Investigation of dibutyl phthalate as plasticizer on poly(methyl methacrylate)–lithium tetraborate based polymer electrolytes

Polymer electrolyte membranes, comprising of poly(methyl methacrylate) (PMMA), lithium tetraborate (Li₂B₄O₇) as salt and dibutyl phthalate (DBP) as plasticizer were prepared using a solution casting method. The incorporation of DBP enhanced the ionic conductivity of the polymer electrolyte. The polymer electrolyte containing 70 wt.% of poly(methyl methacrylate)–lithium tetraborate and 30 wt.% of DBP presents the highest ionic conductivity of 1.58 × 10⁻⁷ S/cm. The temperature dependence of ionic conductivity study showed that these polymer electrolytes obey Vogel–Tamman–Fulcher (VTF) type behaviour. Thermogravimetric analysis (TGA) was employed to analyse the thermal stability of the polymer electrolytes. Fourier transform infrared (FTIR) studies confirmed the complexation between poly(methyl methacrylate), lithium tetraborate and DBP.     

The role of zirconium oxide as nano-filler on the conductivity,morphology, and thermal stability of poly(methyl methacrylate)–poly(styrene-co-acrylonitrile)-based plasticized composite solid polymer electrolytes

The plasticized composite solid polymer electrolytes (CSPE) involving polymer blends poly(methyl methacrylate)-poly(styrene-co-acrylonitrile) (PMMA-SAN), plasticizers ethylene carbonate (EC), and propylene carbonate (PC) with lithium triflate (LiCF₃SO₃) as salt and varying concentration of composite nano-filler zirconium oxide (ZrO₂) is prepared by solution casting technique using THF as solvent. The powder X-ray diffraction (XRD) studies reveal amorphous nature of the CSPE samples. Fourier transform infrared (FT-IR) spectroscopy studies reveal interaction of Li⁺ ion with plasticizers, both C=O and OCH₃ group of the PMMA, while nitrile group of SAN is inert. AC impedance and dielectric studies reveal that the ionic conductivity (σ), dielectric constant (ε’), and dielectric loss (ε”) of the prepared CSPE samples increase with increasing content of ZrO₂ nano-filler up to 6 wt% and decrease with further additions. The temperature dependence of ionic conductivity follows Arrhenius relation and indicates ion-hopping mechanism. The sample Z2 (6 wt% ZrO₂) with relaxation time τ of 8.13?×?10^–7 s possess lowest activation energy (E_a?=?0.23 eV) and highest conductivity (2.32?×?10^–4 S cm^?1) at room temperature. Thermogravimetric analysis (TGA) reveals thermal stability of highest conducting sample Z2 up to 321 °C after complete removal of residual solvent, moisture, and its impurities. Differential scanning calorimetric (DSC) studies reveal absence of glass transition temperature (T_g) corresponding to atactic PMMA for the CSPE Z2, while isotactic PMMA component shows T_g around 70 °C, which is due to increased interaction of filler with PMMA leading to change in its tacticity. Scanning electron microscopy (SEM) analysis reveals blending of PMMA/SAN polymers and lithium triflate salt. The incorporation of nano-filler ZrO₂ leads to change in surface topology of polymer matrix. Rough surface of the CSPE Z2 leads to new pathway for ionic conduction leading to maximum ionic conductivity.     

Solid polymer electrolytes in a poly(butadiene-acrylonitrile)–LiBr system

Poly(nitriles) are among the polymer matrices providing high salt solubility and, in some cases, superionic lithium conductivity at ambient temperatures observed in highly concentrated solvent-free polymer electrolytes. However, the properties of these electrolytes in which ionic aggregation prevails remain difficult to reproduce and predict, as current theories do not adequately model their attributes. The development of new concepts for ion transport in highly concentrated solid polymer electrolytes (SPEs) requires a better understanding of the fundamentals of structure formation in a polymer–salt system over a wide concentration range including salt precipitation. In an attempt to approach this goal, a series of fundamental studies was carried out on the systems based on a rubbery random copolymer of butadiene and acrylonitrile (abbreviated as PBAN). In the present work, LiBr with monatomic halide anion was used as a lithium salt. The effect of LiBr concentration (0.05 to 3.35 mol kg^?1) on phase composition, ion–molecular interactions, glass transition temperature, and ionic conductivity was studied by optical microscopy, FTIR, X-ray diffraction, DSC, and impedance measurements. The results were compared with those of PBAN–LiClO₄ and PBAN–LiAsF₆ studied previously. Low salt solubility and separation of a metastable cubic CsCl-type polymorph of LiBr were established. The highest conductivity of ～10^?4 S cm^?1 at >50 °C was observed for heterogeneous samples comprising this phase. While the conductivity of PBAN–LiBr was lower than that of PBAN–LiClO₄ and PBAN–LiAsF₆, this study provides a new insight into the nature of polymer electrolyte systems.     

Conduction mechanism of lithium bis(oxalato)borate–cellulose acetate polymer gel electrolytes

Polymer gel electrolytes (PGE) belonging to salt–solvent–polymer hybrid systems are prepared using a mixture of lithium bis(oxalato)borate (LiBOB), γ-butyrolactone (γ-BL), and cellulose acetate (CA). The increase in ionic conductivity of PGE is due to the dissociation of ion aggregates, as confirmed by Fourier transform infrared analysis. The highest conductivity attained by the PGE is 7.05 mS cm^?1 at 2.4 wt.% CA. The plots of conductivity–temperature show a classical Arrhenius relationship. The electrical properties of the sample with the highest conductivity are analyzed using electrical permittivity and electric modulus formalism studies. Meanwhile, the frequency-dependent conductivity of the polymer gel electrolyte adheres to Jonscher’s power law. Conduction mechanism study also shows that the 2.4 wt.% CA PGE is in agreement with the small polaron hopping model.     

Effect of lithium thiocyanate addition on the structural and electrical properties of biodegradable poly(ε-caprolactone) polymer films

Polymer electrolyte films of biodegradable poly(ε-caprolactone) (PCL) doped with LiSCN salt in different weight ratios were prepared using solution cast technique. The effect of crystallinity and interaction between lithium ions and carbonyl groups of PCL on the ionic conduction of PCL:LiSCN polymer electrolytes was characterized by X-ray diffraction (XRD), optical microscopy, Fourier transform infrared spectroscopy (FTIR) and AC impedance analysis. The XRD results revealed that the crystallinity of the PCL polymer matrix decreased with an increase in LiSCN salt concentration. The complexation of the salt with the polymer and the interaction of lithium ions with carbonyl groups of PCL were confirmed by FTIR. The ionic conductivity was found to increase with increasing salt concentration until 15 wt% and then to decrease with further increasing salt concentration. In addition, the ionic conductivity of the polymer electrolyte films followed an Arrhenius relation and the activation energy for conduction decreased with increasing LiSCN concentration up to 15 wt%. UV–vis absorption spectra were used to evaluate the optical energy band gaps of the materials. The optical energy band gap shifted to lower energies with increasing LiSCN salt concentration.     

Preparation and characterization of PVAc–PMMA-based solid polymer blend electrolytes

In the present work, a novel blend polymer electrolyte membrane using poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA), and lithium per chlorate (LiClO₄) in different compositions has been prepared by the solution-casting technique. Their chemical, structural characters, thermal behavior, surface morphology, and ionic conductivity were studied using Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric/differential thermal analyzer, scanning electron microscopy, and AC impedance analyzer, respectively. A maximum ionic conductivity value of 1.67 × 10⁻⁴ S/cm at 303 K is obtained for PVAc–PMMA–LiClO₄ complexes in the ratio of 25 × 75, keeping LiClO₄ constant as 10 wt.% among all the compositions studied.     

Effect of LiBOB as additive on electrochemical properties of lithium–sulfur batteries

The effect of varying amounts (in the range 1–10 wt.%) of LiBOB (lithium bis(oxalato) borate) as additive in mixed liquid electrolyte on the electrochemical performance of lithium–sulfur batteries is investigated at room temperature. The electrochemical impedance spectroscopy (EIS) of lithium anode with LiBOB has two semicircles, corresponding to charge transfer impedance and ion migration impedance, respectively. The lithium anode with LiBOB shows a higher ion migration impedance, which could reduce the ionic diffusion rate in the anode. Scanning electron microscopy (SEM) observations shows that lithium anode with LiBOB has a smoother and denser surface morphology than the anode without LiBOB. The lithium–sulfur batteries with LiBOB shows the improvement of both the discharge capacity and cycle performance, a maximum discharge capacity of 1,191 mA h g⁻¹ is obtained with 4 wt.% LiBOB. The lithium–sulfur batteries with 4 wt.% LiBOB can maintain a reversible capacity of 756 mA h g⁻¹ after 50 cycles.     

Structural,thermal and electrical properties of polyvinyl alcohol/poly(vinyl pyrrolidone)–sodium nitrate solid polymer blend electrolyte

Sodium ion conducting solid polymer blend electrolyte thin films have been prepared by using polyvinyl alcohol (PVA)/poly(vinyl pyrrolidone) (PVP) with NaNO₃ by solution cast technique. The prepared films were characterized by various methods. The complexation of the salt with the polymer blend was identified by X-ray diffraction (XRD) and Fourier transforms infrared spectroscopy (FTIR), Differential scanning calorimetry was used to analyze the thermal behavior of the samples, and the glass transition temperature is low for the highest conducting polymer material. The scanning electron microscopy gives the surface morphology of the polymer electrolytes. The frequency and temperature dependent of electrical conductivities of the films were studied using impedance analyzer in the frequency range of 1 Hz to 1 MHz. The highest electrical conductivity of 50PVA/50PVP/2 wt% NaNO₃ concentration has been found to be 1.25 × 10^?5 S cm^?1 at room temperature. The electrical permittivity of the polymer films have been studied for various temperatures. The transference number measurements showed that the charge transport is mainly due to ions than electrons. Using this highest conducting polymer electrolyte, an electrochemical cell is fabricated and the parameters of the cells are tabulated.     

Effect of different anions of lithium salt and MMT nanofiller on ion conduction in melt-compounded PEO–LiX–MMT electrolytes

Polymer nanocomposite electrolyte (PNCE) films composed of poly(ethylene oxide) (PEO), lithium salt ( \textLiX;  \textX = ClO₄ ^- ,  BF₄ ^- ,  CF₃SO₃ ^- {\text{LiX}};\;{\text{X}} = ClO_4^{ - },\;BF_4^{ - },\;C{F_3}SO_3^{ - } ) and montmorillonite (MMT) clay as nanofiller were prepared by melt-compounded hot-pressed technique at 70 °C under 3 tons of pressure. The ionic conductivity and relaxation behaviour of the films were investigated by dielectric relaxation spectroscopy in the frequency range of 20 Hz to 1 MHz at ambient temperature. The results revealed that the ionic conductivity of the PNCE films having 20:1 stoichiometric ratio of ethylene oxide monomer units to the lithium cation are governed by the size of different anions and the dissociation constant of salt, and also MMT concentration. It was found that PEO–LiBF₄ film has comparative high dc ionic conductivity, whereas both the LiBF₄ and LiClO₄ containing PNCE films exhibit anomalous conductivity behaviour with varying MMT concentration. The PEO–LiCF₃SO₃ film has two orders of magnitude low value of dc ionic conductivity as compared to that of the other salts electrolyte films, but its conductivity enhances by one order of magnitude when 2 wt.% MMT is added as filler. A correlation between the values of ionic conductivity, conductivity relaxation time and the real part of permittivity at 1 MHz were found and the same was discussed in relation to the transient ion-dipolar type cross-linked structural behaviour of the polymeric nanocomposite electrolytes.     

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.     

Studies on structural,optical and cluster size of poly(m-toluidine)–polyvinyl chloride blends

Poly(m-toluidine) (PmT), a derivative of polyaniline, has been prepared by chemical oxidation polymerization method. The synthesized PmT powder is blended with plasticized polyvinyl chloride (PVC) to achieve 20 μm thick self-supported films. These films were irradiated with 60 MeV Si⁵⁺ ions at three different fluences whose S _e (electronic energy loss) value is found to be 1.988×10³ KeV/μ m, an order of magnitude larger than 60 MeV C⁵⁺ (2.958×10² KeV/μ m). Fourier transform infrared (FTIR), X-ray diffraction (XRD) and ultraviolet-visible (UV) absorption studies of pre- and post-irradiated films of PmT–PVC blends were carried out to study the heavy ion irradiation effects on these polymer blends. An overall change in the structure of the polymer blend has been observed from FTIR studies. UV-visible spectra show a decrease in the optical band gap (E _g) and an increase in cluster size with increasing fluence. An effort is made to compare these results with our earlier studies. We found that the variation in S _e plays an important role in the structural and optical properties of PmT–PVC blends.     

Spectroscopic studies on ion dynamics of PVP–NH4SCN polymer electrolytes

Proton-conducting polymer electrolyte comprising of poly(N-vinyl pyrrolidone) (PVP) and ammonium thiocyanate (NH₄SCN) are prepared by solvent casting method with different polymer–salt concentrations. The changes in the Raman spectra with increasing NH₄SCN concentration state that the free ion concentration is maximum for 20 mol% NH₄SCN concentrated system. At higher salt concentrations (25 mol%), the effective number of charge carriers decreases due to the formation of ion aggregates as confirmed by the Raman analysis. Solid-state NMR and MAS NMR studies are performed to obtain the information about the ionic structure, mobility of the charge carriers, and also to gain insight into the polymer–salt interactions in the polymer electrolytes. The results of ionic transference number show that the charge transport in these polymer electrolytes is mainly due to ions.     

Effect of nano γ-Al2O3 addition on ion dynamics in polymer electrolytes

Polymer electrolytes, which hold the key of successful operation of all solid state ionic devices, have been investigated. An amorphous polymer was used to facsimile fast ion transport in the gel polymer electrolytes (GPE) and room temperature conductivity >10⁻³ S/cm can be attained. Further, these electrolytes were transformed into composites by dispersing inorganic particles of γ-Al₂O₃ (11 nm in size) in varying wt.%. An enhancement in the conductivity for an optimum concentration using LiClO₄ as a salt can be obtained and is described in terms of free charge carrier concentration, while the other family of Lithium salts viz. LiTf, LiIm, LiBETI decreases the conductivity marginally. FTIR spectroscopy supports the observed decrease in terms of more association between fillers and salts. It has been realized that the mechanical integrity of these composites increases manifold, without affecting the conductivity, significantly.     

A Study on Properties of Poly(vinyl chloride)/Poly(α-methylstyrene-acrylonitrile) Binary Blends

Blends of poly(vinyl chloride) (PVC) and poly(α-methylstyrene-acrylonitrile) (α-MSAN) with variable composition of 0 to 100 wt% were prepared by melt mixing. Properties of binary blends were extensively studied by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), heat distortion temperature (HDT), mechanical properties, melt flow rate (MFR), and scanning electron microscope (SEM). A single glass transition temperature (T_g ) was observed by DSC and DMTA, indicating miscibility between PVC and α-MSAN. The results of ATR-FTIR indicated that specific strong interactions were not present in the blends and the miscibility was due to interaction between –CN and PVC. With increasing amount of α-MSAN, considerable increase occurred in HDT, flexural strength, and flexural modulus compared with reverse s-shaped decrease in impact strength and elongation at break. Synergism was observed in tensile strength and MFR. No phase separation was observed in SEM photographs, indicating miscibility between PVC and α-MSAN. In addition, morphology of the impact-fractured surfaces, including roughness and non-fused particles, correlated well with the mechanical properties and MFR.     

Electrical properties of proton conducting solid biopolymer electrolytes based on starch–chitosan blend

Two systems (salted and plasticized) of starch–chitosan blend-based electrolytes incorporated with ammonium chloride (NH₄Cl) are prepared via solution cast technique. The incorporation of 25 wt% NH₄Cl has maximized the room temperature conductivity of the electrolyte to (6.47?±?1.30)?×?10^?7 S cm^?1. Conductivity is enhanced to (5.11?±?1.60)?×?10^?4 S cm^?1 on addition of 35 wt% glycerol. The temperature dependence of conductivity for all electrolytes is Arrhenian, and the value of activation energy (E _a ) decreases with increasing conductivity. Conductivity is found to be influenced by the number density (n) and mobility (μ) of ions. The complexation between the electrolytes components is proven by Fourier transform infrared analysis. The relaxation time (t _r ) for selected electrolytes is found to decrease with increasing conductivity and temperature. Conduction mechanism for the highest conducting electrolyte in salted and plasticized systems is determined by employing Jonscher’s universal power law.     

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.     

Poly ethylene oxide (PEO)–LiI polymer electrolytes embedded with CdO nanoparticles

Improvement of electrical conductivity of poly ethylene oxide (PEO)–LiI polymer electrolytes is necessary for their use in solid state lithium ion battery. In this study a new kind of PEO–LiI-based polymer electrolytes embedded with CdO nanoparticles with improved electrical conductivity has been prepared and characterized. The electron microscopic studies confirm that CdO nanoparticles of average size 2.5 nm are dispersed in the PEO matrix. The glass transition temperature of the PEO–LiI electrolyte decreases with the introduction of CdO nanoparticle in the polymer matrix. X-ray diffraction, electron microscopic, and differential scanning calorimetry studies show that the amorphous phase of PEO increases with the introduction of CdO nanoparticle and that the increase in amorphous phase is maximum for 0.10 wt% CdO doping. The electrical conductivity of the sample with 0.10 wt% CdO increases by three orders in magnitude than that of the PEO–LiI electrolyte. The electrical conductivity of PEO–LiI electrolyte embedded with CdO nanoparticle exhibits VTF behavior with reciprocal temperature indicating a strong coupling between the ionic and the polymer chain segmental motions.     

Preparation of poly(vinyl alcohol)–silicone based hybrid membranes for the pervaporation separation of water–acetic acid mixtures

Hybrid membranes were prepared using poly(vinyl alcohol) (PVA) and tetraethylorthosilicate (TEOS) via hydrolysis followed by condensation. The obtained membranes were characterized by Fourier transform infrared spectroscopy, wide-angle x-ray diffraction and differential scanning calorimetry. A remarkable decrease in degree of swelling was observed with increasing TEOS content in membranes and is attributed to the formation of hydrogen bonding and covalent bonds in the membrane matrix. The pervaporation performance of these membranes for the separation of water–acetic acid mixtures was investigated in terms of feed concentration and the content of TEOS used as cross-linking agent. The membrane containing 1 : 2 mass ratio of PVA and TEOS gave the highest separation selectivity of 1116 with a flux of 3.33 × 10^?2kg/m²h at 30°C for 10 mass% of water in the feed. Except for membrane M-1, the observed values of water flux are close to the values of total flux in the investigated composition range, signifying that the developed membranes are highly water selective. From the temperature dependence of diffusion and permeation values, the Arrhenius apparent activation parameters have been estimated. The resulting activation energy values obtained, showing that water permeation is lower than that of acetic acid, suggest that the membranes have higher separation efficiency. The activation energy values calculated for total permeation and water permeation are close to each other for all the membranes except membrane M-1, signifying that coupled-transport is minimal because of the higher selective nature of membranes. The negative heat of sorption values (ΔH _s) for water in all the membranes suggests a Langmuir mode of sorption.     

Development of poly(glycerol suberate) polyester (PGS)–PVA blend polymer electrolytes with NH<Subscript>4</Subscript>SCN and its application

Besides commercially available synthetic polymers, the present work has been undertaken to explore the significance of poly(glycerol suberate) (PGS) polyester synthesised under lab scale in energy storage device. In this regard, a blend polymer electrolyte comprising of polyvinyl alcohol (PVA), poly(glycerol suberate) (PGS) polyester along with the various proportions of ammonium thiocyanate (NH₄SCN) was prepared adopting solution casting technique. The synthesised polyester PGS was characterised by Fourier transform infrared (FT-IR) spectroscopy, ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy. The prepared electrolyte film was subjected to FT-IR analysis to study the complexation that has occurred within the blend. Its amorphous nature was revealed from X-ray diffraction (XRD) studies. Influence of NH₄SCN on the glass transition temperature (T_g) was drawn from differential scanning calorimetry (DSC) technique. The dispersion of dopant within the polymer matrix was supported by scanning electron microscopy (SEM) followed by its elemental composition from energy dispersive spectroscopy (EDS). From the AC impedance technique, maximum conductivity of 3.01?×?10^?4 S cm^?1 was elicited for the optimised electrolyte (1 g PVA?+?0.75 g PGS?+?0.6 g NH₄SCN). Frequency-dependent dielectric and modulus spectra were analysed to study the mechanism of transportation. Transport parameters evaluated by Wagner’s polarisation method proved that the conductivity was predominantly due to cations. Proton conducting battery was configured with the highest conducting electrolytic film and its cell parameters are presented.