Ionic transport properties of PVdF-HFP-MMT intercalated nanocomposite electrolytes based on ionic liquid, 1-butyl-3-methylimidazolium bromide

Ionic conductivity and transport properties of polyvinylidenefluoride–co-hexafluoropropylene– montmorillonite intercalated nanocomposite electrolytes based on ionic liquid 1-butyl-3-methylimidazolium bromide have been studied for various concentrations of montmorillonite clay. Ionic conductivity of the order of 10^?3?S?cm^?1 at room temperature with thermal stability up to about 235 °C has been obtained for the electrolyte system. The electrolyte system has superior properties at 5 wt% of clay loading with highly amorphous morphology as seen from selected area electron diffraction micrograph. Scanning electron microscope studies show that the electrolyte system has highly porous morphology and the ionic liquid is trapped in the pores. Dielectric properties of the electrolyte system have been studied to investigate the relaxation processes occurring in the system. Variation of real part of dielectric permittivity with frequency shows two relaxation processes occurring in the system, slow at low frequency and fast at high frequency. Kohlrausch exponential parameter has been calculated from modulus formalism, and the values show that the distribution of conductivity relaxation times becomes narrower with increasing clay loading.     

Pressure-induced crystallization of 1-butyl-3-methylimidazolium hexafluorophosphate

We have investigated the pressure-induced crystallization of 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]) associated with the conformational changes of [bmim]⁺ by Raman spectroscopy. [bmim]⁺ has trans-trans and gauche-trans (GT) conformers of the butyl side chain at ambient pressure. Our result revealed that liquid to solid-phase transition occurs at 0.2–0.4 GPa region, where the GT conformer becomes dominant. We found that the GT dominant state continues up to 4 GPa.     

1-butyl-3-methylimidazolium chloride assisted electrospinning of SAN/MWCNTs conductive reinforced composite membranes

The aim of this research was to investigate how the addition of IL [Bmim]Cl* and MWCNTs** into SAN*** solution will influence the viscosity and the electrical conductivity of the electrospinning solution and to find out the impact of IL and CNTs on the electrical and mechanical properties of the obtained membranes and on the morphology of the produced nanofibres. MWCNTs were added into two types of SAN solutions, with and without [Bmim]Cl, and then electrospinning was performed. All membranes were investigated by SEM analysis. The electrical conductivity and viscosity of the solutions were measured and their effect on the morphology of the fibres, as well as electrical and mechanical properties was estimated.     

Electrical and electromechanical properties of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide-blended cellulose

The effect of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMITFSI) blending on the electromechanical and electrical properties of cellulose was premeditated by taking bending actuator test and electrical impedance analysis. Dispersion of BMITFSI in cellulose matrix was carried out by solution blending technique. Upon blending BMITFSI, bending displacement of the actuator was enhanced by eight times as compared to that of the pristine cellulose. Similar improvement in the AC conductivity of cellulose was observed. The effect of BMITFSI content and humidity on electromechanical and electrical properties of BMITFSI-loaded cellulose was discussed.     

The impact of 1-butyl-3-methylimidazolium chloride on electrospinning process of SAN polymer solutions and electrospun fiber morphology

The aim of this research was to investigate how addition of IL [Bmim]Cl¹ into SAN² solution in 1,2-DCE³ will influence electrospinning variables, stability of process and morphology of obtained nanofibers and find out the appropriate way of utilizing [Bmim]Cl in the electrospinning process. The solutions of pure SAN in 1,2-DCE of different concentrations (10–20%) and solutions with different concentrations (0.5–20%) of IL were spun at different variables (10–20 cm and 10–20 kV). All results were investigated by optical and SEM microscopy. Also solution parameters like electrical conductivity, surface tension and viscosity were measured and their effect on the obtained fibers morphology estimated.     

Electrochemical behavior of cobalt from 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid

The electrodeposition of metallic cobalt from a 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid was investigated. The electrochemical behavior of Co(II) in the ionic liquid on a platinum working electrode at 60 °C was studied by cyclic voltammetry and chronoamperometry. The results from the cyclic voltammetry showed that the electrodeposition of metallic Co in the ionic liquid was an irreversible process and controlled by the diffusion of Co(II) on a platinum working electrode. The average value of αn_α was calculated to be 0.35 and the diffusion coefficient (D₀) of Co(II) was calculated to be 1.76 × 10⁻⁸ cm²/s at 60 °C. Chronoamperometric results indicated that the electrodeposition of Co on a platinum working electrode followed the mechanism of instantaneous nucleation and three-dimensional growth with diffusion-controlled. The cobalt plating was uniform, dense, shining in appearance with good adhesion to the platinum substrate at 60 °C. The scanning electron microscope (SEM) micrographs were used to confirm that the cobalt plating was denser and finer at 60 °C. Energy dispersive X-ray analysis (EDAX) profile showed that the obtained plating was pure cobalt. X-ray diffraction (XRD) pattern indicated that there was a preferred orientation direction and the average size of cobalt grains was 40 nm.     

Study on ionic conductivity and dielectric properties of PEO-based solid nanocomposite polymer electrolytes

The ionic conductivity and dielectric properties of the solid nanocomposite polymer electrolytes formed by dispersing a low particle-sized TiO₂ ceramic filler in a poly (ethylene oxide) (PEO)-AgNO₃ matrix are presented and discussed. The solid nanocomposite polymer electrolytes are prepared by hot press method. The optimum conducting solid polymer electrolyte of polymer PEO and salt AgNO₃ is used as host matrix and TiO₂ as filler. From the filler concentration-dependent conductivity study, the maximum ionic conductivity at room temperature is obtained for 10 wt% of TiO₂. The real part of impedance (Z′) and imaginary part of impedance (Z″) are analyzed using an LCR meter. The dielectric properties of the highest conducting solid polymer electrolyte are analyzed using dielectric permittivity (ε′), dielectric loss (ε″), loss tangent (tan δ), real part of the electric modulus (M′), and imaginary part of the electric modulus (M″). It is observed that the dielectric constant (ε′) increases sharply towards the lower frequencies due to the electrode polarization effect. The maxima of the loss tangent (tan δ) shift towards higher frequencies with increasing temperature. The peaks observed in the imaginary part of the electric modulus (M″) due to conductivity relaxation shows that the material is ionic conductor. The enhancement in ionic conductivity is observed when nanosized TiO₂ is added into the solid polymer electrolyte.     

Dissolution and Regeneration in Films of Natural Luffa in 1-butyl-3-methylimidazolium Chloride

Regenerated cellulose film was successfully prepared from natural luffa, a new cellulose raw material. A pretreatment of natural luffa was carried out by an alkali and hydrogen peroxide mixed solution. The dissolution process of the pretreated luffa in 1-butyl-3-methylimidazolium chloride ([BMIM]C1) was observed by polarized optical microscope. The structures and properties of the luffa films were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric (TGA), and porosity measurements. The results showed that the luffa fibers were transformed to fibrils after the pretreatment. [BMIM]Cl was a good non-derivatizing solvent for the luffa cellulose. The solution conditions were 80°C and 10 h for a 15% solution. After being regenerated, as films, from the luffa/[BMIM]Cl solution, the crystalline structure of the luffa film was transformed completely from cellulose I to cellulose II. The film showed the strong characteristic functional groups of cellulose in FTIR results. The surface of the film was smooth with a compact structure. The porosity of the film was 66.2% and the average pore size was 17.8 nm. It was thermally stabile up to 280°C.     

Ionic transport properties of protonic conducting solid biopolymer electrolytes based on enhanced carboxymethyl cellulose - NH<Subscript>4</Subscript>Br with glycerol

The present work investigates the ionic conductivity as well as its transport properties of carboxymethyl cellulose–NH₄Br plasticized with various weight percentage of glycerol for solid biopolymer electrolytes (SBEs) prepared by solution-casting technique. It was shown from the FTIR analysis that the complexation transpires at C=O and C–O^? from COO^? of CMC upon the addition of glycerol into the SBEs system. The highest room temperature ionic conductivity of ~10^?3 S cm^?1 was achieved at 6 wt.% of glycerol owing to the broadening in the amorphous state as demonstrated in the XRD analysis. The conductivity-temperature plots were found to be in good agreement with the conventional Arrhenius relationship. It was further shown that the conducting element is mainly due to the protonation of H⁺ where ionic mobility and diffusion coefficient was found to contribute towards the enhancement in the ionic conductivity of SBEs system.     

1-乙基-3-甲基咪唑四氟硼酸盐离子液体的量子化学研究

采用量子化学的从头算(abinitio)和密度泛函(DFT)方法,在6311++G计算水平上研究了离子液体1乙基3甲基咪唑四氟硼酸盐在气相模型下的离子对结构.经振动分析得到了离子对的红外谱,并利用自然键轨道(NBO)分析了阴阳离子与离子对的电荷布居差异.计算结果表明,离子对中存在氢键等弱相互作用.运用Counterpoise方法消除基组重叠误差,得到阴阳离子间的相互作用能为346.78kJ/mol.     

Lithium ion conductivity and dielectric properties of P(VdCl-co-AN-co-MMA)-LiCl-EC triblock co-polymer electrolytes

Lithium ion conducting polymer electrolytes based on triblock polymer P(VdCl-co-AN-co-MMA)–LiCl were prepared using a solution casting technique. XRD studies show that the amorphous nature of the polymer electrolyte has been increased due to the addition of LiCl. The maximum amorphous nature has been observed for 40 m% P(VdCl-co-AN-co-MMA)/60 m% LiCl samples. The FTIR study of the lithium ion conducting polymer membrane confirms the complex formation between the polymer P(VdCl-co-AN-co-MMA) and LiCl. The lithium ion conductivity is found to be 1.6 × 10^?5 Scm^?1 for the 40 m% P(VdCl-co-AN-co-MMA)/60 m% LiCl sample at room temperature. This value is found to be greater than that of pure polymer whose conductivity is found to be 1.5 × 10^?8 Scm^?1. To improve ionic conductivity, ethylene carbonate has been added as a plasticizer to the 40 m% P(VdCl-co-AN-co-MMA)/60 m% LiCl sample. When we add 0.6 m% of ethylene carbonate, it has been observed that the lithium ion conductivity has increased to 1.3 × 10^?3 Scm ^?1 . This value is two orders of magnitude greater than the 40 m% P(VdCl-co-AN-co-MMA)/60 m% LiCl sample. It is also observed from XRD patterns of 40 m% P(VdCl-co-AN-co-MMA)/60 m % LiCl/0.6 m % EC that the amorphous nature has been increased further. A dielectric study has been performed for the above membranes.     

Ionic conductivity of polymer electrolytes based on phosphate and polyether copolymers

Linear polyphosphate random copolymers (LPC) composed of phosphate as a linking agent with poly(ethylene glycol) (PEG) and/or poly(tetramethylene glycol) (PTMG) were synthesized to increase local segmental motion for improved ion transport. Ionic conductivity and thermal behavior of LPC series–LiCF₃SO₃ complexes were investigated with various compositions, salt concentrations and temperatures. The PEG(70)/PTMG(30)/LiCF₃SO₃ electrolyte exhibited ionic conductivity of 8.04×10⁻⁵ S/cm at 25°C. Salt concentration with the highest ionic conductivity was considerably dependent on EO/TMO compositions in LPC series–salt systems. Relationship between solvating ability and chain flexibility with various compositions and salt concentrations was investigated through theoretical aspects of the Adam–Gibbs configurational entropy model. Temperature dependence on the ionic conductivity in LPC6 series–salt systems suggested the ion conduction follows the Williams–Landel–Ferry (WLF) mechanism, which is confirmed by Vogel–Tamman–Fulcher (VTF) plots. The ionic conductivity was affected by segmental motion of the polymer matrix. VTF parameters and apparent activation energy were evaluated by a non-linear least square minimization method. These results suggested that the solvating ability of the host polymer might be a dominant factor to improve the ionic conductivity rather than chain mobility.     

Thermal,dielectric and conductivity studies on PVA/Ionic liquid [EMIM][EtSO4] based polymer electrolytes

Polymer electrolyte films of (PVA+15 wt% LiClO₄)+x wt% Ionic liquid (IL) 1-ethyl-3-methylimidazolium ethylsulfate [EMIM][EtSO₄] (x=0, 5, 10, 15) were prepared by solution cast technique. These films were characterized using TGA, DSC, XRD and ac impedance spectroscopic techniques. XRD result shows that amorphosity increases as the amount of the IL in PVA+salt (LiClO₄) is increased. DSC results confirm the same (except (PVA+15 wt% LiClO₄)+10 wt% IL). The dielectric and conductivity measurements were carried out on these films as a function of frequency and temperature. The addition of IL significantly improved the ionic conductivity of polymer electrolytes. Relaxation frequency vs. temperature plot for (PVA+15 wt% LiClO₄)+x wt% IL were found to follow an Arrhenius nature. The dielectric behavior was analyzed using real and imaginary parts of dielectric constant, dielectric loss tangent (tan δ) and electric modulus (M′ and M″).     

Influence of water on the surface structure of 1-hexyl-3-methylimidazolium chloride

The molecular surface structure of an ionic liquid (IL) with and without the presence of water was studied with the surface sensitive technique neutral impact collision ion scattering spectroscopy (NICISS). The IL chosen is 1-hexyl-3-methylimidazolium chloride, which is known to be hydrophilic. Binary mixtures were investigated within the water mole fraction range 0.43 ≤ χ_water ≤ 0.71 at 283 K. During approximately 3 h exposition time in vacuum, we have observed a very low water loss rate from sample. The NICISS measurements suggest that admixture of water to [HMIm]Cl leads to a layered surface structure. Three layers were identified (layer 1 — cations, layer 2 — cations and water, layer 3 — cations, water, and anions). While the first layer is unaffected by water, the thickness of the second layer depends on the water concentration. The thickness of layer 2 is relatively constant for water concentrations χ_water ≤ 0.61, but increases for water contents χ_water ≥ 0.68. The concentration range 0.61 ≤ χ_water ≤ 0.68 seems to play a key role in water network formation.     

1-羟乙基-3-甲基咪唑氯盐水溶液蒸汽压和凝固特性研究

1-羟乙基-3-甲基咪唑氯盐([HOEtMIM][Cl])是一种亲水性极强的离子液体,与水可以组成吸收式制冷工质对,具有良好的工业应用前景.在制冷工程应用中,离子液体水溶液的低温特性研究非常重要,包括低温段的水溶液蒸汽压数据和凝固特性,而[HOEtMIM][Cl]的相关研究缺乏.本文对水的质量分数分别为17.10%、24.29%、38.03%、49.89%、69.94%,温度范围(278.15K~408.15K)的[HOEtMIM][Cl]水溶液的汽液相平衡进行了测定;并对水的质量分数范围为1.3%~90.0%,温度范围为150K~360K的离子液体水溶液的凝固特性进行了测定,揭示其在低温应用时可能出现的固化问题.获得的蒸汽压及凝固特性数据对该离子液体水溶液应用于制冷系统设计具有重要意义.     

Ionic conductivity,ionic transport and electrochemical characterizations of plastic crystal polymer electrolytes

In this work, the plastic crystal polymer electrolytes (PCPEs), composed of polyacrylonitrile (PAN), succinonitrile (SN) and lithium bis(trifluoromethane)sulfonimide (LiTFSI) were prepared. The concentrations of lithium salt were varied by weight percentage from 10 wt% to 50 wt%. The ionic conductivity of the PCPE films increases with the increase of lithium salt, where the highest value recorded is in the order of ~10^?2 S cm^?1. The temperature-dependence conductivity analysis shows that the PCPE films exhibit Arrhenius behaviour when subjected to the temperature range from 303 K to 343 K. The decrease in crystallinity was confirmed by X-ray diffraction (XRD) and Differential Scanning Calorimetry (DSC) analyses. The cationic transport number also increases with the increase of salt which corresponds well to their conductivity values. It is found that the films are electrochemically stable up to ~3.6 V as revealed by the linear sweep voltammetry (LSV) analysis. The cyclic voltammetry (CV) plots of the films shown no substantial change in the redox peaks which mean that the charge transfer reaction is reversible.     

AC conductivity and dielectric properties of sulphate glasses

AC conductivity and dielectric properties of sulphate glasses have been studied as a function of temperature, frequency and variation in interalkali concentration. AC conductivity at frequencies well beyond the dielectric loss peaks seems to arise from local motion of alkali ions within the neighbouring potential wells. Activation energies for AC conductivity were found to be very much lower than those for DC conductivity. Further, AC conductivity seems to be independent of interalkali variation, whereas ε′ and tan δ show a mild degree of mixed alkali effect. The observations made here have been explained on the basis of a structural model earlier proposed by us for these glasses. Communication No. 167 from Solid State and Structural Chemistry Unit.     

Low-frequency dielectric properties and conductivity of a polyvinylcaprolactam-water system

The dielectric relaxation and conductivity of polyvinylcaprolactam (PVCL)-water systems of different compositions (with water contents of ∼1, 5, and 24 wt %) were studied by means of dielectric spectroscopy (10⁻¹–10⁷ Hz) at −100−50°C. It was found that the conductivity of samples with a low content of water upon cooling has an activation character, whereas a cooperative mechanism of conduction holds for the PVCL-water system with 24 wt % water, which switches to an activation character of interactions of water with polymer changes in the course of a glass transition.