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1.
Thin films of biodegradable corn starch-based biopolymer electrolytes were prepared by solution casting technique. Lithium hexafluorophosphate (LiPF6) and 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BmImTf) were employed as lithium salt and ionic liquid, respectively. With reference to the temperature dependence study, Arrhenius relationship was observed. The highest ionic conductivity of (6.00 ± 0.01) × 10−4 S cm−1 was obtained at 80 °C. Based on x-ray diffraction (XRD) result, the peaks became broader with doping of ionic liquid revealing the higher amorphous region of the biopolymer electrolytes. Ionic liquid-based biopolymer electrolytes exhibited lower glass transition temperature (T g).  相似文献   

2.
A composite of aminosilane-grafted TiO2 (TA) and graphene oxide (GO) was prepared via a hydrothermal process. The TiO2/graphene oxide-based (TA/GO) anode was investigated in an ionic liquid electrolyte (0.7 M lithium bis(trifluoromethanesulfonyl)imide (LiNTf2)) in ionic liquid (N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (MPPyrNTf2)) at room temperature and in sulfolane (1 M lithium hexafluorophosphate (LiPF6) in tetramethylene sulfolane (TMS)). Scanning and transmission electron microscopy (SEM and TEM) observations of the anode materials suggested that the electrochemical intercalation/deintercalation process in the ionic liquid electrolyte with vinylene carbonate (VC) leads to small changes on the surface of TA/GO particles. The addition of VC to the electrolyte (0.7 M LiNTf2 in MPPyrNTf2 + 10 wt.% VC) considerably increases the anode capacity. Electrodes were tested at different current regimes in the range 5–50 mA g?1. The capacity of the anode, working at a low current regime of 5 mA g?1, was ca. 245 mA g?1, while a current of 50 mA g?1 resulted in a capacity of 170 mA g?1. The decrease in anode capacity with increasing current rate was interpreted as the result of kinetic limits of electrode operation. A much lower capacity was observed for the system TA/GO│1 M LiPF6 in TMS + 10 wt.% VC│Li.  相似文献   

3.
Quaternary polymer electrolyte (PE) based on poly(acrylonitrile) (PAN), 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid (EMImBF4), sulfolane (TMS) and lithium hexafluorophosphate salt (LiPF6) (PAN-EMImBF4-sulfolane-LIPF6) was prepared by the casting technique. Obtained PE films of ca. 0.2–0.3 mm in thickness showed good mechanical properties. They were examined using scanning electron microscopy (SEM), thermogravimetry (TGA, DSC), the flammability test, electrochemical impedance spectroscopy (EIS) and galvanostatic charging/discharging. SEM images revealed a structure consisting of a polymer network (PAN) and space probably occupied by the liquid phase (LiPF6 + EMImBF4 + sulfolane). The polymer electrolyte in contact with an outer flame source did not ignite; it rather underwent decomposition without the formation of flammable products. Room temperature specific conductivity was ca. 2.5 mS cm?1. The activation energy of the conding process was ca. 9.0 kJ mol?1. Compatibility of the polymer electrolyte with metallic lithium and graphite anodes was tested applying the galvanostatic method. Charge transfer resistance for the C6Li → Li+ + e? anode processes, estimated from EIS curve, was ca. 48 Ω. The graphite anode capacity stabilizes at ca. 350 mAh g?1 after the 30th cycle (20 mA g?1).  相似文献   

4.
Biodegradable corn starch–lithium perchlorate (LiClO4)-based solid polymer electrolytes with addition of nano-sized fumed silica (SiO2) were prepared by solution casting technique. Ionic conductivity at ambient temperature was measured by AC impedance spectroscopy. Upon addition of nano-sized SiO2, the ionic conductivity at room temperature is increased. The optimum ionic conductivity value obtained was 1.23?×?10?4?S?cm?1 at 4?wt% SiO2. This may be attributed to the low crystallinity of the polymer electrolytes resulting from the dispersed nanosilica particles. Fourier–transform infrared spectroscopy studies confirmed the complexation between corn starch, lithium perchlorate, and silica. The thermal properties of the prepared samples were investigated with differential scanning calorimetry and thermogravimetric analysis. The surface morphology of the polymer electrolytes confirmed the agglomeration of particles after excess dispersion of inorganic filler. This was proven in the scanning electron microscopy studies.  相似文献   

5.
The paper reported a green and efficient extraction strategy to lithium isotope separation. A 4-methyl-10-hydroxybenzoquinoline (ROH), hydrophobic ionic liquid—1,3-di(isooctyl)imidazolium hexafluorophosphate ([D(i-C8)IM][PF6]), and hydrophilic ionic liquid—1-butyl-3-methylimidazolium chloride (ILCl) were used as the chelating agent, extraction medium and ionic associated agent. Lithium ion (Li+) first reacted with ROH in strong alkali solution to produce a lithium complex anion. It then associated with IL+ to form the Li(RO)2IL complex, which was rapidly extracted into the organic phase. Factors for effect on the lithium isotope separation were examined. To obtain high extraction efficiency, a saturated ROH in the [D(i-C8)IM][PF6] (0.3 mol l?1), mixed aqueous solution containing 0.3 mol l?1 lithium chloride, 1.6 mol l?1 sodium hydroxide and 0.8 mol l?1 ILCl and 3:1 were selected as the organic phase, aqueous phase and phase ratio (o/a). Under optimized conditions, the single-stage extraction efficiency was found to be 52 %. The saturated lithium concentration in the organic phase was up to 0.15 mol l?1. The free energy change (ΔG), enthalpy change (ΔH) and entropy change (ΔS) of the extraction process were ?0.097 J mol?1, ?14.70 J mol K?1 and ?48.17 J mol?1 K?1, indicating a exothermic process. The partition coefficients of lithium will enhance with decrease of the temperature. Thus, a 25 °C of operating temperature was employed for total lithium isotope separation process. Lithium in Li(RO)2IL was stripped by the sodium chloride of 5 mol l?1 with a phase ratio (o/a) of 4. The lithium isotope exchange reaction in the interface between organic phase and aqueous phase reached the equilibrium within 1 min. The single-stage isotope separation factor of 7Li–6Li was up to 1.023 ± 0.002, indicating that 7Li was concentrated in organic phase and 6Li was concentrated in aqueous phase. All chemical reagents used can be well recycled. The extraction strategy offers green nature, low product cost, high efficiency and good application prospect to lithium isotope separation.  相似文献   

6.
Four vinyl monomers containing a covalently bonded cation ethylimidazolium and various anions—Br?, (CF3SO2)2N?, (CN)2N?, and CF3SO 3 ? —have been synthesized. High-molecular-mass polymers (M w up to 1.84 × 106) having the structure of ionic liquids have been prepared via the free-radical polymerization of 1-vinyl-3-ethylimidazolium in bulk and molecular and ionic solvents. The thermal stability and heat resistance of the resulting polymer salts have been estimated. It has been demonstrated that the thermal characteristics of these salts significantly depend on the nature of anions. The glass-transition temperatures of the polymers range from 19 to 235°C. The ionic conductivity of the polymer salts and their compositions with individual ionic liquids has been studied in the frequency range 50–106 Hz. The highest conductivity (1.5 × 10?5 S/cm) is exhibited by the polymer containing the (CN)2N? anion.  相似文献   

7.
The graphene anode was investigated in an ionic liquid electrolyte (0.7 M lithium bis(trifluoromethanesulfonyl)imide (LiNTf2)) in room temperature ionic liquid (N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (MPPyrNTf2)). SEM and TEM images suggested that the electrochemical intercalation/deintercalation process in the ionic liquid electrolyte without vinylene carbonate (VC) leads to small changes on the surface of graphene particles. However, a similar process in the presence of VC results in the formation of a coating (SEI—solid electrolyte interface) on the graphene surface. During charging/discharging tests, the graphene electrode working together with the 0.7 M LiNTf2 in MPPyrNTf2 electrolyte lost its capacity, during cycling and stabilizes at ca. 200 mAh g?1 after 20 cycles. The addition of VC to the electrolyte (0.7 M LiNTf2 in MPPyrNTf2?+?10 wt.% VC) considerably increases the anode capacity. Electrodes were tested at different current regimes: ranging between 50 and 1,000 mA g?1. The capacity of the anode, working at a low current regime of 50 mA g?1, was ca. 1,250 mAh g?1, while the current of 500 mA g?1 resulted in capacity of 350 mAh g?1. Coulombic efficiency was stable and close to 95 % during ca. 250 cycles. The exchange current density, obtained from impedance spectroscopy, was 1.3?×?10?7 A cm?2 (at 298 K). The effect of the anode capacity decrease with increasing current rate was interpreted as the result of kinetic limits of the electrode operation.  相似文献   

8.
The present investigation deals with electrochemical double layer capacitors (EDLCs) made up of ionic liquid (IL)-based gel polymer electrolytes with chemically treated activated charcoal electrodes. The gel polymer electrolyte comprising of poly(vinylidine fluoride-co-hexafluropropylene) (PVdF-HFP)–1-ethyl-2,3-dimethyl-imidazolium-tetrafluroborate [EDiMIM][BF4]–propylene carbonate (PC)–magnesium perchlorate (Mg(ClO4)2) exhibits the highest ionic conductivity of ~8.4?×?10?3?S?cm?1 at room temperature (~20 °C), showing good mechanical and dimensional stability, suitable for their application in EDLCs. Activation of charcoal was done by impregnation method using potassium hydroxide (KOH) as activating agent. Brunauer–Emmett–Teller (BET) studies reveal that the effective surface area of treated activated charcoal powder (1,515 m2?g?1) increases by more than double-fold compared to the untreated one (721 m2?g?1). Performance of EDLCs has been tested using cyclic voltammetry, impedance spectroscopy, and charge–discharge techniques. Analysis shows that chemically treated activated charcoal electrodes have almost triple times more capacitance values as compared to the untreated one.  相似文献   

9.
Ionic liquid monomer couples were prepared by the neutralization of 1‐vinylimidazole with vinylsulfonic acid or 3‐sulfopropyl acrylate. These ionic liquid monomer couples were viscous liquid at room temperature and showed low glass transition temperature (Tg) at ?83 °C and ?73 °C, respectively. These monomer couples were copolymerized to prepare ion conductive polymer matrix. Thus prepared ionic liquid copolymers had no carrier ions, and they showed very low ionic conductivity of below 10?9 S cm?1. Equimolar amount of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to imidazolium salt unit was then added to generate carrier ions in the ionic liquid copolymers. Poly(vinylimidazolium‐co‐vinylsulfonate) containing equimolar LiTFSI showed the ionic conductivity of 4 × 10?8 S cm?1 at 30 °C. Advanced copolymer, poly(vinylimidazolium‐co‐3‐sulfopropyl acrylate) which has flexible spacer between the anionic charge and polymer main chain, showed the ionic conductivity of about 10?6 S cm?1 at 30 °C, which is 100 times higher than that of copolymer without spacer. Even an excess amount of LiTFSI was added, the ionic conductivity of the copolymer kept this conductivity. This tendency is completely different from the typical polyether systems. Copyright © 2002 John Wiley & Sons, Ltd.  相似文献   

10.
Carboxyl methylcellulose (CMC) solid polymer electrolytes were prepared by utilizing oleic acid (OA) and different wt.% of propylene carbonate (PC) by using the solution casting technique. An ionic conductivity study of the films was done by using impedance spectroscopy. The highest ionic conductivity gained is 2.52 × 10?7 S cm?1 at ambient temperature for sample CMC-OA-PC 10 wt.%. From transference number measurement (TNM), the value of cation diffusion coefficient, D+, and ionic mobility, μ+, was higher than the value of anion diffusion coefficient, D?, and ionic mobility, μ?. Thus, the results prove that the present samples were proton conductors.  相似文献   

11.
Three nanosized polyaniline (PAn) powders doped with ionic liquid and dodecyl benzene sulfonic acid (DBSA) or hydrochloric acid have been prepared for the first time in an ionic liquid-water emulsion system. The oil-phase ionic liquid is used as both a monomer solvent and doped counterion. The effects of different counterions on the properties (molecular weight, electrical conductivity, glass transition temperature, electrochemical activity) of PAn are investigated. PAn codoped with 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid and DBSA shows the highest molecular weight (81 104 g mol?1), the highest electrical conductivity (1.85 S cm?1), the lowest glass transition temperature (181°C) and the highest redox reaction current density; PAn doped with an ionic liquid only exhibits the lowest conductivity (0.0018 S cm?1) and a lower redox reaction current density. PAn codoped with ionic liquid and HCl shows higher conductivity. They also exhibit good electrochemical stability and charge-discharge performance. These indicate that codoping of different counterions under acidic conditions could improve the degree of oxidation and doping ratio of PAn and could result in high electrical conductivity and good electrochemical properties.  相似文献   

12.
A number of new ionic vinyl monomers composed of 1-vinylimidazolium cation with diethoxy- and dihydroxyphosphoryl groups and various anions—Br?, (CN)2N?, and (CF3SO2)2N?—are synthesized. The free-radical polymerization of the monomers in solutions of molecular and ionic solvents yields new polymer analogs of ionic liquids, and their molecular-mass characteristics, solubility, heat resistance, thermal stability, and electrical conductivity are estimated. It is shown that the incorporation of bulky phosphorylalkyl side substituents into the vinylimidazolium polycation causes a decrease in the glass-transition temperature and an increase in the ionic conductivity of polymer salts. The highest ionic conductivity (2.6 × 10?5 S/cm at 25°C) is exhibited by the polymer with the (CN)2N? anion.  相似文献   

13.
A simple, rapid and efficient ionic liquid based on dispersive liquid-phase microextraction (IL-DLPME) method was developed for the determination of three triazine and two phenylurea herbicides in water samples. IL (1-hexyl-3-methylimidazolium hexafluorophosphate [C6MIM][PF6]) that dispersed completely into the water solution under controlled temperature was used as the extraction solvent. The analytes were easily concentrated into the ionic liquid phase. This technique combined the process of extraction and concentration of the analytes into one step and avoided use of the more common, toxic organic solvents. The factors affecting the extraction efficiency such as the IL volume, sample pH, extraction time, centrifugal time, dissoluble temperature and ionic strength were optimized. The extracts were analyzed by high-performance liquid chromatography (HPLC) coupled with diode array detector (DAD). Under the optimized conditions, recoveries (50.5–109.1%) were obtained for the target analytes in water samples. The calibration curves were linear and the correlation coefficient ranged from 0.9947 to 0.9973 in the concentration levels of 5–100 μg L?1. The relative standard deviations (RSDs, n?=?5) were 6.80–10.78%. The limit of detections (LODs) for the five polar herbicides were between 0.46 μg L?1 and 0.89 μg L?1.  相似文献   

14.
Proton-conducting free standing gel polymer electrolyte (GPE) films containing protic ionic liquid, 1-butyl-3-methylimidazolium hydrogen sulphate, immobilized in blend of poly(vinylidenefluoride-co-hexafluoropropylene) and poly(vinylpyrrolidone) have been prepared by solution-cast technique. Films have been characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscope (SEM), differential scanning calorimetry (DSC), complex impedance spectroscopy, and cyclic voltammetry. Ionic conductivity of the semicrystalline and porous GPE films has been obtained as ~3.9?×?10?3 S cm?1 at room temperature. Protonic nature of conduction in the films has been established by performing cyclic voltammetry and complex impedance spectroscopy on the cells having both blocking (stainless steel) and both reversible electrodes (Zn + ZnSO4.7H2O). The electrochemical stability window of the films has been found as ~3.8 V. The highest conducting film has been used as a separator and proton conductor to fabricate a proton battery of configuration Zn + ZnSO4.7H2O |GPE film| PbO2 + V2O5. The battery shows an open circuit voltage of ~1.62 V. Energy density of the cell has been obtained as 35.2 W h kg?1 for low current drain. Rechargeability of the cell has been tested for ten cycles. The maximum discharge capacity of the cell has been obtained as ~2.50 mA h g?1 during the first discharge cycle.  相似文献   

15.
A new plasticized nanocomposite polymer electrolyte based on poly (ethylene oxide) (PEO)-LiTf dispersed with ceramic filler (Al2O3) and plasticized with propylene carbonate (PC), ethylene carbonate (EC), and a mixture of EC and PC (EC+PC) have been studied for their ionic conductivity and thermal properties. The incorporation of plasticizers alone will yield polymer electrolytes with enhanced conductivity but with poor mechanical properties. However, mechanical properties can be improved by incorporating ceramic fillers to the plasticized system. Nanocomposite solid polymer electrolyte films (200–600 μm) were prepared by common solvent-casting method. In present work, we have shown the ionic conductivity can be substantially enhanced by using the combined effect of the plasticizers as well as the inert filler. It was revealed that the incorporating 15 wt.% Al2O3 filler in to PEO: LiTf polymer electrolyte significantly enhanced the ionic conductivity [σ RT (max)?=?7.8?×?10?6 S cm?1]. It was interesting to observe that the addition of PC, EC, and mixture of EC and PC to the PEO: LiTf: 15 wt.% Al2O3 CPE showed further conductivity enhancement. The conductivity enhancement with EC is higher than PC. However, mixture of plasticizer (EC+PC) showed maximum conductivity enhancement in the temperature range interest, giving the value [σ RT (max)?=?1.2?×?10?4 S cm?1]. It is suggested that the addition of PC, EC, or a mixture of EC and PC leads to a lowering of glass transition temperature and increasing the amorphous phase of PEO and the fraction of PEO-Li+ complex, corresponding to conductivity enhancement. Al2O3 filler would contribute to conductivity enhancement by transient hydrogen bonding of migrating ionic species with O–OH groups at the filler grain surface. The differential scanning calorimetry thermograms points towards the decrease of T g , crystallite melting temperature, and melting enthalpy of PEO: LiTf: Al2O3 CPE after introducing plasticizers. The reduction of crystallinity and the increase in the amorphous phase content of the electrolyte, caused by the filler, also contributes to the observed conductivity enhancement.  相似文献   

16.
Organic-inorganic hybrid membranes based on poly(ethylene oxide) (PEO) 6.25 wt%/poly(vinylidene fluoride hexa fluoro propylene) [P(VdF-HFP)] 18.75 wt% were prepared by using various concentration of nanosized barium titanate (BaTiO3) filler. Structural characterizations were made by X-ray diffraction and Fourier transform infrared spectroscopy, which indicate the inclusion of BaTiO3 in to the polymer matrix. Addition of filler creates an effective route of polymer-filler interface and promotes the ionic conductivity of the membranes. From the ionic conductivity results, 6 wt% of BaTiO3-incorporated composite polymer electrolyte (CPE) showed the highest ionic conductivity (6 × 10?3 Scm?1 at room temperature). It is found that the filler content above 6 wt% rendered the membranes less conducting. Morphological images reveal that the ceramic filler was embedded over the membrane. Thermogravimetric and differential thermal analysis (TG-DTA) of the CPE sample with 6 wt% of the BaTiO3 shows high thermal stability. Electrochemical performance of the composite polymer electrolyte was studied in LiFePO4/CPE/Li coin cell. Charge-discharge cycle has been performed for the film exhibiting higher conductivity. These properties of the nanocomposite electrolyte are suitable for Li-batteries.  相似文献   

17.
Four functionalized ionic liquids based on imidazolium cations with vinyl or alllyl group and TFSI? anion were synthesized as electrolyte additives for high-voltage Li-ion battery to stabilize carbonate-based electrolytes on the surface of 5 V class cathode materials. The electrochemical behaviors and surface morphology of LiNi0.5Mn1.5O4 cathode had been investigated by cyclic voltammetry, charge–discharge test, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM), respectively. Cycle life and rate performance of the Li/LiNi0.5Mn1.5O4 cells containing 1.2 M LiPF6 in ethylene carbonate/ethyl methyl carbonate can be improved by adding 1-allyl-3-vinyl imidazolium bis(trifluoromethanesulphonyl)imide ([AVIm][TFSI]). The addition of 3 wt.% [AVIm][TFSI] results in high discharge capacity of above 130 mAh g?1. Surface analysis of the cathode material (XPS and SEM) suggested that a stable and compact polymer film was formed on the LiNi0.5Mn1.5O4 cathode by electroinitiated polymerization of imidazolium cation with vinyl and allyl group.  相似文献   

18.
A number of methacrylate ionic monomers with different structures and mobilities of ionic centers were synthesized. The free-radical polymerization of these monomers in solution affords high-molecular-mass (M sD = 0.5 to 2.5 × 106) thermally stable (T dec > 170°C) polyelectrolytes or cationic or anionic “polymeric ionic liquids.” The conductivities of polycation- and polyanion-derived coatings are (7.4 × 10?10)?(7.6 × 10?7) and (4.9 × 10?10)-(1.6 × 10?7) S/cm (25°C), respectively. As exemplified by poly(1-[3-(methacryloyloxy)propyl]-3-methylimidazolium bis[(trifluoromethanesulfonyl)imide]), the molecular mass and glasstransition temperature of the polymer affect the ionic conductivity of the film coating. The transition from linear polyelectrolytes to crosslinked systems based on ionic monomers and poly(ethylene glycol dimethacrylate) 750 leads to the formation of elastic films featuring satisfactory strength, reduced glass-transition temperatures (?8 to +15°C), and increased ionic conductivity (up to 3.2 × 10?6 S/cm (25°C)).  相似文献   

19.
ABSTRACT

A series of novel star-shaped ionic liquid crystals (ILCs) compounds with various counterions (derived from HBF4, HPF6, CF3COOH, d-MH-SO3H, H3PO4, p-Toluenesulfonic acid) were designed and synthesised starting from precursors of pyridines and liquid crystalline monomer cholesteryl 4-bromobutanoate. Inducing various counterions by use of ionic self-assembly due to electrostatic attraction of various ion clusters was one of the most essential factors for intermolecular separation. The chemical structures, liquid crystalline properties, self-assembly behaviour and ionic conductivity of these compounds were researched during multiple experimental techniques. The star-shaped ILCs showed a smectic A (SmA) mesophase. The d-spacing of star-shaped ILCs increased slightly due to the increase volume of anion. The clearing temperatures of the pyridinium salts suggested that the effect of the stabilisation on the SmA structures was in the order H2PO4?>BF4?>TS?>D-MH-SO3?>CF3COO?>PF6?. All these star-shaped ILCs displayed ionic conductivity in mesophase. It was noted that the conductivity (σ) increased with the increase of the anion size and temperature.  相似文献   

20.
Simultaneous electrochemical generation and functionalization of nano-sized graphite from graphite had been carried out in a non-fluoroanion-based ionic liquid, namely, triethylmethylammonium methylsulfate (TEMAMS) containing water and acetonitrile (AN) in different weight ratios. The oxygen-based functional groups attached with the exfoliated material had been identified using Fourier transform infrared spectroscopy (FTIR), and morphological changes were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). A symmetrical supercapacitor was fabricated using the exfoliated nano-sized graphite, and the influence of surface functionalities on its performance was investigated using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic charge–discharge cycles (CC). The highest specific capacitance (C sp) value of 140 F g?1 at 0.25 A g?1 was obtained in 1.0 M H2SO4, followed by aqueous TEMAMS (125 F g?1), TEMAMS/acetonitrile (115 F g?1), and TEMAMS (106 F g?1) at 0.10 A g?1.  相似文献   

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