation between the crystal dispersity and the reciprocal crystal growth time is revealed. The dispersity of K₂SO₄ crystals and the dispersity of the solid-solution dendrites in aluminum alloys are found to exhibit the same character of their dependences on the reciprocal crystal growth time.