Nanocomposite Polymer Electrolyte Films Research Articles

Role of copper ion dissociation in DC conductivity studies of nanocomposite polymer electrolyte films

Role of copper ion dissociation in DC conductivity studies of nanocomposite polymer electrolyte films

To Study the Effect of Nanoparticle TiO2 on Sodium (Na+) – Ion Conducting Solid Polymer Electrolyte System: [80PEO:20NaPF6

AbstractTo study the effect of nanofiller particle TiO2 on sodium (Na+) – ion conducting solid polymer electrolyte (SPE) film: [80PEO:20NaPF6] and nanocomposite polymer electrolyte (NCPE): [80PEO:20NaPF6] + xTiO2, where x = 1–9 wt. (%) have been prepared. SPE film composition: [80PEO:20NaPF6] selects as Ist‐phase host and nano‐sized (<100 nm) filler materials TiO2 as IInd‐phase dispersoid. Both SPE and NCPE films have been prepared by the hot‐press technique. Filler particle‐dependent conductivity study reveals the NCPE system: [80PEO:20NaPF6] + 8TiO2 as the highest conducting composition with σrt − 3.53 × 10−6 S cm−1, which is approximately one order of magnitude higher than the SPE optimum conducting composition (OCC) (σrt) ≈ 7.78 × 10−7 S cm−1. Ion transport properties for both SPE and NCPE system have been evaluated in terms of ionic conductivity (σ) and total ionic (tion)/cationic (t+) transference numbers using combined AC/DC techniques in order to evaluate its usefulness in all‐solid‐state battery applications. Structural/thermal properties have been characterized using X‐ray diffraction (XRD) and differential scanning calorimetry (DSC) techniques. A cyclic voltammetry (CV) study has been performed in SPE and NCPE OCC film to evaluate the electrochemical performance for battery application.

Improving the polyethylene oxide/carboxymethyl cellulose blend's optical and electrical/dielectric performance by incorporating gold quantum dots and copper nanoparticles: nanocomposites for energy storage applications

Herein, nanocomposite polymer electrolyte films were prepared from the blend of two polymers, polyethylene oxide (PEO) and carboxymethyl cellulose (CMC), stuffed with various contents of gold quantum dots (AuQDs) and copper nanoparticles (CuNPs) as hybrid nanofiller via the solution casting method. AuQDs were prepared using laser ablation in liquid (LAL). TEM images showed that the average size of AuQDs is nearly 6.21 nm with a spherical shape. The effects of AuQDs and the hybrid nano-filler (AuQDs and CuNPs) on the PEO/CMC blend structural, optical, and electrical/dielectric characteristics have been investigated and discussed. XRD results revealed that the crystallinity degree of the nanocomposite samples decreased with increasing AuQDs/CuNPs content. Also, UV–Vis spectroscopy analysis uncovered that the optical energy gap reduced as the hybrid nanofillers' content increased. At room temperature, the electrical impedance spectroscopy (EIS) measurements showed that the hybrid nanofiller loading increases the electrolyte films’ electrical conductivity. In the dielectric properties, space charges polarization revealed higher values, where the dielectric constant (ε′) increased at lower frequency regions. The Nyquist diagram showed a semicircular shape at the lower frequencies part with a linear shape at the higher frequencies part with decreasing radius; two equivalent circuit models could be the best fit. These results suggest that these nanocomposite electrolyte films could be candidates for capacitors and flexible energy storage devices.

Effect of ZnO nanoparticle content on the amorphousness of conducting jackfruit seed starch-PVA blend polymer electrolyte

Nanocomposite polymer electrolyte films based on a blend of two polymers jackfruit seed starch (JSS) and poly (vinyl alcohol) (PVA) complexed with nano-particle zinc oxide (ZnO) (i.e., (50 wt% JSS/50 wt% PVA) + x wt% ZnO where x = 0, 2, 4, 6, 8, 10, 12 and 14) were prepared by using the casting solution method. Electrochemical impedance spectroscopy (EIS) has been employed between the frequencies of 10 Hz and 1 MHz to get the optimum values of the conductivity of the prepared polymer electrolyte films. The effect of ZnO nano-filler concentration on the chemical bonding, crystallinity, morphology, and ionic conductivity has been studied. The maximum ionic conductivity at ambient temperature of 1.10 × 10–6 S cm−1 was obtained for (50 wt% JSS/50 wt% PVA) + 10 wt% ZnO JSS-PVA blend film and it is attributed to the highest amorphous content.

Effect of TiO2 Nano-Filler on Electrical Properties of Na+ Ion Conducting PEO/PVDF Based Blended Polymer Electrolyte

Nanocomposite polymer electrolyte (NCPE) films based on a blend of two polymers poly (ethylene oxide) (PEO) and poly (vinylidene fluoride) (PVDF) complexed with sodium perchlorate (NaClO4) salt and Nano-filler titanium dioxide (TiO2) (i.e., (80 wt% PEO/20 wt% PVDF) + 7.5 wt% NaClO4 + x wt% TiO2 where x = 3, 6, 9, 12, 15, and 18) were prepared and characterized as potential candidates for battery applications. Electrochemical impedance spectroscopy (EIS) has been employed between the frequencies 10 Hz and 4 MHz to investigate electrical, dielectric and electric modulus properties of the prepared NCPE films. Effect of TiO2 Nano-filler concentration on the structural, ionic conductivity, and dielectric relaxation has been studied. The AC conductivity of the NCPE films at high frequencies obeys Jonscher’s power law. The values of DC ionic conductivity calculated by fitting the AC conductivity spectra to the best fit of Joncher’s power law are consistent with the values of DC ionic conductivity calculated from the bulk resistance (Rb) of the NCPE films. The ionic conductivity that depends on temperature follows the Arrhenius rule between the temperatures 298 and 328 K. The maximum ionic conductivity at ambient temperature 8.75 × 10–5 S/cm was obtained for (80 wt% PEO/20 wt% PVDF) + 7.5wt% NaClO4 + 15 wt% TiO2 NCPE film and it is attributed to the decrease in crystallinity. Using Wagner’s polarization technique ionic transport numbers of various NCPE films were measured.

Effect of active MgO nano-particles dispersion in small amount within magnesium-ion conducting polymer electrolyte matrix

This paper reports effect of dispersing active MgO nano-particles in small amount within magnesium-ion conducting polymer electrolyte matrix. The electrolyte films are prepared by solution casting techniques and experimental techniques are employed to carry out structural, electrochemical and mechanical analysis. SEM and AFM micrographs demonstrate a variation in surface morphology and maximum roughness height with the incorporation of MgO nano-particles within the polymer electrolyte matrix. The nano-composite polymer electrolyte film with optimized concentration of 1 wt% MgO nano-particles delivered an ionic conductivity of 1.49 × 10−4 S cm−1 at 25 °C, though its crystallinity is higher than the pristine. In depth, ion-conduction has been probed with the help of dielectric and modulus behavior of electrolyte system as a function of MgO nano-particles concentration, frequency and temperature. The mechanical studies reveal a Young’s modulus of 150 N mm−2, mechanical strength of 2.7 Kgf and stress of 2.6 N mm−2 at a maximum load of 10 Kgf for the optimized electrolyte film. The reported electrolyte can be utilized in rechargeable Mg batteries due to its high conductivity, flexibility and mechanically stability.

Optimization of polymer electrolytes with the effect of concentration of additives in PEO-NH4HF2polymer electrolytes

In the present work, nanocomposite polymer electrolyte films were prepared by solution casting technique using nanosized fumed silica to polyethylene oxide (PEO)-based polymer electrolytes containing ammonium bifluoride (NH4HF2). The ionic conductivity of 1.19 × 10−5S cm−1has been observed at room temperature (25°C) for 3 wt% fumed silica in PEO-10 wt% NH4HF2polymer electrolytes after which the conductivity was observed to decrease. Furthermore, the addition of high dielectric constant plasticizer propylene carbonate (PC) in the optimized composition of nanocomposite polymer electrolytes has increased the number of charge carriers by the large dissolution of ionic salt, amorphous content, and hence the ionic conductivity. Maximum ionic conductivity obtained at room temperature was found to be 1.55 × 10−4S cm−1in the case of PEO-10 wt% NH4HF2-3 wt% fumed silica-0.3 (ml) PC polymer electrolytes which is five orders of magnitude higher than that of the polymer host material. Temperature-dependent ionic conductivity, activation energy, and dielectric constant studies have been described for all the compositions of polymer electrolytes. Ionic conductivity and dielectric constant studies were determined from impedance data. Polymer electrolytes containing both fumed silica and PC highlight that there is no phase transition in the polymer electrolyte and temperature dependence of ionic conductivity in the temperature range is of almost Arrhenius type. The lowest activation energy value for the highest conducting polymer electrolyte was found to be 0.172 eV. Change in melting temperature, % crystallinity ( χc), and mechanical properties have also been observed in polymer electrolytes containing fumed silica as well as PC as studied by Differential Scanning Calorimetry/Thermogravimetric Analysis (DSC/TGA) and universal testing machine, respectively.

Ion Transport and Materials Characterization Studies on Hot-Press Cast Zn2+ Conducting Nano-Composite Polymer Electrolyte (NCPE) Films: [90 PEO: 10 Zn (CF3SO3)2] + xAl2o3

Investigations on ion-transport and materials properties of poly (ethylene oxide) (PEO) based Zn2+ conducting Nano-Composite Polymer Electrolyte (NCPE) membranes: [90 PEO: 10 Zn (CF3SO3)2] + xAl2O3, have been reported. NCPE films have been prepared by a completely dry hot-press cast technique using Solid Polymer Electrolyte (SPE) composition: [90 PEO: 10 Zn (CF3SO3)2] as I phase and Al2O3 nano-filler particles (< 50 nm) as II- Phase dispersoid. In an earlier study, SPE used here as I phase host has been identified as optimum room temperature conducting film exhibiting (srt) ~1.01 x 10-5 S/cm. As a consequence of fractional dispersal of nano-filler particles in SPE, additional srt enhancement of an order of magnitude was obtained. This has been referred as NCPE OCC film. Ion transport behavior in NCPE OCC has been characterized in terms of ionic conductivity (?), total ionic (tion)/cation (t+) transport numbers which have been measured using different ac/dc techniques. Temperature dependent conductivity study has also been carried out to understand the mechanism of ion transport and to compute activation energy (Ea) from ‘log s-1/T’ plot. Materials and thermal properties have been characterized with the help of SEM, XRD, FTIR and DSC / TGA techniques.

Gamma irradiation effects on conductivity and dielectric behaviour of PEO-based nano-composite polymer electrolyte systems

The effect of gamma irradiation on physical and electrical properties of polyethylene oxide (PEO)-based nano-composite polymer electrolyte films was investigated. The structural change induced and the reduction in crystallinity of the electrolyte film before and after irradiation were confirmed by FTIR spectra and X-ray diffraction studies. Microstructural studies carried out by scanning electron microscope technique reveal significant change in the surface morphology on irradiation. The bulk conductivities of the films were studied using standard impedance spectroscopic technique. A maximum ionic conductivity of 1.717 × 10−4 S cm−1 was observed for 40 kGy radiation dose, which is higher than earlier reported studies. Ion dynamics behaviour of the films was studied by frequency-dependent conductivity measurements which follow universal power law. The dielectric constant tends to be higher for films with higher lithium ion conductivity.

Effect of carbon nanotubes as dispersoid in polymer electrolyte matrix

The present work deals with the characterization of a thin film polymer electrolyte based on poly(N-vinyl pyrrolidone) (PVP) doped with ammonium iodide (NH4I) and carbon nanotubes (CNT) as dispersoid to develop nanocomposite polymer electrolyte films using solution cast method. Carbon nanotubes were incorporated in PVP:NH4I matrix in different concentration. Electrochemical impedance spectroscopy technique was used for characterizing the polymer electrolyte system. 0.4 wt% MCNT containing system shows maximum conductivity (8.23 × 10−2 S/cm). The temperature dependent conductivity studies reveal the Arrhenius behavior. Differential scanning calorimetry analysis shows the decrease in the glass transition temperature (Tg) from 345 (60:40 PVP:NH4I) to 339 K (60:40 + 0.4 wt% PVP:NH4I + CNT). Dielectric phenomenon, concentration of charge carrier density (N) and dissociation factor also supports the conductivity data while ionic transference number (tion) studies confirms the ionic conductive nature of the electrolyte system.

Study of electrical and electrochemical behavior on copper ion conducting nano-composite polymer electrolyte

Poly (ethylene oxide) (PEO)-based nano-composite polymer electrolyte (NCPE) membranes: [85PEO: 15Cu(ClO4)2.6H2O] + x Al2O3, where x = 0, 1, 2, 3, 4, 5, 6, 7, 8 wt%, have been casted by hot-press technique. Solid polymer electrolyte (SPE) composition: [85PEO: 15Cu(ClO4)2.6H2O] (wt%) is highest conducting film with room temperature conductivity (σ rt) ~ 1.59 × 10−6 S/cm, has been used as the Ist-phase host matrix and Al2O3 filler particles of nano-dimension (~ 50 nm) as IInd-phase dispersoid. The fractional dispersal of Al2O3 filler (viz. x = 2 wt%) in Ist-phase SPE host resulted into nearly four orders increase in the room temperature conductivity than that of pure PEO. This NCPE film: [85PEO: 15Cu (ClO4)2.6H2O] + 2 Al2O3 has been referred to as optimum conducting composition (OCC) NCPE film. X-Ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and Thermogravimetric Analysis (TGA) techniques have been used to study the structural, spectroscopic, morphological, and thermal responses, respectively, of SPE/NCPE OCC film material. The ion transport behavior has been characterized in terms of basic ionic parameters viz. conductivity (σ), total ionic (t ion)/cation (t +) transference numbers which have been evaluated using different ac/dc techniques. Temperature dependent conductivity measurement in SPE/NCPE OCC film was done in order to understand the mechanism of ion transport and to evaluate activation energy (E a) from “log σ–1/T” plot.

Preparation and characterization of new nanocomposite polymer films containing NiO nanofillers

ABSTRACTNanocomposite solid polymer films based on the poly(exo‐N‐phenyl‐7‐oxanorbornene‐5,6‐dicarboximide) (PPhONDI)/LiClO4/NiO system have been designed, and the effect of inorganic NiO nanofiller in different amounts on the film properties has been examined. The exo‐PPhONDI/LiClO4/NiO polymer system is the first solid nanocomposite polymer electrolyte film example based on a ring‐opening metathesis polymerization (ROMP) host polymer. The NiO nanoparticles were prepared by two‐step chemical syntheses, and the thermoplastic host polymer, exo‐PPhONDI, was synthesized via ROMP. Composite polymer films were prepared by the solution‐casting method. The amount of nanoparticles was varied from 1 to 15 wt % of NiO. The conductivity of the nanocomposite solid polymer systems was influenced by the NiO nanofiller concentration. The composite films based on exo‐PPhONDI ROMP polymer with the highest conductivity were achieved for the composition with 8 wt % of NiO nanofiller and 10 wt % of LiClO4 dopant. The prepared films were characterized using X‐ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, and scanning electron microscopy (SEM). The SEM results showed that the filler was well distributed in the polymer matrix. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45938.

Synthesis and characterization of ion transport behavior in Cu2+-conducting nano composite polymer electrolyte membranes

Synthesis and characterization of ion transport behavior in Cu2+-conducting nano composite polymer electrolyte (NCPE) films: [90PEO: 10Cu(CF3SO3)2] + x CuO have been reported. NCPE films have been formed by hot-press casting technique using solid polymer electrolyte (SPE) film composition: [90PEO: 10Cu(CF3SO3)2] as 1st-phase host and nanoparticles of CuO in varying wt.(%) as 2nd-phase active filler. SPE: [90PEO: 10Cu(CF3SO3)2] was identified earlier as highest conducting film with room temperature conductivity (σrt) ~ 3.0 x 10−6 S cm−1, which is three orders of magnitude higher than that of pure polymer host PEO with σrt ~ 3.2 × 10−9 S cm−1. Filler particle concentration dependent conductivity study revealed NCPE film: [90PEO: 10Cu(CF3SO3)2] + 3%CuO as optimum conducting composition (OCC) exhibiting σrt ~ 1.14 × 10−5 S cm−1. Hence, by the fractional dispersal of 2nd-phase active filler into 1st-phase SPE host, σ-enhancement of approximately an order of magnitude has further been obtained. Ion transport behavior in NCPE OCC film has been characterized in terms of basic ionic parameters viz. ionic conductivity (σ), total ionic transference (tion)/cationic (t+) numbers. Temperature dependent conductivity measurement has also been done to explain the mechanism of ion transport and to compute activation energy (Ea). Materials characterization and hence, confirmation of complexation of salt in polymeric host and/or dispersal of filler particles in SPE host have been done by scanning electron microscopy (SEM), energy dispersive x-ray spectrometer (EDS), x-ray diffraction (XRD), Fourier transform infra-red (FTIR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). All-solid-state battery in the cell configuration: Cu (Anode) || SPE host/NCPE OCC film || C + I2 + Electrolyte) (Cathode) has been fabricated and cell performance has been studied under two load resistances viz. 60 and 100 kΩ. Each NCPE cell gave on an open circuit voltage (OCV) ~ 0.68 V. Some important battery parameters have also been evaluated from the plateau regions of cell potential discharge profiles.

Simulation Model of Multiple Cluster Fractals Cultured in Nanocomposite Polymer Electrolyte Film

This work contributes to the melioration of the modeling and simulation of laboratory cultured fractals using poly (vinylidene fluoride-co-hexafluoropropylene)/poly (ethyl methacrylate)-ammonium trifluorome-thanesulfonate nanocomposite polymer electrolyte films as the media of growth. Main focus is given to fractals and fractal growth models particularly DLA (Diffusion Limited Aggregation). The DLA cluster formed through DLA is formed by particles moving in Brownian motion (diffusion) which meet and stick together randomly (aggregation) to form the cluster. The simulation of multiple cluster fractals is done using DLA methods incorporating different parameters such as its sticking coefficient, lattice geometry and number of particles. To compare the simulation with the real patterns obtained, one vital aspect would be the calculation of their fractal dimension values. The computer program developed is able to calculate the fractal dimension value of each of the simulated fractal patterns. Suitable fractal dimension calculation method is employed according to its usefulness and efficiency. Fractal growth modeling and simulation such as done here can contribute to the understanding of other related studies concerning fractal growth found in areas including medical (nervous systems, cancer growth and more).

Impedance and dielectric studies of nanocomposite polymer electrolyte systems using MMT and ferroelectric fillers

Impedance and dielectric properties of nanocomposite polymer electrolyte systems modified with nano size MMT and ferroelectric fillers have been investigated for varying lithium to oxygen ratios. The changes in the structural properties of the electrolyte samples were characterized by X-ray diffraction (XRD) and differential scanning calorimetric (DSC) technique. The ion transport number estimated by DC polarization technique is found to be between 0.86 and 0.95. The bulk conductivities of nanocomposite polymer electrolyte films were studied using impedance spectroscopic technique. The impedance plot shows high frequency semicircle, due to the bulk effect of sample and maximum ionic conductivity of 2.15 × 10−4 Scm−1 was observed for (PEO)4LiCBSM at 323 K with lithium to oxygen ratio 1: 4. The complex impedance data was used to evaluate ionic conductivity and dielectric relaxation process, to understand the ion transport mechanism in these systems.

Effects of Silica Nanostructures in Poly(ethylene oxide)-Based Composite Polymer Electrolytes.

The present work describes the synthesis of some poly(ethylene oxide)-based nanocomposite polymer electrolyte films using various silica nanostructures as the inorganic filler by simple solution mixing technique, in which the nature of the silica nanostructures play a vital role in modulating their electrochemical performances at room temperature. The silica nanostructures are prepared by ammonical hydrolysis of tetraethyl orthosilicate following the modified St6ber method. The resulting films are characterized by X-ray diffraction and differential scanning calorimeter to study their crystallinity. Room temperature AC impedance spectroscopy is utilized to determine the Li+ ion conductivity of the resulting films. The observed conductivity values of various NCPE films depend on the nature of silica filling as well as on their surface characteristics and also on the varying PEO-Li+ ratio, which is observed to be in the order of 10(-7)-10(-6) S cm(-1).

Field enhanced Li ion conduction in nanoferroelectric modified polymer electrolyte systems

Nanocomposite polymer electrolyte (NCPE) films based on polyethylene oxide (PEO) complexed with lithium perchlorate (LiClO4) and nanosized ferroelectric ceramic fillers such as BaTiO3, SrTiO3 have been prepared using solution cast technique. The films showed very good mechanical stability when exposed to ambient atmospheres for prolonged periods. Lithium ion transport studies revealed that the conductivity is predominantly ionic. The effect of electric field on ionic conductivity of NCPE films was investigated. One order enhancement in conductivity due to the field was observed at 323 K. NCPE films exhibited conductivity of 3.46 × 10−5 Scm−1 at 323 K. NCPE films were characterized using differential scanning calorimetry (DSC) and X-ray diffraction (XRD) technique. The DSC and XRD studies revealed reduced crystallinity which confirmed the higher amorphous phase and hence the improved ionic conductivity.

Structural, thermal, electrical, and dielectric properties of synthesized nanocomposite solid polymer electrolytes

In the present article, polyvinyl alcohol (PVA) polymer, sodium iodide (NaI) salt, and fumed silica nanoparticles nanofiller have been used for the preparation of solid polymer electrolyte films. Fourier transform infrared spectroscopy has been performed to study the vibrational change due to the complexation among polymer, salt, and nanofiller. X-Ray diffraction has been carried out to study the structural changes in the PVA:NaI (60:40) polymer electrolyte films with fumed silica nanoparticles as dopant. Differential scanning calorimetry studies show decreasing trend in the glass transition temperature for nanocomposite polymer electrolyte films. Thermogravimetric analysis has been performed to study the thermal degradation of the sample. Determination of transference number using Wagner’s polarization technique indicates that the ions are the dominant mobile species. Maximum conductivity of approximately 3.8 × 10−3 S cm−1 at room temperature has been estimated for PVA:NaI (60:40) film containing 0.5% fumed silica nanoparticles with low value of activation energy. Dielectric relaxation studies with temperature show shifts of the relaxation time toward higher value for samples of nanocomposite polymer electrolyte films.

Effect of nano TiO2 filler on the structural and electrical properties of PVP based polymer electrolyte films

A composite polymer electrolyte system based on PVP:KIO4 with dispersed nano TiO2 filler in different concentrations was prepared by solution casting. Structural investigations were carried out using X-ray diffraction, Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM). Electrical conductivity measurements were performed by a computer controlled phase sensitive multimeter (PSM 1700) in the frequency and temperature range 1 Hz–1 MHz and 303–373 K, respectively. It was observed that the magnitude of conductivity increased with increase in the nano TiO2 filler concentration as well as with temperature. The addition of nano TiO2 filler to the PVP:KIO4 electrolyte system was found to result in enhancement of the ionic conductivity. The maximum ionic conductivity 0.665 × 10−3 S/cm was obtained for 10 wt% nano TiO2 filler in the composite at room temperature. The conducting species of charge transport in these nano composite polymer electrolyte films were examined by the Watanabe technique and it was found that the charge transport is predominantly due to cations. Using these polymer electrolytes (KIO4 complexed and TiO2 nano composite), electrochemical cells were fabricated with the configuration of K/(Polymer film)/(I2 + C + electrolyte), and discharge characteristics were studied under a constant load of 100 kΩ. Various cell parameters, such as open circuit voltage, short circuit current, power density and energy density were determined.

Dielectric study of hot-pressed nanocomposite polymer electrolytes

Ion-conducting nanocomposite polymer electrolyte films based on poly(ethylene oxide)-NaPO3 3: 1 with up to 15 wt % of SiO2 have been prepared using recently developed hot-press technique instead of conventional solution cast method. With 7 wt % of SiO2, the film conductivity has been enhanced by an order of magnitude. The materials have been characterized by Fourier transform infrared spectrometry and thermogravimetric analysis. For the composition with the highest conductivity, the temperature dependences of ionic mobility, mobile ions concentration, ionic transference number, and ionic drift velocity have been determined. Dielectric constant and dielectric loss have been measured. The conductivity enhancement has been discussed on the basis of existing theories of dielectrics.