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1.
In this study, the electrical, dielectric and morphological analysis of composite solid polymer electrolytes containing polyethylene oxide, alumina nano-fillers and tetrapropylammonium iodide are conducted. The temperature dependence of conductivity shows activation energy of 0.23, 0.20 and 0.29 eV for electrolytes containing 0, 5 and 15 wt.% alumina, respectively, when data fitted to the Arrhenius equation. These activation energy values are in good agreement with those determined from dielectric measurements. The result confirms the fact that conductivity is activated by both the mobility and the charge carrier density. The conductivity isotherms demonstrated the existence of two peaks, at 5 and 15 wt.% Al2O3 composition. The highest conductivity values of 2.4 × 10?4, 3.3 × 10?4 and 4.2 × 10?4 S cm?1 are obtained for the sample with 5 wt.% Al2O3 at 0, 12 and 24 °C, respectively, suggesting an enhancement of conductivity compared with that of alumina free samples.  相似文献   

2.
Poly (acrylonitrile) (PAN) and ammonium chloride (NH4Cl)-based proton conducting polymer electrolytes with different compositions have been prepared by solution casting technique. The amorphous nature of the polymer electrolytes has been confirmed by XRD analysis. The FTIR analysis confirms the complex formation of the host polymer (PAN) with the salt (NH4Cl). DSC measurements show a decrease in Tg with the increase in salt concentration. The conductivity analysis shows that the 25 mol% ammonium chloride doped polymer electrolyte has a maximum ionic conductivity, and it has been found to be 6.4 × 10?3 Scm?1, at room temperature. The temperature dependence of conductivity of the polymer electrolyte complexes appears to obey the Arrhenius nature. The activation energy (Ea = 0.23 eV) has been found to be low for 25 mol% salt doped polymer electrolyte. The dielectric behavior has been analyzed using dielectric permittivity (ε*), and the relaxation frequency (τ) has been calculated from the loss tangent spectra (tan δ). Using this maximum ionic conducting polymer electrolyte, the primary proton conducting battery with configuration Zn + ZnSO4·7H2O/75 PAN:25 NH4Cl/PbO2 + V2O5 has been fabricated and their discharge characteristics have been studied.  相似文献   

3.
Polymer blended films of polyethylene oxide (PEO)?+?polyvinyl pyrrolidone (PVP):lithium perchlorate (LiClO4) embedded with silver (Ag) nanofiller in different concentrations have been synthesized by a solution casting method. The semi-crystalline nature of these polymer films has been confirmed from their X-ray diffraction (XRD) profiles. Fourier transform infrared spectroscopy (FTIR) and Raman analysis confirmed the complex formation of the polymer with dopant ions. Dispersed Ag nanofiller size evaluation study has been done using transmission electron microscopy (TEM) analysis. It was observed that the conductivity increases when increasing the Ag nanofiller concentration. On the addition of Ag nanofiller to the polyethylene oxide (PEO)?+?polyvinyl pyrrolidone (PVP):Li+ electrolyte system, it was found to result in the enhancement of ionic conductivity. The maximum ionic conductivity has been set up to be 1.14?×?10?5 S cm?1 at the optimized concentration of 4 wt% Ag nanofiller-embedded (45 wt%) polyethylene oxide (PEO)?+?(45 wt%) polyvinyl pyrrolidone (PVP):(10 wt%) Li+ polymer electrolyte nanocomposite at room temperature. Polyethylene oxide (PEO)?+?polyvinyl pyrrolidone (PVP):Li+ +Ag nanofiller (4 wt%) cell exhibited better performance in terms of cell parameters. This is ascribed to the presence of flexible matrix and high ionic conductivity. The applicability of the present 4 wt% Ag nanofiller-dispersed polyethylene oxide (PEO)?+?polyvinyl pyrrolidone (PVP):Li+ polymer electrolyte system could be suggested as a potential candidate for solid-state battery applications. Dielectric constants and dielectric loss behaviours have been studied.  相似文献   

4.
Nanocomposite polymer electrolyte thin films of polyvinyl alcohol (PVA)-orthophosphoric acid (H3PO4)-Al2O3 have been prepared by solution cast technique. Films are irradiated with 50 MeV Li3+ ions having four different fluences viz. 5?×?1010, 1?×?1011, 5?×?1011, and 1?×?1012 ions/cm2. The effect of irradiation on polymeric samples has been studied and characterized. X-ray diffraction spectra reveal that percent degree of crystallinity of samples decrease with ion fluences. Glass transition and melting temperatures have been also decreased as observed in differential scanning calorimetry. A possible complexation/interaction has been shown by Fourier transform infrared spectroscopy. Temperature-dependent ionic conductivity shows an Arrhenius behavior before and after glass transition temperature. It is observed that ionic conductivity increases with ion fluences and after a critical fluence, it starts to decrease. Maximum ionic conductivity of ~2.3?×?10?5 S/cm owing to minimum activation energy of ~0.012 eV has been observed for irradiated electrolyte sample at fluence of 5?×?1011 ions/cm2. The dielectric constant and dielectric loss also increase with ion fluences while they decrease with frequency. Transference number of ions shows that the samples are of purely ionic in nature before and after ion irradiation.  相似文献   

5.
Proton-conducting polymer electrolytes based on biopolymer, agar-agar as the polymer host, ammonium bromide (NH4Br) as the salt and ethylene carbonate (EC) as the plasticizer have been prepared by solution casting technique with dimethylformamide as solvent. Addition of NH4Br and EC with the biopolymer resulted in an increase in the ionic conductivity of polymer electrolyte. EC was added to increase the degree of salt dissociation and also ionic mobility. The highest ionic conductivity achieved at room temperature was for 50 wt% agar/50 wt% NH4Br/0.3% EC with the conductivity 3.73?×?10?4 S cm?1. The conductivity of the polymer electrolyte increases with the increase in amount of plasticizer. The frequency-dependent conductivity, dielectric permittivity (ε′) and modulus (M′) studies were carried out.  相似文献   

6.
In the present work, a series of five different nanocomposite polymer electrolytes (NCPEs) have been reported with varying contents of ceria, CeO2 nanofiller suitably incorporated within an optimized composition having 75:25 wt% ratio of poly(vinylidenefluoride-co-hexafluoropropylene) [(PVDF-co-HFP)] and zinc trifluoromethanesulfonate (ZnTf) in the form of films obtained by mean of solution casting technique with a general formula [75 wt% PVDF-co-HFP:25 wt% ZnTf]-x wt% CeO2 where x = 1, 3, 5, 7, and 10, respectively. The chosen NCPE system is found to exhibit the maximum electrical conductivity of 3 × 10?4 S cm?1 for 5 wt% loading of CeO2 nanofiller at ambient temperature. The observed conductivity enhancement has been attributed to the occurrence of an increase in the amorphous content as confirmed by X-ray diffraction (XRD) analysis. Detailed Fourier transform infrared (FTIR) spectral analysis has indicated the feasibility of complexation of the host polymer matrix with ZnTf salt and CeO2 nanofiller. The incorporation of CeO2 nanofiller has further increased the decomposition voltage of the polymer electrolyte from 2.4 to 2.7 V as revealed from the voltammetric studies performed on such NCPEs, thereby suggesting the suitability of these NCPE films with an enhanced electrical conductivity as new electrolytes in order to design and fabricate eco-friendly zinc rechargeable batteries and other electrochemical devices.  相似文献   

7.
A solid polymer electrolyte (SPE) composites consisting blend of poly(ethylene oxide) (PEO) and poly(ethylene glycol) (PEG) as the polymer host with LiCF3SO3 as a Li+ cation salt and TiO2 nanoparticle which acts as a filler were prepared using solution-casting technique. The SPE films were characterized by X-ray diffraction and Fourier transform infrared analysis to ensure complexation of the polymer composites. Frequency-dependent impedance spectroscopy observation was used to determine ionic conductivity and dielectric parameters. Ionic conductivity was found to vary with increasing salt and filler particle concentrations in the polymer blend complexes. The optimum ambient temperature conductivity achieved was 2.66?×?10?4?S?cm?1 for PEO (65 %), PEG (15 %), LiCF3SO3 (15 %), ethylene carbonate (5 %), and TiO2 (3 %) using weight percentage. The dielectric relaxation time obtained from a loss tangent plot is fairly consistent with the conductivity studies. Both Arrhenius and VTF behaviors of all the composites confirm that the conductivity mechanism of the solid polymer electrolyte is thermally activated.  相似文献   

8.
A. K. Nath  A. Kumar 《Ionics》2014,20(12):1711-1721
Swift heavy ion (SHI) irradiation has been used as a tool to enhance the electrochemical properties of ionic liquid-based nanocomposite polymer electrolytes dispersed with dedoped polyaniline (PAni) nanorods; 100 MeV Si9+ ions with four different fluences of 5?×?1010, 1?×?1011, 5?×?1011, and 1?×?1012 ions cm?2 have been used as SHI. XRD results depict that with increasing ion fluence, crystallinity decreases due to chain scission up to fluence of 5?×?1011 ions cm?2, and at higher fluence, crystallinity increases due to cross-linking of polymer chains. Ionic conductivity, electrochemical stability, and dielectric properties are enhanced with increasing ion fluence attaining maximum value at the fluence of 5?×?1011 ions cm?2 and subsequently decrease. Optimum ionic conductivity of 1.5?×?10?2 S cm?1 and electrochemical stability up to 6.3 V have been obtained at the fluence of 5?×?1011 ions cm?2. Ac conductivity studies show that ion conduction takes place through hopping of ions from one coordination site to the other. On SHI irradiation, amorphicity of the polymer matrix increases resulting in increased segmental motion which facilitates ion hopping leading to an increase in ionic conductivity. Thermogravimetric analysis (TGA) measurements show that SHI-irradiated nanocomposite polymer electrolytes are thermally stable up to 240–260 °C.  相似文献   

9.
Frequency dependences of the real (?′) and imaginary (?″) parts of the complex permittivity, the dielectric loss tangent (tanδ), and the ac conductivity (σac) in frequency range f = 5 × 104?3.5 × 107 Hz have been investigated for TlGa1 ? x Er x Se2 crystals of various compositions. It has been established that the relaxation dispersion of ?′ and ?″ takes place for the studied crystals. The influence of the erbium content in the crystals on their dielectric coefficients has been studied. The ac conductivity of the TlGa1 ? x Er x Se2 single crystals in the high-frequency range obeys the law σacf 0.8, which is characteristic of the hopping mechanism of charge transfer over the states localized in the vicinity of the Fermi level. Parameters of the states localized in the band gap of TlGa1 ? x Er x Se2 and the influence of the composition of the crystals on these parameters have been evaluated.  相似文献   

10.
A series of nano-crystalline ceria-based solid solution electrolyte, Ce0.8La0.2?x MgxO2?δ (x?=?0.0, 0.05, 0.10, 0.15, and 0.2), were synthesized via the polyvinyl alcohol (PVA) assisted combustion method, and then characterized to the crystalline structure, powder morphology, sintering micro-structure, and electrical properties. Present study showed that Ce0.8La0.2?x Mg x O2?δ was exceedingly stable as a cubic phase in all temperature range and exhibited fine crystals ranging from 15 to 20 nm. After sintering at 1,400 °C, the as-prepared pellets exhibited a dense micro-structure with 96 % of theoretical density. The electrical conductivity was studied using AC impedance spectroscopy and it was observed that the composition Ce0.8La0.1?Mg0.1O2?δ showed higher electrical conductivity of 0.020 S?cm?1 at 700 °C. The thermal expansion was measured using dilatometer technique in the temperature range 30–1,000 °C. The average thermal expansion coefficient of Ce0.8La0.1?Mg0.1O2?δ was 12.37?×?10?6 K?1, which was higher than that of the commonly used SOFC electrolyte YSZ (~10.8?×?10?6 K?1).  相似文献   

11.
A nanohybrid C-LiMnPO4 is important to tailor its electrochemical properties useful for Li+-ion batteries and photo-catalysis. In this article, we report a simple in situ C-LiMnPO4 synthesis, wherein the LiMnPO4 grows from a supersaturated solution LiOH·H2O, MnSO4·H2O, and H3PO4 in water at 200 °C in an autoclave in a hydrothermal reaction and bonds in situ to nascent carbon of a surface layer on a surface reaction with a long chain hydrocarbon used during the reaction. A phase pure C-LiMnPO4 is formed in a shape of nanorods (Pnma orthorhombic crystal structure), with 100–150 nm diameters, 150–800 nm lengths, and 2–3 nm thickness of a co-bonded C-sp2 surface layer. The LiMnPO4 rigidly co-bonds to C-sp2 via O2? in the PO4 3? polygons in a joint surface layer that a single molecular bonding extends well up to 600 °C, with a due mass loss on an extended heating in air. The sample contains fine pores with an average 3.0 nm diameter and a 9.0 m2/g surface area. At room temperature, it develops a huge dielectric permittivity ε r~1.9 × 105 near 1 Hz frequencies, which on raising the frequency decays progressively to a fairly steady ε r~1.5 × 103 at ≥1 kHz. Bare LiMnPO4 is a low dielectric phase, ε r < 10. A non-Debye type of dielectric relaxation is shown in the modulus plots. As frequency approaches to 105 Hz, nearly three orders of larger ac conductivity, 2.5 × 10?5 Scm?1 at 106 Hz, develop over a carbon-free LiMnPO4 value useful for the applications.  相似文献   

12.
In this work, we investigate the electrical, structural, and thermal properties of composite polymer electrolytes (CPEs). Different mass fractions of antimony trioxide filler, Sb2O3, are added into poly(acrylic acid) (PAA)-based polymer electrolytes with N-lithiotrifluoromethane sulphonamide [LiN(SO2CF3)2] (LiTFSI) as doping salt. Characteristics such as alternating current (AC)–impedance spectroscopy, attenuated total reflectance–Fourier transform infrared (ATR-FTIR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) are analyzed. The highest ionic conductivity of (2.15?±?0.01)?×?10?4 S cm?1 is achieved at room temperature with addition of 6 wt% of fillers. The ionic transportation is further proven in a transference number study under DC polarization, whereas ATR-FTIR is employed to explore the complexation between PAA, LiTFSI, and Sb2O3. TGA reveals the improved thermal stability of CPEs. The glass transition temperature (T g) is reduced upon addition of Sb2O3 as shown in DSC analysis.  相似文献   

13.
Solid polymer electrolytes based on polyacrylonitrile (PAN) doped with ammonium thiocyanate (NH4SCN) in different molar ratios of polymer and salt have been prepared by solution-casting method using DMF as solvent. The increase in amorphous nature of the polymer electrolytes has been confirmed by XRD analysis. A shift in glass transition temperature (T g) of the PAN?:?NH4SCN electrolytes has been observed from the DSC thermograms which indicates the interaction between the polymer and the salt. From the AC impedance spectroscopic analysis, the ionic conductivity has been found to increase with increasing salt concentration up to 30 mol% of NH4SCN beyond which the conductivity decreases and the highest ambient temperature conductivity has been found to be 5.79?×?10?3 S cm?1. The temperature-dependent conductivity of the polymer electrolyte follows an Arrhenius relationship which shows hopping of ions in the polymer matrix. The dielectric loss curves for the sample 70 mol% PAN?:?30 mol% NH4SCN reveal the low-frequency β-relaxation peak pronounced at high temperature, and it may be caused by side group dipoles. The ionic transference number of polymer electrolyte has been estimated by Wagner’s polarization method, and the results reveal that the conductivity species are predominantly ions.  相似文献   

14.
Solid polymer electrolytes based on potato starch (PS) and graphene oxide (GO) have been developed in this study. Blending GO with PS has improved the ionic conductivity and mechanical properties of the electrolytes. In this work, series of polymer blend consisting of PS and GO as co-host polymer were prepared using solution cast method. The most amorphous PS-GO blend was obtained using 80 wt% of PS and 20 wt% of GO as recorded by X-ray diffraction (XRD). Incorporation of 40 wt% lithium trifluoromethanesulfonate (LiCF3SO3) into the PS-GO blend increases the conductivity to (1.48 ± 0.35) × 10?5 S cm?1. Further enhancement of conductivity was made using 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]). The highest conductivity at room temperature is obtained for the electrolyte containing 30 wt% of [Bmim][Cl] with conductivity value of (4.8?0 ± 0.69) × 10?4 S cm?1. Analysis of the Fourier transform infrared spectroscopy (FTIR) spectra confirmed the interaction between LiCF3SO3, [Bmim][Cl], and PS-GO blend. The variation of the dielectric constant and modulus studies versus frequency indicates that system of PS-GO-LiCF3SO3-[Bmim][Cl] obeys non-Debye behavior.  相似文献   

15.
Nano-composite polymer electrolytes containing poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), ammonium tetrafluoroborate (NH4BF4), and nano-size fumed silica (SiO2) have been prepared and characterized by complex impedance spectroscopy. Ionic conductivity of polymer has been found to increase with the addition of NH4BF4, and a maximum conductivity of 3.62 × 10?6 S/cm has been obtained at 30 wt% NH4BF4. The formation of ion aggregates at high concentration of salt has been explained by Bjerrum’s law and mass action considerations. The conductivity of polymer electrolytes has been increased by three orders of magnitude (10?6 to 10?3 S/cm) with the addition of plasticizer, and a maximum conductivity of 1.10 × 10?3 S/cm has been observed at 80 wt% DMA. An increase in conductivity with the addition of nano-size fumed silica is attributed due to the formation of space-charge layers. A maximum conductivity of 7.20 × 10?3 S/cm has been observed for plasticized nano-composite polymer electrolytes at 3 wt% SiO2. X-ray diffraction analysis of polymer electrolyte system was also carried out. A small change in conductivity of nano-composite polymer electrolytes observed over the 30–130 °C temperature range and for a period of 30 days is also desirable for their use in various applications.  相似文献   

16.
In this study, the effects of addition of sodium citrate dosages and different pH levels on the electrochemical behavior of CoFeNiCu alloy baths (electrolytes containing metal ions) were investigated. Stability (Pourbiax) diagrams and also speciation diagrams of cobalt, iron, nickel and copper, in conventional and citrate-added CoFeNiCu bath, were calculated by ChemEQL V.3.0 software. Stability diagrams showed that addition of 20 g?L?1 sodium citrate to the bath increased the pH of formed detrimental metal hydroxides (especially Fe(OH)3 from pH 3.4 to pH?~?6.9) through forming stable complexed species that were more stable than metal hydroxides at low pH levels (< ~3). According to the speciation diagrams, both pH level and sodium citrate dosage had noticeable effect on the distribution of species in the baths. Generally, at low pH level and/or sodium citrate dosage, Co++, Fe++, Ni++, and Cu++ species were dominant. The concentration of complexed species of Co(C6H5O7)? ( at pH?>?~ 7.5 or sodium citrate dosage?>?~ 30 g?L?1), Fe(C6H5O7)? (at pH?>?~ 5.5 or sodium citrate dosage?>?~ 25 g?L?1), Ni(C6H5O7)? (at pH?>?~ 6 or sodium citrate dosage?>?~ 30 g?L?1), and Cu(OHC6H5O7)2? ( at pH?>?~ 8 or sodium citrate dosage?>?~ 20 g?L?1) became significant. The effects of sodium citrate and reverse potential (E λ) on cyclic voltammetry curves were also studied. The addition of sodium citrate in the bath shifted the reduction potential of metals towards more negative potentials. Moreover, in order to deposit cobalt, iron, and nickel simultaneously with copper, it was necessary to increase E λ value gradually with sodium citrate dosage; otherwise, only copper would have deposited from citrate-added CoFeNiCu bath. The study of speciation diagrams showed that reduction of metals from CoFeNiCu bath with natural pH (no acid or base is added to adjust pH and it was?~?5.2) and containing 20 g?L?1 of sodium citrate mainly occurred directly from complexed species.  相似文献   

17.
The BICO0.20–xNIxVOX solid electrolyte was synthesized by the standard solid-state reaction. The effect of Ni(II) substitution for Co(III) on phase stabilization and oxide-ion performance has been investigated in the compositional range 0?≤?x?≤?0.20 using X-ray powder diffraction, differential thermal analysis and AC impedance spectroscopy. The highly conductive γ′-phase was effectively stabilized at room temperature for compositions with x?≥?0.13 whose thermal stability increases with Ni content. The complex plane plots of impedance were typically represented at temperatures below 380?°C, suggesting a major contribution of polycrystalline grains to the overall electrical conductivity. The dielectric permittivity measurements revealed the fact that suppression of the ferroelectric transition is compositionally dependent. Interestingly, the maximum ionic conductivity at lower temperatures (~2.56?×?10?4?S?cm?1 at 300?°C) was observed for the composition with x?=?0.13. The variation of low-temperature conductivity with Ni content was accompanied with a general drop in the corresponding values of ΔELT. However, the local minimum high-temperature conductivity, σ600?°C?~?2.26?×?10?2?S?cm?1 for x?=?0.10, coupled with a local maximum value of ΔEHT?~?0.48?eV was attributed to an increased defect trapping effect correlated with the V(V)?→?V(IV) reduction at elevated temperatures.  相似文献   

18.
The studies on solid polymer electrolyte (SPE) films with high ionic conductivity suitable for the realization of all solid-state Na-ion cells? form the focal theme of the work presented in this paper. The SPE films are obtained by the solution casting technique using the blend solution of poly (ethylene oxide) (PEO) with ethylene carbonate (EC) and propylene carbonate (PC) and complexed with sodium nitrate. Structural and thermal studies of SPE films are done by XRD, FTIR spectroscopy, and TGA techniques. Surface morphology of the films is studied using the FESEM. The ionic conductivity of SPE films is determined from the electrochemical impedance spectroscopy studies. For the SPE film with 16 wt% of NaNO3 used for reacting with the polymer blend of PEO with EC and PC, the ionic conductivity obtained is around 1.08 × 10?5 S cm?1. Addition of the Al2O3 as the filler material is found to enhance the ionic conductivity of the SPE films. The studies on the Al2O3 modified SPE film show an ionic conductivity of 1.86 × 10–4 S cm?1, which is one order higher than that of the SPE films without the filler content. For the SPE film dispersed with 8 wt% of Al2O3, the total ion transport number observed is around 0.9895, which is quite impressive from the perspective of the applications in electrochemical energy storage devices. From the cyclic voltammetry studies, a wide electrochemical stability window up to 4 V is observed, which further emphasizes the commendable electrochemical behavior of these SPE films.  相似文献   

19.
In the present study, AgFeP2O7 was prepared by a solid-state reaction method. Rietveld refinement of the X-ray diffraction pattern suggests the formation of the single phase desired compound with monoclinic structure at room temperature. Not only were the impedance spectroscopy measurements of our compound carried out from 209 Hz to 5 MHz over the temperature range of 553 K–698 K but its AC conductivity as well as the dielectric relaxation were evaluated. Impedance measurements show AgFeP2O7 an ionic conductor being the conductivity 1.04?×?10–?5–?1cm–?1) at 573 K. The conductivity and modulus formalisms provide nearly the same activation energies for electrical relaxation of mobile ions revealing that transport properties in this material appear to be due to an ionic hopping mechanism dominated by the motion of the Ag+ ions along tunnels presented in the structure of the investigated material.  相似文献   

20.
Solid polymer polyethylene glycol (PEG)-based electrolytes composed with zinc acetate Zn(CH3COO)2 have been prepared by using solution blending. We proposed a scheme of PEG–zinc acetate for battery application. The structure confirmation was done by using X-ray diffraction studies detecting the phase variation. The thermal properties demonstrate the optimization of melting point (T m) as a function of loading zinc acetate. The impedance analysis reveals that the role of ionic conductivity depends on the controlled concentration of Zn(CH3COO)2. Optimum ionic conductivity σ?~?1.55?×?10?6 S?cm?1 at room temperature (303 K) was observed for 70:30 composition. The linear variation in log σ vs 1000/T plot is based on the Arrhenius-type thermally activated process. The simultaneous discharge profile was confirmed by the solid-state electrochemical cell. Hence, the PEG–zinc acetate composition was suggested for polymer electrolyte battery application.  相似文献   

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