Structural and dielectric studies of amorphous and semicrystalline polymers blend‐based nanocomposite electrolytes

The solid polymeric nanocomposite electrolyte (SPNE) films based on the blend of amorphous poly(methyl methacrylate) (PMMA) and semicrystalline poly(ethylene oxide) (PEO) (PMMA:PEO = 80:20 wt %) doped with lithium perchlorate (LiClO₄) salt and montmorillonite (MMT) clay nanofiller were prepared by classical solution cast, ultrasonic assisted solution cast and ultrasonication along with microwave irradiated solution cast followed by melt‐pressing methods. The X‐ray diffraction study of these electrolytes revealed the amorphous behavior with intercalated MMT structures. The suppressed crystallinity of PEO in the blend electrolyte complexes confirmed the existence of single discrete PEO chains confined within the PMMA domains. The dielectric relaxation spectroscopy of these materials was performed over the frequency range 20 Hz to 1 MHz, at ambient temperature. The presence of a singular relaxation peak in the loss tangent and electric modulus spectra of these electrolytes confirms a coupled cooperative chain segmental dynamics of the blend polymer owing to their miscible amorphous morphology. The behavior of transient complexes formed between the polymers functional groups, lithium cations and the intercalated MMT nanoplatelets was explored. The ambient temperature ionic conductivity of these electrolytes depends on the structural dynamics and the sample preparation methods. It is revealed that the presence of PEO in the PMMA matrix mainly governs the structural, dielectric, and ionic properties of these SPNE films. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41311.     

Ionic conductivity,dielectric behavior,and HATR–FTIR analysis onto poly(methyl methacrylate)–poly(vinyl chloride) binary solid polymer blend electrolytes

Solid polymer electrolytes comprising blends of poly(vinyl chloride) (PVC) and poly(methyl methacrylate) (PMMA) as host polymers and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) as dopant salt were prepared by solution‐casting technique. The ionic conductivity and dielectric behavior were investigated by using AC‐impedance spectroscopy in the temperature range of 298–353 K. The highest ionic conductivity of (1.11 ± 0.09)×10^?6 S cm^?1 is obtained at room temperature. The temperature dependence of ionic conductivity plots showed that these polymer blend electrolytes obey Arrhenius behavior. Conductivity–frequency dependence, dielectric relaxation, and dielectric moduli formalism were also further discussed. Apart from that, the structural characteristic of the polymer blend electrolytes was characterized by means of horizontal attenuated total reflectance–Fourier transform infrared (HATR–FTIR) spectroscopy. HATR–FTIR spectra divulged the interaction between PMMA, PVC, and LiTFSI. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of nanofiller concentration on conductivity and dielectric properties of poly(ethylene oxide)–poly(methyl methacrylate) polymer electrolytes

This paper reports the effect of nanofiller concentration on the conductivity and dielectric properties of the poly(ethylene oxide)–poly(methyl methacrylate)–poly(ethylene glycol)–AgNO₃–Al₂O₃ polymer electrolyte system. The preparation of polymer films was done using the solution‐casting technique and characterization of the films was carried out using scanning electron microscopy, differential scanning calorimetry and ionic transport techniques. The ionic conductivity, investigated using impedance spectroscopy, was expected to show interesting behaviour at below and above the melting temperature of poly(ethylene oxide) in the polymer blend films. Complex impedance data were analysed in an alternating current conductivity and dielectric permittivity formalism in order to throw light on the transport mechanism. The effect of nanofiller concentration on conduction and relaxation processes at various temperatures was studied. © 2013 Society of Chemical Industry     

Studies of solvent effect on the conductivity of 2‐mercaptopyridine‐doped solid polymer blend electrolytes and its application in dye‐sensitized solar cells

Solvents and electrolytes play an important role in the fabrication of dye‐sensitized solar cells (DSSCs). We have studied the poly(ethylene oxide)‐poly(methyl methacrylate)‐KI‐I₂ (PEO‐PMMA‐KI‐I₂) polymer blend electrolytes prepared with different wt % of the 2‐mercaptopyridine by solution casting method. The polymer electrolyte films were characterized by the FTIR, X‐ray diffraction, electrochemical impedance and dielectric studies. FTIR spectra revealed complex formation between the PEO‐PMMA‐KI‐I₂ and 2‐mercaptopyrindine. Ionic conductivity data revealed that 30% 2‐mercaptopyridine‐doped PEO‐PMMA‐KI‐I₂ electrolyte can show higher conductivity (1.55 × 10^?5 S cm^?1) than the other compositions (20, 40, and 50%). The effect of solvent on the conductivity and dielectric of solid polymer electrolytes was studied for the best composition (30% 2‐mercaptopyridine‐doped PEO‐PMMA‐KI‐I₂) electrolyte using various organic solvents such as acetonitrile, N,N‐dimethylformamide, 2‐butanone, chlorobenzene, dimethylsulfoxide, and isopropanol. We found that ac‐conductivity and dielectric constant are higher for the polymer electrolytes processed from N,N‐dimethylformamide. This observation revealed that the conductivity of the solid polymer electrolytes is dependent on the solvent used for processing and the dielectric constant of the film. The photo‐conversion efficiency of dye‐sensitized solar cells fabricated using the optimized polymer electrolytes was 3.0% under an illumination of 100 mW cm^?2. The study suggests that N,N‐dimethylformamide is a good solvent for the polymer electrolyte processing due to higher ac‐conductivity beneficial for the electrochemical device applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42489.     

Dielectric,transport and thermal properties of clay based polymer‐ nanocomposites

The polymer nanocomposite films (PNC) with varying amounts of organically modified sodium montmorillonite (DMMT) clay in poly(methyl methacrylate) (PMMA) based polymer matrix were prepared by solution cast technique. Dielectric measurements were carried out on these films as a function of frequency at 30°C and 100°C. The addition of clay significantly improved the ionic conductivity. Transport parameters, such as the diffusion coefficient (D), number density (n) and mobility (μ) of charge carriers were determined using a new approach, which is based on impedance spectroscopy. The temperature‐dependent dc conductivity, relaxation and mobility plots obey the Arrhenius rule. The results suggest that the higher ionic conductivity of these PNC films at elevated temperature is not only due to increased mobility of ions, but it is accompanied by a significant increase in carrier concentration. Analysis of DSC thermogram reveals a very high percentage of amorphous content for all samples. A good correlation among dielectric permittivity, carrier concentration, mobility and ionic conductivity has also been observed. POLYM. ENG. SCI., 58:220–227, 2018. © 2017 Society of Plastics Engineers     

Studies on structural,dielectric and charge transport properties of PVA:LiBr solid polymer electrolyte films

In the present study, solid polymer electrolytes (SPEs) based on poly (vinyl alcohol) (PVA) doped with lithium bromide (LiBr) were prepared by solution casting method. Fourier transform infrared spectroscopy results affirm the complexation of LiBr with PVA. X-ray diffraction results exhibit the increase of amorphous nature of the polymer electrolytes, which is also observed in scanning electron microscopy images and atomic force microscopy topographs. Thermogravimetric analysis thermographs endorse the increase of thermal stability of the polymer due to doping. Dielectric studies exhibit non-Debye nature of the polymer electrolytes. Conductivity spectra reveal the maximum ionic conductivity (1.15 × 10⁻⁴ S/cm) for 20 wt% LiBr/PVA electrolyte at ambient temperature. Impedance analysis reveals the decrease of ionic relaxation in the polymer electrolytes and the studied transport properties of the electrolyte show that the major contribution to the conduction in this polymer electrolyte is ions.     

Electrical performance of lithium ion based polymer electrolyte with polyethylene glycol and polyvinyl alcohol network

A solid polymer electrolyte based on lithium hydroxide (LiOH) added with polyethylene glycol and polyvinyl alcohol polymers was synthesized by solution casting. The structural variation with respect to loading wt% of LiOH reveals the semicrystalline property of polymer electrolyte. The differential scanning calorimetry data shows the onset of crystalline to amorphous transition, which occurs nearly to the melting peak, for higher salt content. The structural properties and cross-linking between polymer and salt were demonstrated by polarized optical microscopy. The polymer electrolytes were subjected to AC impedance analysis spectra for obtaining the ionic conductivity at different temperature. The charge carriers relax much faster for higher lithium salt concentration based polymer electrolyte and produces higher conductivity. The highest room temperature conductivity 2.63 × 10^?5 S/cm is obtained for 8 wt% loading of lithium salt based polymer electrolyte, confirming their use in preparation of ion conducting devices.     

Dielectric and electrical characterization of (PEO–PMMA)–LiBF<Subscript>4</Subscript>–EC plasticized solid polymer electrolyte films

Plasticized solid polymer electrolytes (PSPEs) consisting of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend (50/50 wt%) based matrix with lithium tetrafluoroborate (LiBF₄) as dopant ionic salt (10 wt%) and varied concentrations (x = 0, 5, 10 and 15 wt%) of ethylene carbonate (EC) as plasticizer have been prepared. Classical solution-cast (SC) and the ultrasonic assisted followed by microwave irradiated (US–MW) solution-cast methods have been used for the preparation of (PEO–PMMA)–LiBF₄–x wt% EC films, and the same have been hot–pressed to get their smooth surfaces. Dielectric relaxation spectroscopy (DRS) and X–ray diffraction (XRD) techniques have been employed to characterize the dielectric and electrical dispersions and the structural properties of the PSPE films, respectively. It has been observed that the ionic conductivity of these semicrystalline ion-dipolar complexes is governed by their dielectric permittivity and polymers chain segmental dynamics. The increase in ionic conductivity values with the increase of plasticizer concentration in the PSPEs also varies with the films’ preparation methods. The US–MW method prepared PSPE film containing 15 wt% EC has a maximum ionic conductivity (1.86 × 10^?5 S cm^?1) at room temperature, whereas, the films having low concentrations of EC exhibit the conductivity of the order of 10^?6 S cm^?1.     

Preparation and performance analysis of barium titanate incorporated in corn starch‐based polymer electrolytes for electric double layer capacitor application

Polymer electrolyte membranes composing of corn starch as host polymer, lithium perchlorate (LiClO₄) as salt, and barium titanate (BaTiO₃) as composite filler are prepared using solution casting technique. Ionic conductivity is enhanced on addition of BaTiO₃ by reducing the crystallinity and increasing the amorphous phase content of the polymer electrolyte. The highest ionic conductivity of 1.28 × 10^?2 S cm^?1 is obtained for 10 wt % BaTiO₃ filler in corn starch‐LiClO₄ polymer electrolytes at 75°C. Glass transition temperature (T_g) of polymer electrolytes decreases as the amount of BaTiO₃ filler is increased, as observed in differential scanning calorimetry analysis. Scanning electron microscopy and thermogravimetric analysis are employed to characterize surface morphological and thermal properties of BaTiO₃‐based composite polymer electrolytes. The electrochemical properties of the electric double‐layer capacitor fabricating using the highest ionic conductivity polymer electrolytes is investigated using cyclic voltammetry and charge‐discharge analysis. The discharge capacitance obtained is 16.22 F g^?1. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43275.     

Effect of carbon nanotube dispersion on electrochemical and mechanical characteristics of poly(methyl methacrylate)‐based gel polymer electrolytes

Polymer‐based electrolyte of lithium ion batteries and other devices have shortcomings of low ionic conductivity and inadequate mechanical strength. The study presents the preparation of polymethyl methacrylate (PMMA)‐based three‐layered nanocomposite gel polymer electrolytes (NCGPEs) having multiwalled carbon nanotubes (MWCNTs) dispersed in the middle layer of the composites and the effect of dispersoid quantities on the ionic, mechanical, and thermal characteristics of the electrolytes. The NCGPEs were synthesized by solution cast process with the various MWCNTs contents of 0.5, 1.0, 1.5, and 2.0 wt%. Morphology of the NCGPEs has been observed by scanning and transmission electron microscopes (SEMs). Interactions between the constituents of the composite and structural changes of the base polymer were investigated by Fourier transform infrared (FTIR) spectroscopy and X‐ray diffraction (XRD) techniques. The mechanical strength of the NCGPEs increases considerably owing to the dispersion of MWCNTs and the highest strength was found for the dispersion of 2.0 wt% of MWCNTs. The thermal stability of the nanocomposites was investigated by thermo‐gravimetric analysis (TGA). The chemical decomposition temperature of the nanocomposites increases considerably as compared to the gel polymer electrolyte. Ionic conductivity of the composite electrolyte increases with the increase in addition of MWCNTs and the maximum ionic conductivity (10⁻³ S cm⁻¹) of the nanocomposite has been found with the dispersion of 2.0 wt% MWCNTs among all the dispersoid. POLYM. COMPOS., 37:1936–1944, 2016. © 2015 Society of Plastics Engineers     

Poly(methyl methacrylate) based nanocomposite gel polymer electrolytes with enhanced safety and performance

The study presents preparation of poly methyl methacrylate (PMMA) based nanocomposite gel polymer electrolytes consisting of, salt lithium perchlorate (LiClO₄), plasticizer PC/DEC and different proportions of SiO₂ nanofiber by solution casting process. The effect of the composition of the electrolytes on their ionic, mechanical and thermal characteristics was investigated. Morphology of the nanocomposite electrolyte films has been observed by scanning and transmission electron microscopes. Interactions among the constituents of the composite and structural changes of the base polymer were investigated by Fourier Transform Infrared (FTIR) spectroscopy and X-ray diffraction (XRD) techniques. The maximum conductivity i.e. 10^?3 Scm^?1 at room temperature is obtained with the electrolyte composition of 0.6(PMMA)-0.15(PC + DEC)-0.1LiClO₄ (wt%) containing 10 wt% SiO₂ nanofiber and the temperature dependent conductivity data of the electrolyte follows Vogel-Tamman-Fulcher (VTF) behavior.     

Synthesis and electrochemical characterization of PEO-based polymer electrolytes with room temperature ionic liquids

New gel polymer electrolytes containing 1-butyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imide (BMPyTFSI) ionic liquid are prepared by solution casting method. Thermal and electrochemical properties have been determined for these gel polymer electrolytes. The addition of BMPyTFSI to the P(EO)₂₀LiTFSI electrolyte results in an increase of the ionic conductivity, and at high BMPyTFSI concentration (BMPy⁺/Li⁺ = 1.0), the ionic conductivity reaches the value of 6.9 × 10⁻⁴ S/cm at 40 °C. The lithium ion transference numbers obtained from polarization measurements at 40 °C were found to decrease as the amount of BMPyTFSI increased. However, the lithium ionic conductivity increased with the content of BMPyTFSI. The electrochemical stability and interfacial stability for these gel polymer electrolytes were significantly improved due to the incorporation of BMPyTFSI.     

Effect of various plasticizers on the transport properties of hexanoyl chitosan‐based polymer electrolyte

Hexanoyl chitosan that exhibited solubility in tetrahydrofuran was prepared by acyl modification of chitosan. Films of hexanoyl chitosan‐based polymer electrolyte were prepared by the technique of solution casting. Ethylene carbonate, propylene carbonate, and diethyl carbonate with different dielectric constants were employed as the plasticizing solvents and lithium trifluoromethanesulfonate (LiCF₃SO₃) was used as the salt. The importance of dielectric constant affecting conductivity and transport properties of hexanoyl chitosan:LiCF₃SO₃ electrolytes have been examined in the present study. An enhancement in the ionic conductivity has been found on plasticization, and the magnitude of conductivity increment strongly depended on the dielectric constant of the plasticizer. Transport properties such as activation energy and charge carrier concentration have been calculated to obtain information that may be used to elucidate the mechanism of conductance. In addition to conductivity studies, thermal studies and transference number measurements were performed to correlate the phase structure and diffusion phenomena to the conductivity behavior of hexanoyl chitosan‐based polymer electrolyte. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101:4474–4479, 2006     

Electrochemical investigations on the effect of dispersoid in PVA based solid polymer electrolytes

Various compositions of TiO₂ dispersed PVA‐PMMA‐LiBF₄‐EC based electrolytes were prepared using solution casting technique. The prepared electrolytes were characterized using AC impedance, XRD, SEM, FTIR, etc. The ionic conductivity value is increased with the increase in filler content (up to 8 wt %) and then decreased with the increase in filler content. The results are described using Vogel–Tamman–Fulcher theory. The thermal and transport properties of the electrolyte exhibiting maximum conductivity have also been studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3950–3956, 2007     

Ionic conductivity and dielectric behavior of novel poly(vinyl formal)‐based single‐ion‐conductor polymer electrolytes

Novel single‐ion‐conductor polymer (SCP) electrolytes based on oxalate‐chelated‐borate‐structure‐grafted poly(vinyl formal) (PVFM) were synthesized via a solution casting technique. The influence of the molar ratio of ? OH and boron atoms in PVFM on the ionic conductivity (σ) of the SCP electrolytes at different temperatures was investigated with alternating‐current impedance spectroscopy in the frequency range of 0.01 Hz to 1 MHz. The results show that σ of the SCP electrolytes at 15–60 °C was about 10^?6–10^?5 S/cm, and temperature dependence of the conductivity of the electrolytes followed the Vogel–Tamman–Fulcher relationship. The dielectric behaviors of the SCP electrolytes were analyzed in view of the dielectric permittivity and dielectric modulus of the electrolytes. Dielectric analysis revealed that the transport of Li⁺ ions in the PVFM‐based SCP electrolytes mainly followed a hopping mechanism coupled with the segmental motion of the polymer chain. Additionally, a dielectric relaxation was found in the high‐frequency region; this was a thermally activated result and also implied the appearance of carrier hopping. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43510.     

Poly(vinylidene fluoride-hexafluoropropylene)/organo-montmorillonite clays nanocomposite lithium polymer electrolytes

Polymer-clay nanocomposite (PCN) materials were prepared by intercalation of an alkyl-ammonium ion spacing/coupling agent and a polymer between the planar layers of a swellable-layered material, such as montmorillonite (MMT). The nanocomposite lithium polymer electrolytes comprising such PCN materials and/or a dielectric solution (propylene carbonate) were prepared and discussed. The chemical composition of the nanocomposite materials was determined with X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy, which revealed that the alkyl-ammonium ion successfully intercalated the layer of MMT clay, and thus copolymer poly(vinylidene fluoride-hexafluoropropylene) entered the galleries of montmorillonite clay. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) were used to investigate the electrochemical properties of the lithium polymer electrolyte. Equivalent circuits were proposed to fit the EIS data successfully, and the significant contribution from MMT was thus identified. The resulting polymer electrolytes show high ionic conductivity up to 10⁻³ S cm⁻¹ after gelling with propylene carbonate. The PCN materials exhibit good electrochemical stability and could be potentially used in lithium secondary battery.     

Preparation and ionic conductive properties of all‐solid polymer electrolytes based on multiarm star block polymers

A series of star block polymers with a hyperbranched core and 26 arms are successfully synthesized by atom transfer radical polymerization of styrene (St), and poly(ethylene glycol) methyl ether methacrylate from a hyperbranched polystyrene (HBPS) multifunctional initiator. All‐solid polymer electrolytes composed of these multiarm star polymers and lithium salts are prepared. The influences of polyoxyethylene (PEO) side‐chain length, PEO content, lithium salt concentration and type, and the structure of polymer on ionic conductivity are systematically investigated. The resulting polymer electrolyte with the longest PEO side chains exhibits the best ionic conductive properties. The maximum conductivity is 0.8 × 10^?4 S cm^?1 at 25°C with EO/Li = 30. All the prepared multiarm star block polymers possess good thermal stability. The mechanical property is greatly improved owing to the existence of polystyrene blocks in the multiarm star polymer molecules, and flexible films can be obtained by solution‐casting technique. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of microphase‐separated solvent‐free solid polymer electrolyte nanocomposite films using amphiphilic urethane acrylate precursors

A new solvent‐free solid polymer electrolyte (SPE) films could be fabricated through bulk copolymerization process of amphiphilic urethane acrylate nonionomer (UAN). Amphiphilic UAN chain having polypropylene oxide‐based hydrophobic segment and polyethylene oxide‐based hydrophilic segment can not only dissolve lithium salt by complex formation with lithium cations but also be copolymerized with various monomers to form microphase‐separated polymeric matrix. Unlike conventional SPE systems showing higher conductivity with polar polymers and polar solvents, our SPE films prepared by copolymerization of UAN and hydrophobic monomers exhibited relatively higher conductivity. Dissolving lithium salts in UAN/hydrophobic monomer mixtures caused hydrophilic/hydrophobic microphase separation, which was more favorable for ionic conduction of lithium ions, resulting in the higher ionic conductivity than the SPE films fabricated using UAN/hydrophobic monomer mixture. This microphase‐separated structure of SPE films could be also confirmed by transmission electron microscope (TEM) images. Ionic conductivity of our SPE films could be also improved by dispersing clay minerals within SPE films. Three types of clay having different surface properties were used to fabricate clay/SPE nanocomposite films. Ionic conductivity of nanocomposite films depended on dispersibliity of clay nanoparticles with a SPE film, which was confirmed by measuring X‐ray diffraction and TEM. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Novel electrospun polymer electrolytes incorporated with Keggin‐type hetero polyoxometalate fillers as solvent‐free electrolytes for lithium ion batteries

In this study, solvent‐free nanofibrous electrolytes were fabricated through an electrospinning method. Polyethylene oxide (PEO), lithium perchlorate and ethylene carbonate were used as polymer matrix, salt and plasticizer respectively in the electrolyte structures. Keggin‐type hetero polyoxometalate (Cu‐POM@Ru‐rGO, Ni‐POM@Ru‐rGO and Co‐POM@Ru‐rGO (POM, polyoxometalate; rGO, reduced graphene oxide)) nanoparticles were synthesized and inserted into the PEO‐based nanofibrous electrolytes. TEM and SEM analyses were carried out for further evaluation of the synthesized filler structures and the electrospun nanofibre morphologies. The fractions of free ions and crystalline phases of the as‐spun electrolytes were estimated by obtaining Fourier transform infrared and XRD spectra, respectively. The results showed a significant improvement in the ionic conductivity of the nanofibrous electrolytes by increasing filler concentrations. The highest ionic conductivity of 0.28 mS cm^?1 was obtained by the introduction of 0.49 wt% Co‐POM@Ru‐rGO into the electrospun electrolyte at ambient temperature. Compared with solution‐cast polymeric electrolytes, the electrospun electrolytes present superior ionic conductivity. Moreover, the cycle stability of the as‐spun electrolytes was clearly improved by the addition of fillers. Furthermore, the mechanical strength was enhanced with the insertion of 0.07 wt% fillers to the electrospun electrolytes. The results implied that the prepared nanofibres are good candidates as solvent‐free electrolytes for lithium ion batteries. © 2020 Society of Chemical Industry     

Effect of plasticizers in poly(vinyl alcohol)‐based hybrid solid polymer electrolytes

Hybrid solid polymer electrolyte films consisting of poly(vinyl alcohol) (PVA), poly(methyl methacrylate) (PMMA), LiBF₄, and ethylene carbonate/propylene carbonate (EC/PC) were prepared with a solvent‐casting technique. The complexation was investigated with Fourier transform infrared and X‐ray diffraction. The ionic conductivities of the electrolyte films were determined with an alternating‐current impedance technique for various temperatures in the range of 302–373 K. The maximum conductivity value, 1.2886 × 10^?3 S/cm, was observed for a PVA–PMMA–LiBF₄–EC complex. Thermogravimetry/differential thermal analysis was performed to ascertain the thermal stability of the electrolyte with the maximum conductivity value. For an examination of the cyclic and reversible performance of the film, a cyclic voltammetry study was carried out. The surface morphology of the EC‐and PC‐based electrolytes was examined with scanning electron microscopy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2794–2800, 2003