Conductivity relaxation in Ag+ ion conducting PEO–PMMA–PEG polymer blends

In this paper, the electrical conductivity and relaxation studies in two different temperature regions (T?<?T _m and T?>?T _m) on plasticized PEO–PMMA blend polymer electrolyte system with AgNO₃ salt are reported. The polymer electrolyte system has been prepared by solution cast technique and characterized by X-ray diffraction and differential scanning calorimetry. The conduction and relaxation processes at various temperatures have been investigated in the framework of modulus formalism. The distribution of relaxation times is discussed using Argand plot. Variation in ionic conductivity of polymer blends is discussed with the increase of PEO as well as with temperature.     

Preparation and characterization of a new PEO-PPG blend polymer electrolyte system

This paper reports on preparation and characterization of thin films of a new zinc ion conducting blended polymer electrolyte system containing polyethylene oxide [PEO] and polypropylene glycol [PPG] complexed with zinc triflate [Zn(CF₃SO₃)₂] salt. The room temperature ionic conductivity (σ _298K) data of such PEO-PPG polymer blends prepared by solution casting technique were found to be of the order of 10^?5 S cm^?1, whereas the optimized composition containing 90:10 wt% ratio of PEO and PPG possessed an appreciably high ionic conductivity of 7.5?×?10^?5 S cm^?1. Subsequently, six different weight percentages of zinc triflate viz., 2.5, 5, 7.5, 10, 12.5 and 15, respectively, were added into the above polymer blend and resulting polymer-salt complexes were characterized by means of various analytical tools. Interestingly, the best conducting specimen namely 87.5 wt% (PEO:PPG)-12.5 wt% Zn(CF₃SO₃)₂ exhibited an enhanced room temperature ionic conductivity of 6.9?×?10^?4 S cm^?1 with an activation energy of 0.6 eV for ionic conduction. The present XRD results have indicated the occurrence of characteristic PEO peaks and effects of salt concentration on the observed intensity of these diffraction peaks. Appropriate values of degree of crystallinity for different samples were derived from both XRD and DSC analyses, while an examination of surface morphology of the blended polymer electrolyte system has revealed the formation of homogenous spherulites involving a rough surface and relevant zinc ionic transport number was found to be 0.59 at room temperature for the best conducting polymer electrolyte system thus developed.     

New polymer electrolyte based on (PVA–PAN) blend for Li-ion battery applications

A polymer blend electrolyte based on polyvinyl alcohol (PVA) and polyacrylonitrile (PAN) was prepared by a simple solvent casting technique in different compositions. The ionic conductivity of polymer blend electrolytes was investigated by varying the PAN content in the PVA matrix. The ionic conductivity of polymer blend electrolyte increased with the increase of PAN content. The effect of lithium salt concentrations was also studied for the polymer blend electrolyte of high ionic conductivity system. A maximum ionic conductivity of 3.76×10⁻³ S/cm was obtained in 3 M LiClO₄ electrolyte solution. The effect of ionic conductivity of polymer blend electrolyte was measured by varying the temperature ranging from 298 to 353 K. Linear sweep voltammetry and DC polarization studies were carried out to find out the stability and lithium transference number of the polymer blend electrolyte. Finally, a prototype cell was assembled with graphite as anode, LiMn₂O₄ as cathode, and polymer blend electrolyte as the electrolyte as well as separator, which showed good compatibility and electrochemical stability up to 4.7 V.     

Structural, conductivity, and dielectric characterization of PEO–PEG blend composite polymer electrolyte dispersed with TiO2 nanoparticles

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.     

Investigations on the effect of complexation of NaF salt with polymer blend (PEO/PVP) electrolytes on ionic conductivity and optical energy band gaps

Sodium ion conducting polymer blend electrolyte films, based on polyethylene oxide (PEO) and polyvinyl pyrrolidone (PVP) complexed with NaF salt, were prepared using solution casting technique. The complexation of the salt with the polymer blend was confirmed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and UV-vis spectroscopy. Electrical conductivity of the films was measured with impedance analyzer in the frequency range of 1 Hz to 1 MHz and in the temperature range of 303-348 K. It was observed that the magnitude of conductivity increased with the increase in the salt concentration as well as the temperature. UV-vis absorption spectra in wavelength region of 200-800 nm were used to evaluate the optical properties like direct and indirect optical energy band gaps, optical absorption edge. The optical band gaps decreased with the increase in Na⁺ ion concentration. This suggests that NaF, as a dopant, is a good choice to improve the electrical properties of PEO/PVP polymer blend electrolytes.     

Effect of ethylene carbonate concentration on structural and electrical properties of PEO–PMMA polymer blends

Polyethylene oxide–polymethyl methacrylate (PEO–PMMA) polymer blend electrolyte system complexed with silver salt having different ethylene carbonate (EC) concentrations was prepared using solution cast technique. Complex formation and change in structural and microstructural properties have been studied by X-ray diffraction, Fourier transform infrared, and scanning electron microscopy analysis. The thermal properties of polymer films have been examined by the differential scanning calorimetry technique. Addition of plasticizer is observed to lower melting temperature. Electrical response of polymer films has been measured as a function of EC concentration and temperature using complex impedance spectroscopy. Complex impedance data are used to analyze the conductivity, permittivity, and modulus formalism to understand the conduction mechanism. The temperature dependence of electrical conductivity of polymer electrolytes shows a sudden rise at the melting temperature of PEO.     

Effect of nanofillers on thermal and transport properties of potassium iodide–polyethylene oxide solid polymer electrolyte

In order to enhance the ionic conductivity of polyethylene oxide (PEO)–KI(80:20) based alkaline polymer electrolytes, nanosized inorganic filler ZnS has been incorporated into PEO–KI matrix and the corresponding nanocomposite polymer electrolytes are synthesized by the usual solution casting procedure. Atomic force microscope image of composite polymer electrolyte exhibits that the introduction of ZnS nanoparticles changes the surface morphology and aggregates them to form an arborization pattern. The prepared nanocomposite polymer electrolyte reveals an ionic conductivity of about 10^?4 S cm^?1 for 5 wt% ZnS at room temperature.     

Effects of plasticizer and nanofiller on the dielectric dispersion and relaxation behaviour of polymer blend based solid polymer electrolytes

Solid polymer electrolytes consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend (50:50 wt/wt%) with lithium triflate (LiCF₃SO₃) as a dopant ionic salt at stoichiometric ratio [EO + (CO)]:Li⁺ = 9:1, poly(ethylene glycol) (PEG) as plasticizer (10 wt%) and montmorillonite (MMT) clay as nanofiller (3 wt%) have been prepared by solution cast followed by melt–pressing method. The X–ray diffraction study infers that the (PEO–PMMA)–LiCF₃SO₃ electrolyte is predominantly amorphous, but (PEO–PMMA)–LiCF₃SO₃–10 wt% PEG electrolyte has some PEO crystalline cluster, whereas (PEO–PMMA)–LiCF₃SO₃–10 wt% PEG–3 wt% MMT electrolyte is an amorphous with intercalated and exfoliated MMT structures. The complex dielectric function, ac electrical conductivity, electric modulus and impedance spectra of these electrolytes have been investigated over the frequency range 20 Hz to 1 MHz. These spectra have been analysed in terms of the contribution of electrode polarization phenomenon in the low frequency region and the dynamics of cations coordinated polymer chain segments in the high frequency region, and also their variation on the addition of PEG and MMT in the electrolytes. The temperature dependent dc ionic conductivity, dielectric relaxation time and dielectric strength of the plasticized nanocomposite electrolyte obey the Arrhenius behaviour. The mechanism of ions transportation and the dependence of ionic conductivity on the segmental motion of polymer chain, dielectric strength, and amorphicity of these electrolytes have been explored. The room temperature ionic conductivity values of the electrolytes are found ∼10⁻⁵ S cm⁻¹, confirming their use in preparation of all-solid-state ion conducting devices.     

Poly(ethylene oxide)-lithium difluoro(oxalato)borate new solid polymer electrolytes: ion–polymer interaction,structural, thermal,and ionic conductivity studies

Solid polymer electrolytes based on high molecular weight poly(ethylene oxide) (PEO) complexed with lithium difluoro(oxalato)borate (LiDFOB) salt in various EO:Li molar ratios from 30:1 to 8:1 were prepared by using solution casting technique. Ion–polymer interaction, structural, thermal, and ionic conductivity studies have been reported by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), polarized optical microscopy (POM), differential scanning calorimeter (DSC), and impedance analysis. FTIR spectral studies suggested that the interaction of Li⁺ cations with the ether oxygen of PEO, where a triple peak broad band centered at 1105 cm^?1, corresponds to C–O–C stretching and extreme deformation occurs. XRD, POM, and DSC indicated that the inclusion of LiDFOB salt could reduce the crystallinity of PEO. The melting temperature of PEO shifted to lower temperature side by the addition of LiDFOB. The glass transition temperature obtained for the system 10:1 was ?38.2 °C. An increase in the ionic conductivity from 3.95?×?10^?9 to 3.18?×?10^?5 S/cm at room temperature (23 °C) was obtained through the addition of LiDFOB to a high molecular weight PEO. In addition, the ionic conductivity of the polymer electrolyte films followed an Arrhenius relation, and the activation energy decreased with increasing LiDFOB concentration.     

Effect of polysorbate plasticizer on the structural and ion conduction properties of PEO–NH<Subscript>4</Subscript>PF<Subscript>6</Subscript> solid polymer electrolyte

Effects of a new plasticizer, polysorbate 80, on the structural and electrochemical properties of PEO–NH₄PF₆ polymer electrolyte system have been investigated. X-ray diffraction studies show significant increase in amorphicity of the solid polymer electrolyte on introduction of the plasticizer, which is also supported by lesser-dense spherulites observed in the SEM micrographs. The room temperature ionic conductivity of the electrolyte shows an increase of about two orders of magnitude (σ_max～10^?5 S/cm) on plasticization. The frequency dependence of the conductivity has been found to obey the Jonscher’s power law and slower backward ion hopping on plasticization. The polymer electrolyte shows protonic conduction as confirmed using cyclic voltammetry study. The studies show that polysorbate 80 is a promising plasticizer for semicrystalline polymer electrolytes.     

Structural and electrical characterizations of 50:50 PVA:starch blend complexed with ammonium thiocyanate

The present work deals with the preparation and characterization of polymer blend electrolyte films. Glutaraldehyde is used as a cross-linker to cross-link polymers polyvinyl alcohol (PVA) and starch for the proper film formation. Structural characterizations such as X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) have been performed. X-ray diffraction is done to investigate the amorphous nature of the sample. FTIR study confirms about the complexation of salt with the polymer and interaction of thiocyanate ion with the polymer matrix. Electrical characterizations were done using impedance spectroscopy. DC and AC ionic conductivity was obtained at varying salt concentration in the films which shows maximum ionic conductivity of the polymer electrolyte containing 30 wt% of salt content. The AC conductivity behaviour of the polymer electrolyte follows Jonscher’s power law. Dielectric parameters such as dielectric constant, dielectric loss and loss tangent have been determined. Relaxation time is obtained and decreases to lower value with the increase in the salt concentration in the polymer electrolyte.     

LiClO4-doped plasticized chitosan and poly(ethylene glycol) blend as biodegradable polymer electrolyte for supercapacitors

Biodegradable polymer electrolyte comprising the blend of chitosan (CS) and poly(ethylene glycol) (PEG) plasticized with ethylene carbonate and propylene carbonate, as host polymer, and lithium perchlorate (LiClO₄), as a dopant, was prepared by solution casting technique. The ionic conductivity has been calculated using the bulk impedance obtained through impedance spectroscopy. The variation of conductivity and dielectric properties has been investigated as a function of polymer blend ratio, plasticizer content and LiClO₄ concentration at temperature range of 298–343 K. The DSC thermograms show two broad peaks for CS/PEG blend and increased with increase in the LiClO₄ content. The maximum conductivity has been found to be 1.1?×?10^?4 S cm^?1 at room temperature for 70:30 (CS/PEG) concentration. The electric modulus of the electrolyte film exhibits a long tail feature indicative of good capacitance. The activation energy of all samples was calculated using the Arrhenius plot, and it has been found to be 0.12 to 0.38 eV. A carbon–carbon supercapacitor has been fabricated using this electrolyte, and its electrochemical characteristics and performance have been studied. The supercapacitor showed a fairly good specific capacitance of 47 F?g^?1.     

Exploring low temperature Li+ ion conducting plastic battery electrolyte

We report blend-based plastic polymer electrolyte (i.e., polyethylene oxide (PEO)–polydimethyl siloxane (PDMS)–lithium hexafluorophosphate (LiPF₆)) with substantial improvement in DC conductivity at ambient and subambient temperatures when compared with literature reports. Conductivity variation with salt concentration, investigated within ±30 °C range, indicates an optimum conductivity of 5.6?×?10^?5 S cm^?1 at 30 °C for Ö/Li ~10 with a further lowering by one order at 0 °C and it remains unaltered at ?10 °C. Enhanced conductivity in this blend electrolyte, though lower than two copolymer counterparts, is attributed to very low glass transition temperatures of the host polymers. X-ray diffraction (XRD) and scanning electron microscopy (SEM) suggest an effective blending between the two polymers with an effective interaction between the Li salt and the blend polymer matrix. Raman spectroscopy results indicated that cation (Li⁺) coordination occurs at the C=Ö site in PEO out of the two electron-rich sites (i.e., CÖ and Si–Ö–Si) in the PEO–PDMS blend. The blend electrolytes are predominantly ionic (t _ion ~97 %).     

Incorporation of NH<Subscript>4</Subscript>NO<Subscript>3</Subscript> into MC-PVA blend-based polymer to prepare proton-conducting polymer electrolyte films

Proton-conducting solid polymer blend electrolytes based on methylcellulose-polyvinyl alcohol:ammonium nitrate (MC-PVA:NH₄NO₃) were prepared by the solution cast technique. The structural and electrical properties of the samples were examined by X-ray diffraction (XRD), Fourier transform infrared (FTIR), and electrical impedance (EI) spectroscopy. The shifting and change in the intensity of FTIR bands of the electrolyte samples confirm the complex formation between the MC-PVA polymer blend and the NH₄NO₃ added salt. The observed broadening in the XRD pattern of the doped samples reveals the increase of the amorphous fraction of polymer electrolyte samples. The increase in electrical conductivity of polymer electrolyte samples with increasing salt concentration attributed to the formation of charge-transfer complexes, and to increase in the amorphous domains. A maximum ionic conductivity of about 7.39 × 10^?5 S cm^?1 was achieved at room temperature for the sample incorporating 20 wt% of NH₄NO₃. The DC conductivity of the present polymer system exhibits Arrhenius-type dependence with temperature. The decrease in the values of activation energies with increasing salt concentration indicates the ease mobility of ions. The decrease in dielectric constant with increasing frequency was observed at all temperatures. Optical properties such as absorption edge, optical band gap, and tail of localized state were estimated for polymer blend and their electrolyte films. It was found that the optical band gap values shifted towards lower photon energy from 6.06 to 4.75 eV by altering the NH₄NO₃ salt content.     

Effects of compositions on properties of PEO–KI–I2 salts polymer electrolytes for DSSC

The effects of compositions on properties of PEO/KI/I₂ salts polymer electrolytes were investigated to optimize the photovoltaic performance of solid state DSSCs. XRD pattern for the mole ratio 12:1 of [EO:KI] was showed the formation of complete amorphous complex. DSC results also confirmed the amorphous nature of the polymer electrolyte. The highest value of ionic conductivity is 8.36 × 10^− 5 S/cm at 303 K (ambient temperature) and 2.32 × 10^− 4 S/cm at 333 K (moderate temperature) for the mole ratio 12:1 of EO:KI complex. The effect of contribution of [I⁻] and [I₃⁻] concentration with conductivity were also evaluated. FTIR spectrum reveals that the alkali metal cations were co-ordinated to ether oxygen of PEO. The formation of polyiodide ions, such as symmetric I₃⁻ (114 cm^− 1) and I₅⁻ (145 cm^− 1) caused by the addition of iodine was confirmed by FT Raman spectroscopic measurements. The optimum composition of PEO–KI–I₂ polymer electrolyte system for higher conductivity at ambient and moderate temperatures was reported. A linear Arrhenius type behaviour was observed for all the PEO–KI polymer complexes. Transport number measurements were carried out for several polymer electrolyte compositions. Dye-sensitized solar cells were fabricated by using higher conductivity polymer electrolyte compositions and its photoelectrochemical performance was investigated. The fill factor, short-circuit current, photovoltage and energy conversion efficiency of the DSSC assembled with optimized electrolyte composition were calculated to be 0.563, 6.124 mA/cm², 593 mV and 2.044% respectively.     

Charge carriers dynamics in PEO + NaSCN polymer electrolytes

Sodium-ion-conducting poly(ethylene oxide) (PEO)-based solid polymer electrolyte films mixed with salt sodium thiocyanate (NaSCN) have been prepared by solution-cast method. Films were characterized in detail using optical microscopy, differential scanning calorimetry, and impedance spectroscopy. The drop in ionic conductivity with increasing salt concentration is supported by a decrease in number of charge carriers. Dielectric constant is supported by decreases in numbers of charge carriers and increase in mobility. The maximum ionic conductivity and number of charge carriers for material are found 9.86 × 10^?6 S/m and 1.21 × 10²⁰, respectively, for weight % ratio (95:05) of PEO:NaSCN polymer salt complex. The maximum mobility of material is found 2.58 × 10^?6 m²/Vs for weight % ratio (80:20) of PEO:NaSCN polymer salt complex.     

Effect of liquid crystal ionomer intercalated montmorillonite nanocomposites on PEO/PLA solid polymer electrolytes

A series of solid polymer electrolytes (SPEs) based on poly (ethylene oxide)/polylactic acid (PEO/PLA) with liquid crystal ionomer (LCI) intercalated montmorillonite (MMT) nanocomposites (LCI-MMT) has been prepared by solution blending method. The effects of LCI-MMT on the structural, crystallization, thermal, and ionic conductivity properties of solid polymer electrolytes have been analyzed. It is demonstrated that the incorporation of LCI-MMT into the blend suppressed the crystallinity of PEO and increased the crystallinity of PLA. The maximum ionic conductivity is found to be in the range of 1.05?×?10^?5 S/cm for 0.5 wt% LCI-MMT, which is higher than that of the LCI-MMT-free polymer electrolyte (5.36?×?10^?6 S/cm) at room temperature.     

Ionic transport, thermal, XRD, and phase morphological studies on LiCF3SO3-based PVC–PVdF gel electrolytes

The plasticized polymer electrolyte composed of polyvinylchloride (PVC) and polyvinylidene fluoride (PVdF) as host polymer, the mixture of ethylene carbonate and propylene carbonate as plasticizer, and LiCF₃SO₃ as a salt was studied. The effect of the PVC-to-PVdF blend ratio with the fixed plasticizer and salt content on the ionic conduction was investigated. The electrolyte films reveal a phase-separated morphology due to immiscibility of the PVC with plasticizer. Among the three blend ratios studied, 3:7 PVC–PVdF blend ratio has shown enhanced ionic conductivity of 1.47 × 10⁻⁵ S cm⁻¹ at ambient temperature, i.e., the ionic conductivity decreased with increasing PVC-to-PVdF ratio and increased with increasing temperature. A temperature dependency on ionic conductivity obeys the Arrhenius behavior. The melting endotherms corresponding to vinylidene (VdF) crystalline phases are observed in thermal analysis. Thermal study reveals the different levels of uptake of plasticizer by VdF crystallites. The decrease in amorphousity with increase in PVC in X-ray diffraction studies and larger pore size appearance for higher content of PVC in scanning electron microscopy images support the ionic conductivity variations with increase in blend ratios.     

Conductivity studies on PEO:NaClO3 electrolyte system with different plasticizers

A new ion conducting solid polymer electrolyte thin film based on Polyethylene oxide (PEO) with NaClO₃ salt is prepared by solution-casting method. The solvation of salt with PEO has been confirmed by X-ray diffraction and IR spectral studies. Plasticizer effects were studied in PEO:NaClO₃ system by using low molecular weight polyethylene glycol (PEG), dimethyl formamide (DMF) and propylene carbonate(PC). AC conductivity in the temperature range (308–378 K) was measured to evaluate the conductivity of the polymer electrolytes. From the conductivity data, it was found that the conductivity value of pure PEO increases 10²–10⁴ order of magnitude with the addition of salts as well as plasticizers. From the transference number experiments, it was confirmed that the charge transport in these electrolyte is mainly due to the ions (t_ion≈0.94). Finally, the conductivity value of all PEO: NaClO₃ systems were compared.     

A novel PEO-based composite polymer electrolyte with NaAlOSiO molecular sieves powders

Ion-conducting thin film polymer electrolytes based on poly(ethylene oxide) (PEO) complexes with NaAlOSiO molecular sieves powders has been prepared by solution casting technique. X-ray diffraction, scanning electron microscopy, differential scanning calorimeter, and alternating current impedance techniques are employed to investigate the effect of NaAlOSiO molecular sieves on the crystallization mechanism of PEO in composite polymer electrolyte. The experimental results show that NaAlOSiO powders have great influence on the growth stage of PEO spherulites. PEO crystallization decrease and the amorphous region that the lithium-ion transport is expanded by adding appropriate NaAlOSiO, which leads to drastic enhancement in the ionic conductivity of the (PEO)₁₆LiClO₄ electrolyte. The ionic conductivity of (PEO)₁₆LiClO₄-12 wt.% NaAlOSiO achieves (2.370 ± 0.082) × 10⁻⁴ S · cm⁻¹ at room temperature (18 °C). Without NaAlOSiO, the ionic conductivity has only (8.382 ± 0.927) × 10⁻⁶ S · cm⁻¹, enhancing 2 orders of magnitude. Compared with inorganic oxide as filler, the addition of NaAlOSiO molecular sieves powders can disperse homogeneously in the electrolyte matrix without forming any crystal phase and the growth stage of PEO spherulites can be hindered more effectively.